EP4048718A1 - Adhesion-promoting composition for a textile material and associated reinforcing textile material - Google Patents
Adhesion-promoting composition for a textile material and associated reinforcing textile materialInfo
- Publication number
- EP4048718A1 EP4048718A1 EP20793385.4A EP20793385A EP4048718A1 EP 4048718 A1 EP4048718 A1 EP 4048718A1 EP 20793385 A EP20793385 A EP 20793385A EP 4048718 A1 EP4048718 A1 EP 4048718A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- latex
- composition
- approximately
- adhesion
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/17—Natural resins, resinous alcohols, resinous acids, or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Definitions
- Adhering composition for textile and related reinforcing textile are Adhering composition for textile and related reinforcing textile
- the present invention relates to an adhesive or bonding composition for a textile, in particular a composition for making a textile adhere to a rubber.
- the invention relates in particular to applications in the field of belts, pipes, tires, pneumatic springs (airspring) and, more generally, any part or article made of rubber, or comprising a part made of rubber, in which the rubber comprises a reinforcement. textile on the surface and / or in depth (in the mass).
- the invention therefore also relates to textile reinforcements coated with this adhesive, and the parts or articles incorporating them both on the surface and in depth.
- the textile reinforcement must first and foremost ensure the dimensional stability of the belt.
- the reinforcement is required to have specific mechanical properties in various environments.
- the reinforcement must adhere to the rubber of the belt.
- the reinforcement can be in contact with one rubber or several different rubbers.
- the backing is generally treated with an adhesive. More complex properties may also be required from the reinforcement. For example, the edge of the reinforcement being cut and exposed to the side of the belt, it must not fray, while being easy to cut. To guarantee these other properties, other types of treatments can be applied to the wire.
- the primary aim of the chemical treatments is to make a given reinforcement adhere to the various rubbers that it may encounter.
- the treatments are as varied as there are types of reinforcements [glass, aramid, polyamide (PA), polyethylene terephthalate (PET), etc.] and families of rubbers.
- the heart of the treatment for making a reinforcing textile adhere to the rubber is the so-called resorcinol-formaldehyde-latex or RFL treatment. It is a system mixing a latex (colloidal aqueous dispersion of elastomer or polymer) and thermosetting resins of the phenoplast or aminoplast type. This system is historic, it was widely developed in the 1970s and remains the treatment of choice. Despite numerous replacement attempts, it has so far never been possible to offer a global solution to achieve its performance. It is completely optimized to obtain the maximum static adhesion, that is to say without dynamic stress.
- the heat treatment has an impact on the chemical properties (adhesion) but also on the mechanical properties in the case of synthetic reinforcements. It impacts the withdrawal characteristics, among others.
- the treatment in the ovens results from the consensus between the maintenance of the mechanical properties and the crosslinking of the adhesive.
- the new treatment must therefore be able to adapt to current processing conditions, in order to guarantee the mechanical properties.
- an adhesive allowing a treatment to be carried out at a lower temperature will potentially provide new and interesting properties in certain applications, and will exhibit a favorable energy aspect.
- Thread core treatment which traps the filaments in a matrix and locks the filaments together. It thus gives resistance to fraying and makes the yarn stiff.
- Overcoats in English “overcoats" in the form of commercial adhesion promoters, or solutions of elastomers (sometimes called cementation).
- any change in a formulation does not call into question the functionality of the various chemical and thermal (or physical, more generally) treatments usually used for such and such an application.
- the RFL treatment has emerged as the treatment of choice to allow adhesion between the textile and the rubber.
- the phenomena involved in adhesion are brought into play during the vulcanization of the rubber part, while the RFL treatment itself can be deposited on the textile several months before.
- the term “adhesion” treatment is often used, the term “adhesion” being rather reserved for the state of adhesion.
- latexes are colloidal aqueous dispersions of elastomers or polymers, generally similar in nature to the rubber to be bonded. On the other hand, these latexes do not have real mechanical properties in themselves.
- a thermoset resin thermosetting
- RFL contains formalin and resorcinol which are now suspected carcinogens. It would therefore be interesting to find an alternative to this formalin and to resorcinol or to the RFL composition as a whole.
- the complex properties of RFL both in its implementation and in the properties of use of the end products incorporating it, which were recalled above, make the exercise of finding an alternative solution a real challenge. It would be even more interesting to find such a solution which is more than an alternative, but which allows an increase in performance.
- the objective of the invention is thus to provide new adhesion solutions which make it possible in particular to replace RFLs in their known applications, with performance levels that are close to or even higher, and this with components that are acceptable in the context of sustainable development and under favorable economic conditions.
- Lignosulfonates are offered as a natural adhesive and as a binder of short fibers for making mats (nonwovens) in combination with lignosulfonate hardeners, or as adhesives in multi-layer wood-based products. They have never been proposed in alternative compositions to RFLs and there is no indication that lignosulfonates can prove to be suitable for developing adhesion formulas to ensure a bond with rubbers, with sufficient mechanical performance. They are also used as surfactant in compositions then containing no hardener, as described in JP2002226812 and JP2001234143.
- a subject of the invention is therefore a composition comprising (or based on, consisting essentially of, or consisting of) a lignosulfonate salt, an epoxy hardener of this salt, and a polymer latex, in particular an elastomer. It is in particular an adhesive or adhesion composition for textiles.
- epoxy hardener as described in the invention, it is meant a compound comprising at least 2 epoxy units, or oxacyclopropane, or -CH-CH 2 -0 ring. This compound can additionally react with components such as alcohols by opening the epoxy ring. The presence of two epoxy units allows the reaction with 2 units containing alcohols and therefore a polymerization reaction, also called crosslinking.
- the epoxy hardener according to the invention is therefore a crosslinking agent for the lignosulfonate salt.
- a subject of the invention is also a composition, in particular adhesive or adhesion for textiles, obtained or capable of being obtained by mixing a lignosulfonate salt, an epoxy hardener of this salt, and a latex. of polymer, in particular of elastomer.
- the composition is as obtained or capable of being obtained by mixing a lignosulfonate salt and an epoxy hardener of this salt, in a basic medium, then adding a polymer latex. , in particular of elastomer; or by mixing a lignosulfonate salt in a basic medium and a polymer latex, in particular an elastomer, then adding an epoxy hardener of this salt.
- the composition comprises a product resulting from the reaction between the lignosulfonate salt in a basic medium and the epoxy hardener of this salt.
- compositions can be adhesion compositions for adhering textiles to a rubber or similar material. These compositions are the compositions which can be applied to a substrate, such as in particular a textile, in particular the textiles according to the invention.
- the invention also relates to their method of preparation.
- a subject of the invention is also these compositions which are dried and hardened after suitable treatment such as a heat treatment.
- drying it is understood to mean evaporation of water or of volatile matter.
- curing is meant any polymerization or crosslinking reaction, total or partial, of the compounds present in the composition and capable of reacting under the treatment conditions applied, including without the need for heat treatment.
- These dried and cured compositions are then generally associated with a substrate, such as in particular a textile, in particular the textiles according to the invention, or else with rubber parts, or the like, incorporating these textiles.
- associated is meant that the composition impregnates the textile, coats the textile, or impregnates and coats the textile.
- the coating can be continuous or discontinuous. Impregnation can be complete and full or partial.
- a subject of the invention is also a kit or set comprising a first composition comprising a lignosulfonate salt and a polymer latex, in particular an elastomer, and a second composition comprising an epoxy hardener of the lignosulfonate salt.
- the first and second compositions are suitable and intended to be mixed to form the adhesion composition, before the latter is applied to a textile within the meaning of the invention.
- the invention also relates to a method of applying an adhesion composition according to the invention, to impart adhesion properties to a reinforcing textile, with respect to a rubber or a similar material.
- This process will include drying and curing the composition, by a suitable treatment such as heat treatment.
- the invention also relates to the use of a composition according to the invention or of a dried and hardened adhesion composition, for imparting adhesion properties to a reinforcing textile, with respect to a rubber. or similar material.
- the invention also relates to a reinforcing textile, in particular thread, cord or textile structure, at least partially coated and / or impregnated with an adhesion composition according to the invention, in particular dried and hardened.
- the invention also relates to an article or part made of rubber (or similar material) or comprising a part made of rubber (or similar material), in which the rubber comprises at least one reinforcing textile according to the invention, on the surface and / or integrated. inside the rubber or rubber matrix.
- the first subject of the invention is therefore an adhesive or adhesion composition for textiles, comprising (or based on, consisting essentially of, or consisting of) at least one lignosulfonate salt, at least one epoxy hardener of this salt, and an elastomer latex.
- the lignosulfonate salt and the epoxy hardener of that salt react together to give a reaction product when they are mixed together and whether or not subjected to heat, such as a heat treatment which will be applied to the textile once coated and / or impregnated with the adhesion composition.
- heat such as a heat treatment which will be applied to the textile once coated and / or impregnated with the adhesion composition.
- the lignosulfonate salt is expected to react with the epoxy hardener in a crosslinking reaction by adding the reactive units of lignosulfonate to the epoxy rings and opening this ring, when the compounds are subjected to heat. This heat can be applied during a heat treatment such as the heat treatment applied to a textile after coating and / or impregnation of the adhesion composition.
- reaction product is understood to mean, as goes without saying, the product of the reaction between the lignosulfonate and the epoxy hardener, which does not include any additives which could enter into the final composition.
- composition can in particular be obtained by a process, also subject of the invention, according to which the three ingredients are mixed with stirring.
- the lignosulfonate salt can be dissolved in water, before mixing the solution obtained with the latex and the epoxy. This solubilization can be facilitated by working in a basic medium, by adding a soda and / or ammonia type agent.
- the lignosulfonate salt solution and the latex are mixed first, and only then is the epoxy added.
- the lignosulfonate salt can be dissolved in water with stirring and in the presence of the agent allowing the pH to be basic, the mixture is stirred until solubilization, preferably complete, it is then added, while stirring, to the latex, before incorporating, still with stirring, the hardener (the hardener is preferably dissolved or dispersed beforehand in water, eg with vigorous stirring).
- the hardener is preferably dissolved or dispersed beforehand in water, eg with vigorous stirring.
- the mixture of lignosulfonate salt and the latex is added to the solution or dispersion of epoxy hardener.
- the mixture with the epoxy hardener can be carried out following the preparation of the lignosulfonate and latex mixture, or subsequently, as in the case of the kit or set which is the subject of the invention.
- the composition can be used as a ready-to-use adhesive composition or which can be custom-diluted.
- an aqueous solution of lignosulfonate and of epoxy hardener before adding the mixture with stirring.
- an aqueous dispersion of latex According to a practical modality, the mixture of lignosulfonate salt and epoxy hardener is added to the latex.
- the pH of the solution of lignosulfonate or of lignosulfonate and of hardener is adjusted to be basic, for example by adding sodium hydroxide and / or ammonia, before incorporation of the latex.
- the composition can be used as a ready-to-use adhesive composition or which can be diluted on demand.
- the latex is preferably a basic aqueous dispersion of the polymer (s) and / or elastomer (s). It is also possible to work according to the invention at neutral pH.
- the working pH values can in particular be those mentioned below with regard to the pH of the composition.
- elastomer is understood to mean, in particular, a polymer or copolymer chain whose glass transition temperature (T v ) is less than approximately 25 ° C.
- T v glass transition temperature
- the elastomers are present in the rubber to be adhered and in the latex of the adhesion composition.
- An "elastomer latex” is a colloidal aqueous dispersion of elastomer.
- rubber in English “rubber” or "elastomeric material” is meant here the vulcanized or crosslinked product prepared from elastomer or elastomeric rubber, synthetic or natural, of one or more types, of filler ( s) reinforcing agent (s) (carbon blacks, silica, kaolins ...), plasticizer (s), vulcanizing agent (s) (sulfur, peroxide, metal oxides and the necessary accelerators), any other usual additives for the application in question (for example to facilitate processing, for protection against oxygen, ozone, heat, flame, UV rays).
- the invention relates to both synthetic rubbers and natural rubber. Rubbers, formulated on the basis of elastomers, are materials whose Tg obtained is lower than the service, operating or use temperature of the mechanical parts or assemblies formed with the rubber (s).
- Lignosulphonates are by-products resulting from the transformation of wood, in particular from the treatment of wood for the manufacture of paper pulp according to the process known as “acidic bisulphite cooking process”. This process, which uses a bisulfite, makes it possible, depending on the nature of the counterion used, to obtain the corresponding lignosulfonate salts. These lignosulfonates can also come from a process intended to produce them from wood.
- the lignosulfonate salt can be a sodium, potassium, magnesium, ammonium or calcium salt.
- the adhesion compositions do not include formaldehyde or formalin.
- the adhesion compositions do not include resorcinol.
- the adhesion compositions do not include formaldehyde or formalin, or resorcinol.
- the adhesion compositions do not include an organic solvent. They use water as a solvent, the pH of which can be adjusted as needed.
- the epoxy hardener according to the invention is a polyepoxy compound comprising at least 2 epoxy or epoxy groups or units. Mention may in particular be made of those which contain on average more than one glycidyl or -methyl-glycidyl radical carried by a heteroatom, preferably an oxygen or nitrogen atom, more particularly an oxygen atom, or those which contain on average more than one epoxy-cyclo-hexyl group. It is possible to use several different compounds from the following lists.
- - diglycidyl or polyglycidlyl ethers of aliphatic polyols such as butanediol-1, 4, hexane-diol-1, 6, 1, 2,6-hexane-triol, glycerol, neopentylglycol, ethylene glycol, triethyleneglyycol, 1, 2 propylene glycols or polyalkylene glycols such as polypropylene glycols, or derivatives of polyalkylene glycols, for example polypropylene glycols;
- epoxycyclohexyl groups such as 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate, epoxy-8,9 (epoxy-3,4 cyclohexyl) -3-di-oxa-2,4 spiro 5.5 undecane and l bis- (3,4-epoxy cyclohexylmethyl) adipate, and the like;
- - di- or polyglycidyl esters of polycarboxylic acids such as phthalic acid, terephthalic acid, A -tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, oxalic acid, succinic acid, glutaric acid, dimerized linolenic acid and the like.
- the epoxy hardener can in particular be chosen from the compounds below, it being understood that the composition can incorporate one of them or more of them, in particular 2 of them:
- the epoxy hardener can also be chosen from N-glycidyl derivatives of heterocyclic amines, amides and nitrogenous bases, for example: - N, N-diglycidyl-aniline, - N, N-diglycidyl-toluidine, - N, N, N ', N' tetrakis-glycidyl bis- (4-amino phenyl) -methane, - the triglycidyl derivative of 4-hydroxy aniline, - triglycidyl isocyanurate, - N, N'- diglycidyl-ethylene-urea, - N, N'-diglycidyl-5,5-dimethyl hydantoin, - N, N'-diglycidyl isopropyl-5 hydantoin and - N, N'diglycidyl-5,5-dimethyl-isopropyl-6 dlhydro -5.6 uracil.
- the latex can advantageously be a latex of acrylonitrile / carboxylated butadiene copolymer (XNBR), a latex of acrylonitrile / hydrogenated butadiene (HNBR), a latex of chlorosulfonated polyethylene (CSM), a latex of styrene-butadiene-vinylpyridine copolymer (VPSBR) , a styrene / butadiene copolymer latex (SBR), an acrylonitrile / butadiene copolymer latex (NBR), a polybutadiene latex (BR), a chlorobutadiene latex (CR), a natural rubber latex (NR), a latex polyurethane, or a mixture of at least two of them.
- XNBR acrylonitrile / carboxylated butadiene copolymer
- HNBR acrylonitrile / hydrogenated butadiene
- the dry matter content of the composition by weight can be in particular between approximately 2 and approximately 38%, in particular between approximately 4 and approximately 30%, more particularly between approximately 7 and approximately 25%.
- composition according to the invention may in particular comprise from about 40 to about 95%, preferably from about 55 to about 90% or from about 40 to about 60, 70, 80 or 90% by weight of elastomer relative to to the composition.
- composition is given as a dry matter.
- the hardener / lianosulfonate salt mass ratio can be in particular between approximately 0.01 and approximately 5, more particularly between approximately 0.03 and approximately 1, typically between approximately 0.05 and approximately 0.5. Lower or higher values may prove to be possible depending on the hardener and lignosulfonate salt pairs chosen and this parameter can be determined by a person skilled in the art on the basis of this description.
- the mass ratio [hardener + liqnosulfonatel salt / latex can be in particular between approximately 0.05 and approximately 0.6, more particularly between approximately 0.15 and approximately 0.5. Lower or higher values may prove to be possible according to the compounds chosen in combination and this parameter can be determined by a person skilled in the art on the basis of this description.
- the composition has a neutral or basic pH, in particular a pH of between approximately 7 and approximately 13, in particular between approximately 9 and approximately 13.
- the composition can comprise for this purpose an additive making it possible to adjust the pH, eg soda.
- the composition includes the water of the elastomer latex. Water can still be added, in order to make the applicable composition sufficiently fluid for a conventional application, for example by impregnation.
- the composition may also comprise additives at a content in particular of between approximately 0.01 or 0.1 and approximately 50% by dry mass.
- the composition can in particular comprise an adhesion promoter or adhesion soluble in aqueous medium (for example, silane, blocked isocyanate), a surfactant, a dispersant, an antifoaming agent, a wax (for example microcrystalline hydrocarbon wax in emulsion) , a filler (eg carbon black, silica), a colorant, a metal oxide (eg zinc oxide ZnO), an elastomer crosslinker, an anti-UV agent, an anti-ozone agent, a thermo-agent. protective.
- These agents are additives conventionally used in RFL formulations. They are compatible with the adhesive that is the subject of the invention.
- the textile adhesion composition consists essentially of a lignosulfonate salt, an epoxy hardener this salt, and an elastomer latex, and may comprise one or more additives, in particular a or more of the additives mentioned in the previous paragraph.
- the compositions according to the invention do not comprise a hardener or conventional catalyst for compounds containing an epoxy group or unit, such as triethylenetriamine (TETA) and triethylamine (TEA).
- the viscosity of the adhesion composition is measured at 23 ° C using a Brookfield viscometer, for example equipped with a ULA module suitable for low viscosities.
- the viscosity can be adjusted by adjusting in particular the water content.
- the viscosity can be adjusted to achieve the desired level to allow good application to the textile in the coating or impregnation process used. In the case of impregnation by soaking, this viscosity can in particular be between approximately 1 and approximately 10, typically between approximately 1 and approximately 5 Cp or mPa.s.
- composition according to the invention can be applied to any textile.
- textile within the meaning of the invention, is meant: continuous monofilament yarn, continuous multifilament yarn, staple fiber, any assembly of monofilament and / or multifilament continuous yarns or chopped yarn, including a wick, a cable formed from such yarns by conventional twisting techniques and a "textile structure" formed from the assembly of yarns, twisted or cabled, in particular in the form of fabric, grid, and the like.
- the textiles of the invention, having been treated with the composition according to the invention are designated by the expression “reinforcing textiles”.
- the textile can be organic or inorganic in nature.
- glass in particular E glass or high modulus glass
- basalt carbon
- aramid metal or para
- polyvinyl alcohols cellulose
- high density polyethylenes HDPE
- polyester in particular polyethylene terephthalates, PET
- PA polyamides
- PA polyamides
- PA acrylics
- hybrids aramid yarn + nylon yarn, cabled together; acrylic + glass + copper, wired together
- the textile is a cord or a textile structure of several threads
- the threads can all be organic or inorganic in nature, or the cord or the textile structure can comprise both types of threads, organic and inorganic.
- a subject of the invention is also a process for applying, or using, an adhesion composition according to the invention, to impart adhesion properties to such a textile, in particular with respect to an elastomeric material.
- This use can be broken down in terms of the method of adhering a textile according to the invention.
- This use or method comprises applying said composition to the textile (yarn, cord, textile structure), then drying it.
- This application can be carried out by the methods in use in industry, for coating, in particular by impregnation, as described below.
- the choice of latex, and therefore of the constituent elastomer advantageously leans towards a formula similar to the nature of the constituent elastomer of the rubber to be treated.
- the impregnation of the textiles is carried out by soaking ("dipping") in trays containing the adhesive preparations.
- the wires, cords and cables can in particular undergo either a direct soaking in a tank, or an impregnation by a lick roller, for the application of the adhesion composition.
- the excess of wet preparation is preferably removed, for example by pressing (padding), die, suction or by physical compression between porous supports such as foams.
- the drying and heat-setting of the adhesion composition are then carried out.
- the coated impregnated textile can thus be passed through an oven to allow drying and crosslinking of the adhesion composition.
- the textile After leaving an oven, the textile can again undergo an impregnation step (by soaking or impregnation by a lick roller), then passing through an oven, these steps being repeatable, in particular up to a total of 4 impregnations (2, 3 or 4).
- a derivation system made up of a comb and / or "pig tails" can be used before the impregnation of a multifilament yarn. It allows maximum opening of the multifilament yarn, to promote strong impregnation.
- the excess wet preparation is preferably removed, for example by pressing (padding), suction or by physical compression between porous supports such as foams. After soaking or impregnation, and optionally removing the excess, the adhesive composition is then dried and heat-set.
- the coated impregnated yarn can thus be passed through an oven to allow drying and crosslinking of the adhesion composition.
- the yarn can again undergo an impregnation step (by dipping or impregnation by licker roll), then passing through an oven, these steps can be repeated, in particular up to a total of 4 impregnations. (2, 3 or 4).
- the yarn is then twisted in line.
- the wiring is preferably carried out on an already treated wire, but it is also possible to perform the wiring and then perform the steps of impregnation and drying and heat setting.
- the speeds can range from 1 m / min to 150 m / min, the temperatures of the furnaces from 30 ° C to 350 ° C, more specifically from 100 to 300 ° C, and even more specifically from 140 to 220 ° vs.
- Mechanical tension can also be applied to the textile throughout the process.
- a cord for example made of polyamide such as PA 4-6, is constructed by twisting, then cabling.
- the cord obtained can optionally and advantageously be treated by a first core impregnation intended to block the filaments between them and give the yarn resistance to fraying, also making the yarn stiff ("stiff"); this can be done with a solution of methylene diphenyl diisocyanate in toluene; the impregnated cord is then subjected to drying and heat setting in an oven.
- the cord is then impregnated in a tank containing an adhesive composition of the invention, then dried and heat set in the oven.
- Another embodiment relates to the production of a textile reinforcement for incorporation into profiles and seals, such as window or door seals.
- Such reinforcements can in particular be made from glass yarn containing a sizing with which the adhesive composition is to be compatible. It is possible to proceed from glass strands (in particular E-glass), they are subjected to a derompage (see above) and to an impregnation in the tank containing an adhesion composition of the invention. The impregnated yarns were subjected to drying and heat setting in an oven. On leaving the oven, the yarns undergo a twisting operation. A plurality, for example three, impregnated twists can then be cabled together.
- Another embodiment relates to the production of a textile reinforcement to serve as a reinforcement, braided, coiled, wrapped or knitted in a brake pipe. It is possible to start from a yarn made of organic material, for example polyethylene terephthalate (PET), high density polyethylene (HDPE), or polyamide. It is preferably applied a twist. The yarn, preferably twisted, is treated by impregnation in an adhesion composition of the invention, then by drying and heat setting in an oven.
- PET polyethylene terephthalate
- HDPE high density polyethylene
- a cord is constructed by successive stages of twisting, then cabling.
- the cord obtained is treated by a first core impregnation intended to block the filaments between them and give the yarn resistance to fraying, also making the yarn stiff, for example using a solution. of methylene diphenyl diisocyanate in toluene, then subjected to drying and heat setting in an oven.
- the cord obtained is then treated by impregnation in an adhesion composition of the invention, then by drying and heat-setting in an oven.
- the subject of the invention is also a reinforcing textile coated and / or impregnated with a bonding composition according to the invention.
- the subject of the invention is in particular a reinforcing textile coated and / or impregnated with an adhesion composition capable of being obtained by implementing the methods described here. It also relates to the method of treating the textile to produce the reinforcing textile, by applying the adhesive composition to said textile.
- a subject of the invention is in particular a yarn coated and / or impregnated with an adhesion composition according to the invention.
- the yarn can be a twisted yarn, and the twisting can take place before or after application of the composition, and drying and / or curing thereof.
- This yarn can be impregnated to the core, and this can have been obtained if necessary by breaking the yarn (spacing of the filaments by means known to those skilled in the art) before impregnating it with the composition.
- This yarn can in particular comprise, or be coated with, the cured adhesion composition (dried and / or crosslinked).
- a subject of the invention is also a cord coated and / or impregnated with an adhesion composition according to the invention. This cord can in particular comprise, or be coated with, the cured adhesion composition (dried and / or crosslinked).
- the cord can be formed from at least two wires not coated or impregnated with the adhesive composition, generally each wire is twisted, then the wires are cabled (assembled together and twisted in the opposite direction of the twist of the elementary wires), then the cord is impregnated with the adhesive composition, which is cured after application.
- the cord can also be formed from the assembly of at least two threads coated or impregnated with the adhesive composition, generally each thread is twisted after solidification of the composition, and then the threads are cabled (assembled together and twisted in the opposite direction of the twisting of the elementary wires); one can then provide a coating of the cord with other treatments ("overcoat” or “topcoat”), and its drying.
- the subject of the invention is also a textile structure formed by assembling threads by known techniques such as weaving or by gluing or welding in the case of grids. These textile structures are coated or impregnated with the composition of the invention, and the invention covers such textile structures coated with the cured adhesion composition.
- the adhesion compositions can be applied to textiles within the meaning of the invention by the methods used for RFLs. Firstly, the impregnation is retained, by direct dipping or by means of a lick roller.
- the subject of the invention is also an article or part made of rubber (or one comprising a part made of rubber), comprising at least one reinforcing textile, in particular thread, cord and / or textile structure, according to the invention.
- This reinforcing textile can in particular be applied to the surface of the article or part and / or integrated inside the article or part.
- rubber is a vulcanizable formulation based on natural or synthetic elastomers, such as vulcanized (crosslinked) natural rubber (NR or polyisoprene), or a synthetic, vulcanized (crosslinked) rubber.
- natural or synthetic elastomers such as vulcanized (crosslinked) natural rubber (NR or polyisoprene), or a synthetic, vulcanized (crosslinked) rubber.
- BR polybutadiene
- AU or EU polyurethane
- CR polychloroprene
- VMQ silicone
- FVMQ fluorosilicone
- EPDM ethylene-propylene-diene monomer
- NBR butadiene-acrylonitrile copolymers
- HNBR hydrogenated butadiene-acrylonitrile copolymers
- SBR styrene / butadiene copolymer
- epichlordrin ECO or CO
- butyl IIR
- bromobutyl BIIR
- chlorobutyl CMR
- chlorinated polyethylenes CM
- CSM chlorosulfonated polyethylenes
- XNBR copolymers of ethylene and methyl acrylate (AEM), copolymers of ethylene and vinyl acetate
- a rubber can also be a vulcanizable formulation based on mixtures or cuts of such elastomeric gums.
- the rubber can also be a formulation based on thermoplastic elastomers (so-called “physically crosslinking” elastomers such as SBS, block styrene-butadiene-styrene, for example).
- thermoplastic elastomers so-called “physically crosslinking” elastomers such as SBS, block styrene-butadiene-styrene, for example.
- the subject of the invention is in particular an article or part made of elastomer or rubber comprising, embedded in its mass in elastomer or rubber, or flush with the surface, a reinforcing textile adhered according to the invention, for example one or more threads, individual or cabled or assembled in textile structures, or several of these categories.
- bonded is meant in particular that the reinforcing textile comprises or is coated with the cured (dried and / or crosslinked) adhesive composition.
- the subject of the invention is also an article or part made of elastomer or rubber comprising, embedded in its mass in elastomer or rubber, one or more threads, individual or cabled or else assembled in textile structures, or more of these categories, and comprising in furthermore, glued or adhered to at least one surface of this elastomeric or rubber material, a textile structure according to the invention, these reinforcing textiles being adhered in accordance with the invention.
- the belts can include wires or cords embedded in the mass of elastomer or rubber. They can also comprise, instead of or in addition to the son and cords, a textile structure, in particular a fabric, adhering on the surface, for example on the back in the transmission belt, and on the back and the notch for the belt. distribution
- hoses Flexible or rigid hoses, in particular brake hoses (comprising a braided textile structure, single or double braid), hoses, industrial hoses (comprising a wrapped or spiral textile structure, that is to say manufactured by wrapping or by spiraling), including oil and gas hoses, hoses (knitted textile structure).
- brake hoses comprising a braided textile structure, single or double braid
- industrial hoses comprising a wrapped or spiral textile structure, that is to say manufactured by wrapping or by spiraling
- oil and gas hoses hoses (knitted textile structure).
- Braiding, spiraling, knitting is generally carried out during the implementation of the pipe by extrusion.
- transmission belt based on EPDM or CR
- synchronous belts based on HNBR and CR
- Pipes based on SBR, or EPDM, or an NBR / PVC blend, or epichlorohydrin, or butyl
- Airspring based on CR
- kinetic discs based on CR or NR
- tires thick part comprising several mixtures, based on NR, BR or SBR
- the invention has the advantage of being integrated into the recovery of renewable non-food raw materials. It enables the recovery of lignin, currently a waste from the wood and paper industry. This compound is perfectly harmless, has a low cost, high performance. Its use does not compete with the food market, it is not subject to regulations on chemicals. This is an agro-resource.
- thermosetting material that is to say the formation of a three-dimensional covalent network resulting in a reaction product
- DSC differential scanning calorimeter
- a few grams of sodium lignosulfonate (Arbo N18; Tembec N18) and an epoxy hardener (1, 4 butanediol diglycidyl ether) are homogenized for 2 minutes in an aluminum dish under a hood at room temperature.
- the lignosulfonate salt / epoxy hardener mass ratio is precisely 1.
- a few milligrams of this composition are sealed in an aluminum crucible with a diameter of 43 mm and a depth of 12 mm.
- the sample is then placed in DSC 3+ equipment STAR e SYSTEM from METTLER TOLEDO and subjected to a temperature ramp from 25 to 300 ° C, at 10 ° C per minute, under a flow of nitrogen at 80 ml per minute.
- the total enthalpy variation to which the sample is subjected is recorded by integrating the surface under the exothermic peak using the STAR SW 14.00 software, then normalized in J. g -1 .
- the firing temperature in ° C, where the crosslinking kinetics are the strongest, is measured at the maximum peak (peakmax) of the exothermic peak with an accuracy of +/- 1 ° C.
- compositions containing only an epoxy hardener exhibit zero or low exothermic variations, between 0 and 33% relative to the lignosulphonate salt control.
- compositions containing sodium lignosulphonate and an epoxy hardener exhibit exothermic energy variations of between 595 and 1199% relative to the lignosulphonate salt control. This strong variation in exothermic relative to the control is characteristic of the phenomenon of crosslinking or "baking" of a thermosetting material.
- the role of the epoxy hardener on the lignosulfonate is clearly apparent here.
- the dry extract (or mass concentration) of the preparations is defined as being the percentage of residual dry matter after evaporation of the volatile materials (water, solvent) according to a defined drying method.
- the whole is then subjected to a temperature of 120 ° C until total stabilization of the mass.
- the result is expressed in%.
- the viscosity of the preparation is measured at 23 ° C using a Brookfield viscometer. Unless otherwise specified, the measurement is carried out using a ULA (Ultra Low Viscosity Adaptator) module and a mobile n ° 1 (low viscosity system) at a speed of 60 rpm (revolutions per minute).
- ULA Ultra Low Viscosity Adaptator
- the pH of aqueous preparations is measured using a METLER 340 pH meter, calibrated for measurements in a basic medium using buffer solutions. A glass electrode and 3M KCI electrolyte are used.
- Example C.II-1 Preparation of an adhesive based on sodium lignosulfonate and an epoxy hardener
- a first embodiment of the invention 64.2g of sodium lignosulfonate (Arbo N18; Tembec) are dissolved with stirring in 1184g of water. 2.5 g of a 10% by mass sodium hydroxide solution are then added to the solution, which is kept stirring for 10 minutes to allow complete solubilization. This solution is added with stirring to 983 g of a styrene-butadiene-vinylpyridine copolymer latex (VPSBR). The whole is kept under agitation (150 rpm) during the hardener preparation phase.
- VPSBR styrene-butadiene-vinylpyridine copolymer latex
- 35g of GE100 are stirred vigorously (300rpm) with 230 grams of water. This solution is added to the preparation of lignosulfonate and latex. Stirring is maintained for a few minutes until complete homogenization.
- the preparation has a pH of 10.8, a dry extract of 19.43% and a viscosity of 2.45 mPa.s.
- Hardener / lignosulfonate salt mass ratio from 56% to 116%
- % by mass of dry latex in the composition from 80 to 84%.
- Example C.II-2 Second method of preparing a sodium lignosulfonate adhesive and an epoxy hardener
- a second embodiment of the invention 34.8g of sodium lignosulfonate are introduced into a container and 782g of water are added gradually. The solution is stirred at 200rpm. 20g of a 10% by mass sodium hydroxide solution and 100.7g of 20% by mass ammonia are then successively added with stirring to the preparation. The mixture is stirred at 200rpm for 10 minutes.
- the basic sodium lignosulfonate solution is added with stirring to a latex preparation of a styrene-butadiene copolymer (SBR wet latex; 946g) and to 157g of previously homogenized water.
- SBR wet latex styrene-butadiene copolymer
- Hardener / lignosulfonate salt mass ratio from 217% to 218%.
- % by mass of dry latex in the composition from 78% to 82%.
- Example C.II-3 Third method of preparing an adhesive based on sodium lignosulfonate and an epoxy hardener
- a basic solution of sodium lignosulfonate is prepared by dissolving 19 g of sodium lignosulfonate in 955 g of water and stirring with stirring and adding 19 g of a sodium hydroxide solution at 10% by mass. The preparation is left under stirring at 200rpm for 10 minutes in order to allow total solubilization.
- a basic latex dispersion is prepared by introducing 167g of water into a container, which is then stirred at 200rpm. 1049g of a styrene-butadiene copolymer latex (SBR), then 25g of an ammonia solution at 20% by mass are then introduced successively. The basic lignosulfonate solution is then added with stirring to the latex dispersion.
- SBR styrene-butadiene copolymer latex
- the preparation has a pH of 12.25, a dry extract of 18.33% and a viscosity of 2.25 mPa.s.
- Hardener / lignosulfonate salt mass ratio from 255% to 516%
- % by mass of dry latex in the composition from 68% to 86%.
- Example C.II-4 Fourth method of preparing an adhesive based on potassium lignosulfonate and an epoxy hardener.
- the preparation has a pH of 12.69, a solids content of 19.58% and a viscosity of 2.45 mPa.s.
- Hardener / lignosulfonate salt mass ratio 33% to 134%
- % by mass of dry latex in the composition from 65% to 79%.
- Example C.II-5 Fifth method of preparing an adhesive based on potassium lignosulfonate and an epoxy hardener
- 1306g of this preparation are taken and diluted with stirring in 996g of water.
- 36g of an aqueous dispersion of zinc oxide at 55% by mass, 78g of an aqueous dispersion of carbon black at 35% by mass and 83g of an adhesion promoter (blocked isocyanate) are then successively added with moderate stirring .
- the preparation has a pH of 12.32, a solids content of 14.1% and a viscosity of 1.95 mPa.s.
- Hardener / lignosulfonate salt mass ratio 33% to 135%
- Mass ratio [lignosulfonate salt + hardener] / latex from 20% to 47% % by mass of dry latex in the composition: from 48% to 59%
- compositions of these examples are used in the treatment part of the reinforcing textile.
- the definitions and methods of measurement or control described in this part are generally applicable on request, unless otherwise indicated.
- the mechanical characteristics of the treated textiles such as tensile strength at break (“tensile strengh”), tensile elongation at break (“elongation at break”), shrinkage, temperature shrinkage, steaming (" contraction "), temperature contraction force (“ shrinkage force “), linear mass (“ linear weight “), load rate (“ Dip pick-up “; DPU), stiffness, etc., are measured according to the standards in force in the textile industry. In the context of the present invention, it has been verified that the new treatments do not lead to any modification of these properties, compared to the standard RFL.
- the adhesive preparations of the invention are evaluated for their adhesion performance. After coating the textile, it is deposited in an unvulcanized rubber matrix, so that the surface of the textile in contact with the rubber remains free of any pollution. The matrix containing the textile is then vulcanized by compression, according to temperature, time and pressure conditions specific to each rubber. The textile + vulcanized matrix assembly forms an adhesion test tube.
- Adhesion specimens can take several forms, described in various international standards, such as ISO 36: 2017.
- the test pieces, and by extension the test carried out to determine the adhesion are commonly known to those skilled in the art under names such as Test-T (“pull-out test”, ASTM D2229-04), Test-H (according to standard NF ISO 4647 or ASTM D4776-04), peeling (peel-test), etc.
- the test is then carried out by stressing the specimen until destruction of the interfacial contact zone, tearing of the textile, or tearing of the rubber matrix.
- the adhesion is then evaluated according to criteria such as the appearance of the textile at break, the maximum adhesion force, the average tear-off force, possibly reduced to the thickness of the test piece.
- the coil (s) of untreated wires, cords and cables can be positioned on a creel at the line entry.
- An accumulator system can optionally be used.
- the wires, ropes and cables can be either directly dipped in a tub or impregnated by a lick roller, for the application of the adhesion composition. After soaking or impregnation, the excess of wet preparation is preferably removed, for example by pressing (padding), suction or by foams
- Drying and / or crosslinking of the adhesion composition is then carried out.
- the coated impregnated textile can thus be passed through an oven to allow drying and crosslinking of the adhesion composition.
- the textile can again undergo an impregnation step, then passage through an oven, these steps being able to be repeated, in particular up to a total of 4 impregnations (2, 3 or 4).
- the wires, cords or cables can be received on winders.
- a derivation system made up of a comb and / or "pig tails" can be used at the creel outlet. It allows maximum opening of the multifilament yarn, to promote strong impregnation.
- the yarn is then twisted in line.
- the wiring is preferably carried out on an already treated wire. Additional treatments can be carried out on the cords thus formed.
- the speeds can range from 1 m / min to 150 m / min, the temperatures of the furnaces from 30 ° C to 350 ° C, more specifically from 100 to 300 ° C, and even more specifically from 140 to 220 ° vs.
- Mechanical tension can also be applied to the textile.
- the textiles were treated with the adhesion compositions object of the invention under conditions identical to those applied during a treatment with an RFL.
- Example III-1 Polyamide 4-6 reinforcement treated for belts.
- the inventors set out to present a solution which can be used as a reinforcement in assemblies such as transmission belts or conveyor belts.
- a cable in PA 4-6 of construction 470 / 5x3 dtex (100/125) was built by successive stages of twisting, then cabling.
- the cord obtained was treated by a first impregnation in a solution of methylene diphenyl diisocyanate in toluene, then subjected to drying and heat setting in an oven.
- the cord was then impregnated in a tank containing the adhesion composition (the adhesive) of the invention, at a concentration by mass of dry matter of 20%, instead of the RFL treatment usually applied.
- the various threads impregnated with the various adhesives obtained were evaluated for adhesion to a mixture based on EPDM (ethylene-propylene-diene monomer) accelerated with peroxide.
- the test pieces were produced by compression molding.
- the adhesion values obtained are presented in Table 2, and expressed as% adhesion relative to the adhesion obtained with the control RFL yarn.
- Example III-2 Reinforcement Treated glass for profiles.
- the inventors set out to present an invention which can be used as a reinforcement in profiles and seals, such as window or door seals.
- Such reinforcements are made from glass yarn containing a size with which the adhesive composition must be compatible.
- Example IM-3 Treated polyethylene terephthalate reinforcement for pipes.
- the inventors set out to present a solution which can be used as a reinforcement, braided, spiral, wrapped or knitted in a brake pipe.
- Example 111-3 (a): For this, a 90 Z twist was applied to a polyethylene terephthalate (PET) yarn with a titre of 1100 dtex.
- the yarn obtained was treated by an impregnation in the adhesion composition (the adhesive) object of the invention, then by heat setting in an oven.
- the adhesives used in this example have a solids concentration of 20%.
- the different threads impregnated with the adhesive were evaluated for adhesion to an EPDM rubber compound accelerated with peroxide conventionally used in brake pipes.
- the test pieces were produced by compression molding. A yarn impregnated with RFL, carried out under the same conditions, made it possible to obtain the control adhesion values.
- Example 111-3 In another example, a cord of construction 830 / 2x3 dtex was constructed by successive stages of twisting, then cabling. The cord obtained was treated by a first impregnation in a solution of methylene diphenyl diisocyanate in toluene, then subjected to drying and heat setting in an oven.
- the adhesion compositions (adhesives) used in this example have a solids concentration of 20%.
- the different threads impregnated with the adhesive were evaluated for adhesion on a rubber mixes based on CR.
- the test pieces were produced by compression molding.
- the values obtained are presented in Table 2, and expressed as% adhesion relative to the adhesion obtained with the control RFL yarn.
- Example II 1-1 The Polyamide 4-6 cord of Example II 1-1 treated with the different adhesives of Example C.11-1 showed satisfactory levels of adhesions with respect to EPDM compared to the yarn. RFL impregnated witness. The adhesion levels obtained, as well as the observation of the fracture patterns show that the adhesives evaluated are compatible with the first impregnation applied to the textile.
- the glass cord E of Example III-2 treated with the different adhesives of Examples C.II-2 showed satisfactory levels of adhesion to EPDM compared to the RFL impregnated control yarn. . Although these are lower than those obtained with RFL, they are high enough to guarantee the performance of the application.
- the adhesion levels obtained, as well as the observation of the fracture patterns show that the adhesives evaluated are compatible with the sizing of the glass.
- the glass strands thus treated showed no visual damage or caused excessive fouling on the processing lines. This shows the ability of the adhesives evaluated to impart identical properties to RFL, including mechanical protection properties.
- the PET yarn of Example III-3 (a), treated with the different adhesives of each of Example C. II-3 showed higher levels of adhesion to EPDM compared to the RFL impregnated control wire.
- the PET yarn of Example 111-3 (b), treated with the different adhesives of each of Example C. 11-4 showed satisfactory levels of adhesion with respect to the CR mixture with respect to the yarn. RFL impregnated witness.
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Abstract
The invention relates to an adhesion-promoting composition for a textile material, comprising a salt of lignosulphonate, an epoxy hardener for said salt, comprising at least two epoxide units, and an elastomer latex. The lignosulphonate salt can be a lignosulphonate of sodium, potassium, magnesium, ammonium or calcium. The invention also relates to the use of such a composition for providing a reinforcing textile material with adhesive properties, in relation to a rubber material, to a reinforcing textile material, particularly a textile structure, thread or cord, at least partially coated and/or impregnated with said composition, and to a part consisting of rubber or comprising a rubber material, in which the rubber comprises at least one reinforcing textile material, on the surface thereof and/or integrated into the rubber material.
Description
Composition d’adhérisation pour textile et textile de renfort y relatif Adhering composition for textile and related reinforcing textile
La présente invention concerne une composition adhésive ou d’adhérisation pour textile, en particulier une composition permettant de faire adhérer un textile à un caoutchouc. L’invention concerne notamment les applications dans le domaine des courroies, tuyaux, pneumatiques, ressorts pneumatiques (airspring) et, plus généralement, toute pièce ou article réalisée en caoutchouc, ou comprenant une partie réalisée en caoutchouc, dans laquelle le caoutchouc comprend un renfort textile en surface et/ou en profondeur (dans la masse). L’invention est donc aussi relative aux renforts textiles revêtus de cet adhésif, et les pièces ou articles les incorporant tant en surface qu’en profondeur. The present invention relates to an adhesive or bonding composition for a textile, in particular a composition for making a textile adhere to a rubber. The invention relates in particular to applications in the field of belts, pipes, tires, pneumatic springs (airspring) and, more generally, any part or article made of rubber, or comprising a part made of rubber, in which the rubber comprises a reinforcement. textile on the surface and / or in depth (in the mass). The invention therefore also relates to textile reinforcements coated with this adhesive, and the parts or articles incorporating them both on the surface and in depth.
Arrière-plan de l’invention Background of the invention
Pour prendre l’exemple des courroies de transmission, le renfort textile doit en priorité assurer la stabilité dimensionnelle de la courroie. Pour cela, il est demandé au renfort des propriétés mécaniques spécifiques dans divers environnements. Pour garantir les propriétés requises, et notamment éviter un risque de délaminage, le renfort doit adhérer au caoutchouc de la courroie. Le renfort peut être en contact avec un caoutchouc ou plusieurs caoutchoucs différents. Pour permettre une bonne compatibilité avec le caoutchouc, le renfort est généralement traité avec un adhésif. Des propriétés plus complexes peuvent également être demandées au renfort. Par exemple la tranche du renfort étant coupée et exposée au flanc de la courroie, celui-ci ne doit pas s’effilocher, tout en étant facile à découper. Pour garantir ces autres propriétés, d’autres types de traitements peuvent être apportés au fil. To take the example of transmission belts, the textile reinforcement must first and foremost ensure the dimensional stability of the belt. For this, the reinforcement is required to have specific mechanical properties in various environments. To ensure the required properties, and in particular to avoid a risk of delamination, the reinforcement must adhere to the rubber of the belt. The reinforcement can be in contact with one rubber or several different rubbers. To allow good compatibility with rubber, the backing is generally treated with an adhesive. More complex properties may also be required from the reinforcement. For example, the edge of the reinforcement being cut and exposed to the side of the belt, it must not fray, while being easy to cut. To guarantee these other properties, other types of treatments can be applied to the wire.
Pour obtenir l’ensemble de ces propriétés, il est nécessaire d’apporter une construction au fil, notamment sous forme d’un câblé, et d’apporter plusieurs traitements chimiques et thermiques. To obtain all of these properties, it is necessary to provide a construction to the wire, especially in the form of a cord, and to provide several chemical and heat treatments.
Plusieurs traitements différents étant appliqués sur le renfort textile, il est impératif de s’assurer de la compatibilité de l’adhésif avec le renfort, le caoutchouc et également les autres traitements appliqués au renfort. Since several different treatments are applied to the textile reinforcement, it is imperative to ensure the compatibility of the adhesive with the reinforcement, the rubber and also the other treatments applied to the reinforcement.
Les traitements chimiques visent en priorité à faire adhérer un renfort donné aux différents caoutchoucs qu’il peut rencontrer. Les traitements sont aussi variés qu’il existe de types de renforts [verre, aramide, polyamide (PA), polyéthylène téréphtalate (PET), etc.] et de familles de caoutchoucs.
Le cœur du traitement permettant de faire adhérer un textile de renfort au caoutchouc est ce qu’on appelle le traitement résorcinol-formaldéhyde-latex ou RFL. Il s’agit d’un système mélangeant un latex (dispersion aqueuse colloïdale d’élastomère ou de polymère) et des résines thermodurcissables de type phénoplaste ou aminoplaste. Ce système est historique, il a été largement développé dans les années 70 et reste le traitement de prédilection. Malgré de nombreuses tentatives de remplacement, il n’a jusque-là jamais été possible de proposer une solution globale permettant d’atteindre ses performances. Il est complètement optimisé pour obtenir le maximum d’adhésion statique, c’est-à-dire hors sollicitation dynamique. The primary aim of the chemical treatments is to make a given reinforcement adhere to the various rubbers that it may encounter. The treatments are as varied as there are types of reinforcements [glass, aramid, polyamide (PA), polyethylene terephthalate (PET), etc.] and families of rubbers. The heart of the treatment for making a reinforcing textile adhere to the rubber is the so-called resorcinol-formaldehyde-latex or RFL treatment. It is a system mixing a latex (colloidal aqueous dispersion of elastomer or polymer) and thermosetting resins of the phenoplast or aminoplast type. This system is historic, it was widely developed in the 1970s and remains the treatment of choice. Despite numerous replacement attempts, it has so far never been possible to offer a global solution to achieve its performance. It is completely optimized to obtain the maximum static adhesion, that is to say without dynamic stress.
Le traitement thermique a un impact sur les propriétés chimiques (adhésion) mais aussi mécaniques dans le cas des renforts synthétiques. Il impacte les caractéristiques de retrait, entre autres. Le traitement dans les fours résulte du consensus entre le maintien des propriétés mécaniques et de la réticulation de l’adhésif. The heat treatment has an impact on the chemical properties (adhesion) but also on the mechanical properties in the case of synthetic reinforcements. It impacts the withdrawal characteristics, among others. The treatment in the ovens results from the consensus between the maintenance of the mechanical properties and the crosslinking of the adhesive.
Pour toutes ces raisons, le nouveau traitement doit donc pouvoir s’adapter aux conditions de traitement actuelles, afin de garantir les propriétés mécaniques. Cependant, un adhésif permettant de réaliser un traitement à plus basse température apportera potentiellement des propriétés nouvelles et intéressantes dans certaines applications, et présentera un aspect énergétique favorable. For all these reasons, the new treatment must therefore be able to adapt to current processing conditions, in order to guarantee the mechanical properties. However, an adhesive allowing a treatment to be carried out at a lower temperature will potentially provide new and interesting properties in certain applications, and will exhibit a favorable energy aspect.
Cependant, pour améliorer les performances d’adhésion, ou pour donner de la résistance à l’abrasion, jusqu’à quatre traitements différents peuvent être appliqués successivement sur un textile, ce compris le traitement avec le RFL. Il s’agit des traitements suivants : However, to improve adhesion performance, or to provide abrasion resistance, up to four different treatments can be applied successively to a fabric, including the RFL treatment. These are the following treatments:
1) Le traitement à cœur du fil qui permet de piéger les filaments dans une matrice et de bloquer les filaments entre eux. Il confère ainsi une résistance à l’effilochage et rend le fil raide (en anglais « stiff »). 1) Thread core treatment which traps the filaments in a matrix and locks the filaments together. It thus gives resistance to fraying and makes the yarn stiff.
2) Une pré-activation, pour améliorer l’adhésion. 2) A pre-activation, to improve membership.
3) Le traitement RFL, en une ou deux couches. 3) RFL treatment, in one or two layers.
4) Des sur-revêtements (en anglais « overcoats ») sous forme de promoteurs d’adhésion commerciaux, ou de dissolutions d’élastomères (parfois appelé cémentation). 4) Overcoats (in English "overcoats") in the form of commercial adhesion promoters, or solutions of elastomers (sometimes called cementation).
Il est donc aussi préférable que tout changement dans une formulation ne remette pas en cause la fonctionnalité des différents traitements tant chimiques que thermiques (ou physique, plus généralement) habituellement utilisés pour telle ou telle application. It is therefore also preferable that any change in a formulation does not call into question the functionality of the various chemical and thermal (or physical, more generally) treatments usually used for such and such an application.
En considérant toutes les contraintes évoquées, le traitement RFL s’est imposé comme le traitement de choix pour permettre l’adhésion entre le textile et le caoutchouc. Les phénomènes impliqués dans l’adhésion sont mis en jeu durant la vulcanisation de la
pièce en caoutchouc, alors que le traitement RFL en lui-même peut être déposé sur le textile plusieurs mois avant. C’est pourquoi on utilise souvent le terme de traitement « d’adhérisation », le terme « d’adhésion » étant plutôt réservé à l’état d’adhésion. Dans le RFL, les latex sont des dispersions aqueuses colloïdales d’élastomères ou de polymères, généralement de nature similaire au caoutchouc à lier. En revanche, ces latex n’ont pas de réelles propriétés mécaniques en eux-mêmes. Pour assurer la tenue du système, une résine thermodure (thermodurcissable) est ajoutée. Il s’agit de la résine RF, à base de résorcinol et de formaldéhyde. Via sa polarité, elle permet une bonne adhésion au textile. Elle forme un maillage dans lequel le latex est emprisonné, ce qui rigidifie le système. Ce maillage reste suffisamment souple pour permettre la diffusion des chaînes élastomères dans la matrice et créer alors une bonne adhésion au caoutchouc (enchevêtrement, interactions moléculaires et éventuellement coréticulation lors de la vulcanisation). Considering all the constraints mentioned, the RFL treatment has emerged as the treatment of choice to allow adhesion between the textile and the rubber. The phenomena involved in adhesion are brought into play during the vulcanization of the rubber part, while the RFL treatment itself can be deposited on the textile several months before. This is why the term “adhesion” treatment is often used, the term “adhesion” being rather reserved for the state of adhesion. In RFL, latexes are colloidal aqueous dispersions of elastomers or polymers, generally similar in nature to the rubber to be bonded. On the other hand, these latexes do not have real mechanical properties in themselves. To ensure the durability of the system, a thermoset resin (thermosetting) is added. This is the RF resin, based on resorcinol and formaldehyde. Via its polarity, it allows good adhesion to the textile. It forms a mesh in which the latex is trapped, which stiffens the system. This mesh remains sufficiently flexible to allow the diffusion of the elastomer chains in the matrix and then create good adhesion to the rubber (entanglement, molecular interactions and possibly co-crosslinking during vulcanization).
Le RFL comporte du formol et du résorcinol qui sont aujourd’hui cancérigènes suspectés. Il serait donc intéressant de trouver une alternative à ce formol et au résorcinol ou à la composition RFL dans son ensemble. Les propriétés complexes du RFL, tant au niveau de sa mise en oeuvre que dans les propriétés d’usage des produits finaux l’incorporant, qui ont été rappelées ci-dessus, font de l’exercice de trouver une solution alternative un véritable défi. Il serait encore plus intéressant de trouver une telle solution qui soit plus qu’une alternative, mais qui permette une augmentation des performances. C’est à relever ces défis que se sont attelés les inventeurs. RFL contains formalin and resorcinol which are now suspected carcinogens. It would therefore be interesting to find an alternative to this formalin and to resorcinol or to the RFL composition as a whole. The complex properties of RFL, both in its implementation and in the properties of use of the end products incorporating it, which were recalled above, make the exercise of finding an alternative solution a real challenge. It would be even more interesting to find such a solution which is more than an alternative, but which allows an increase in performance. These are the challenges that the inventors set out to do.
L’invention a ainsi pour objectif de fournir de nouvelles solutions d’adhérisation qui permettent notamment de remplacer les RFL dans leurs applications connues, avec des niveaux de performance proches ou même supérieurs, et ceci avec des composants acceptables dans le cadre du développement durable et dans des conditions économiques favorables. The objective of the invention is thus to provide new adhesion solutions which make it possible in particular to replace RFLs in their known applications, with performance levels that are close to or even higher, and this with components that are acceptable in the context of sustainable development and under favorable economic conditions.
Les lignosulfonates sont proposés comme adhésif naturel et comme liant de fibres courtes pour la réalisation de mats (non-tissés) en combinaison avec des durcisseurs du lignosulfonate, ou comme adhésifs dans les produits multicouches à base de bois. Ils n’ont jamais été proposés dans des compositions alternatives aux RFL et il n’existe aucune indication que les lignosulfonates puissent s’avérer propices à développer des formules d’adhérisation pour assurer une liaison avec des caoutchoucs, avec des performances mécaniques suffisantes. Ils sont également utilisés comme tensioactif dans des compositions ne contenant alors pas de durcisseur, comme cela est décrit dans JP2002226812 et JP2001234143. Lignosulfonates are offered as a natural adhesive and as a binder of short fibers for making mats (nonwovens) in combination with lignosulfonate hardeners, or as adhesives in multi-layer wood-based products. They have never been proposed in alternative compositions to RFLs and there is no indication that lignosulfonates can prove to be suitable for developing adhesion formulas to ensure a bond with rubbers, with sufficient mechanical performance. They are also used as surfactant in compositions then containing no hardener, as described in JP2002226812 and JP2001234143.
Résumé de l’invention
L’invention a donc pour objet une composition comprenant (ou à base de, constituée essentiellement de, ou constituée de) un sel de lignosulfonate, un durcisseur époxy de ce sel, et un latex de polymère, notamment d’élastomère. Il s’agit notamment d’une composition adhésive ou d’adhérisation pour textile. Summary of the invention A subject of the invention is therefore a composition comprising (or based on, consisting essentially of, or consisting of) a lignosulfonate salt, an epoxy hardener of this salt, and a polymer latex, in particular an elastomer. It is in particular an adhesive or adhesion composition for textiles.
Par durcisseur époxy tel que décrit dans l’invention, il est entendu un composé comprenant au moins 2 motifs époxydes, ou oxacyclopropane, ou cycle -CH-CH2-0. Ce composé peut réagir par addition avec des composants tels que des alcools par ouverture du cycle époxyde. La présence de deux motifs époxydes permet la réaction avec 2 motifs contenant des alcools et donc une réaction de polymérisation, aussi appelée réticulation. Le durcisseur époxyde selon l’invention est donc un agent de réticulation du sel de lignosulfonate. By epoxy hardener as described in the invention, it is meant a compound comprising at least 2 epoxy units, or oxacyclopropane, or -CH-CH 2 -0 ring. This compound can additionally react with components such as alcohols by opening the epoxy ring. The presence of two epoxy units allows the reaction with 2 units containing alcohols and therefore a polymerization reaction, also called crosslinking. The epoxy hardener according to the invention is therefore a crosslinking agent for the lignosulfonate salt.
L’invention a aussi pour objet une composition, notamment adhésive ou d’adhérisation pour textile, obtenue ou susceptible d’être obtenue par le mélange d’un sel de lignosulfonate, d’un durcisseur époxy de ce sel, et d’un latex de polymère, notamment d’élastomère. Dans un mode de réalisation, la composition est telle qu’obtenue ou susceptible d’être obtenue par le mélange d’un sel de lignosulfonate et d’un durcisseur époxy de ce sel, en milieu basique, puis ajout d’un latex de polymère, notamment d’élastomère ; ou par le mélange d’un sel de lignosulfonate en milieu basique et d’un latex de polymère, notamment d’élastomère, puis ajout d’un durcisseur époxy de ce sel. A subject of the invention is also a composition, in particular adhesive or adhesion for textiles, obtained or capable of being obtained by mixing a lignosulfonate salt, an epoxy hardener of this salt, and a latex. of polymer, in particular of elastomer. In one embodiment, the composition is as obtained or capable of being obtained by mixing a lignosulfonate salt and an epoxy hardener of this salt, in a basic medium, then adding a polymer latex. , in particular of elastomer; or by mixing a lignosulfonate salt in a basic medium and a polymer latex, in particular an elastomer, then adding an epoxy hardener of this salt.
Dans un mode de réalisation, la composition comprend un produit issu de la réaction entre le sel de lignosulfonate en milieu basique et le durcisseur époxy de ce sel. In one embodiment, the composition comprises a product resulting from the reaction between the lignosulfonate salt in a basic medium and the epoxy hardener of this salt.
Les compositions peuvent être des compositions d’adhérisation permettant de faire adhérer des textiles à un caoutchouc ou à un matériau analogue. Ces compositions sont les compositions pouvant être appliquées sur un substrat, tel que notamment un textile, notamment les textiles selon l’invention. L’invention concerne aussi leur procédé de préparation. The compositions can be adhesion compositions for adhering textiles to a rubber or similar material. These compositions are the compositions which can be applied to a substrate, such as in particular a textile, in particular the textiles according to the invention. The invention also relates to their method of preparation.
L’invention a aussi pour objet ces compositions séchées et durcies après traitement adapté tel qu’un traitement thermique. Par séchage, il est entendu évaporation d’eau ou de matière volatile. Par durcissement il est entendu toute réaction de polymérisation ou réticulation, totale ou partielle des composés présents dans la composition et susceptibles de réagir dans les conditions de traitement appliquées, y compris sans nécessité de traitement thermique. Ces compositions séchées et durcies sont alors en général associées à un substrat, tel que notamment un textile, notamment les textiles selon l’invention, ou encore aux pièces en caoutchouc, ou analogue, incorporant ces textiles. Par associé, on entend que la composition imprègne le textile, revêt le textile, ou imprègne et revêt le textile.
Le revêtement peut être continu ou discontinu. L’imprégnation peut être complète et à cœur ou partielle. A subject of the invention is also these compositions which are dried and hardened after suitable treatment such as a heat treatment. By drying, it is understood to mean evaporation of water or of volatile matter. By curing is meant any polymerization or crosslinking reaction, total or partial, of the compounds present in the composition and capable of reacting under the treatment conditions applied, including without the need for heat treatment. These dried and cured compositions are then generally associated with a substrate, such as in particular a textile, in particular the textiles according to the invention, or else with rubber parts, or the like, incorporating these textiles. By associated is meant that the composition impregnates the textile, coats the textile, or impregnates and coats the textile. The coating can be continuous or discontinuous. Impregnation can be complete and full or partial.
L’invention a encore pour objet un kit ou set comprenant une première composition comprenant un sel de lignosulfonate et un latex de polymère, notamment d’élastomère, et une deuxième composition comprenant un durcisseur époxy du sel de lignosulfonate. Les première et deuxième compositions sont aptes et destinées à être mélangées pour former la composition d’adhérisation, avant l’application de cette dernière sur un textile au sens de l’invention. A subject of the invention is also a kit or set comprising a first composition comprising a lignosulfonate salt and a polymer latex, in particular an elastomer, and a second composition comprising an epoxy hardener of the lignosulfonate salt. The first and second compositions are suitable and intended to be mixed to form the adhesion composition, before the latter is applied to a textile within the meaning of the invention.
L’invention concerne aussi un procédé d’application d’une composition d’adhérisation selon l’invention, pour conférer des propriétés d’adhésion à un textile de renfort, vis-à-vis d’un caoutchouc ou d’un matériau analogue. Ce procédé comprendra le séchage et le durcissement de la composition, par un traitement adapté tel qu’un traitement thermique. The invention also relates to a method of applying an adhesion composition according to the invention, to impart adhesion properties to a reinforcing textile, with respect to a rubber or a similar material. . This process will include drying and curing the composition, by a suitable treatment such as heat treatment.
L’invention concerne aussi l’utilisation d’une composition selon l’invention ou d’une composition d’adhérisation séchée et durcie, pour conférer des propriétés d’adhésion à un textile de renfort, vis-à-vis d’un caoutchouc ou d’un matériau analogue. The invention also relates to the use of a composition according to the invention or of a dried and hardened adhesion composition, for imparting adhesion properties to a reinforcing textile, with respect to a rubber. or similar material.
L’invention concerne aussi un textile de renfort, notamment fil, câblé ou structure textile, au moins partiellement revêtu et/ou imprégné d’une composition d’adhérisation selon l’invention, notamment séchée et durcie. The invention also relates to a reinforcing textile, in particular thread, cord or textile structure, at least partially coated and / or impregnated with an adhesion composition according to the invention, in particular dried and hardened.
L’invention concerne aussi un article ou pièce en caoutchouc (ou matériau analogue) ou comportant une partie en caoutchouc (ou matériau analogue), dans laquelle le caoutchouc comprend au moins un textile de renfort selon l’invention, en surface et/ou intégré à l’intérieur du caoutchouc ou de la matrice en caoutchouc. The invention also relates to an article or part made of rubber (or similar material) or comprising a part made of rubber (or similar material), in which the rubber comprises at least one reinforcing textile according to the invention, on the surface and / or integrated. inside the rubber or rubber matrix.
D’autres objets de l’invention apparaîtront à la lecture de la description détaillée qui va suivre. Other objects of the invention will become apparent on reading the detailed description which follows.
Description détaillée detailed description
L’invention a donc pour premier objet une composition adhésive ou d’adhérisation pour textile, comprenant (ou à base de, constituée essentiellement de, ou constituée de) au moins un sel de lignosulfonate, au moins un durcisseur époxy de ce sel, et un latex d’élastomère. The first subject of the invention is therefore an adhesive or adhesion composition for textiles, comprising (or based on, consisting essentially of, or consisting of) at least one lignosulfonate salt, at least one epoxy hardener of this salt, and an elastomer latex.
Sans vouloir être lié à la théorie, on pense que le sel de lignosulfonate et le durcisseur époxy de ce sel, par définition, réagissent ensemble en donnant un produit de réaction lorsque leur mélange est réalisé et soumis ou non à la chaleur, tel qu’un traitement thermique qui sera appliqué sur le textile une fois enduit et/ou imprégné de la composition d’adhérisation. -Il est attendu que le sel de lignosulfonate engage une réaction avec le
durcisseur époxy dans une réaction de réticulation par addition des motifs réactifs du lignosulfonate sur les cycles époxydes et ouverture de ce cycle, lorsque les composés sont soumis à la chaleur. Cette chaleur peut être appliquée lors d’un traitement thermique tels que le traitement thermique appliqué sur un textile après enduction et/ou imprégnation de la composition d’adhérisation. Le durcisseur époxy contenant au moins 2 motifs époxyde, il est attendu une réaction de réticulation, et donc formation d’un polymère ou d’une résine. Dans un mode favorable, il est attendu que cette réaction soit favorisée par la présence d’un milieu basique. Cet état de réaction a été étudié et décrit plus en détail dans la partie I des exemples. On ne peut toutefois pas exclure la possibilité d’un, ou de plusieurs mécanismes réactionnels entre le sel de lignosulfonate et l’époxy lors de la préparation ou du stockage. Par « produit de réaction », on entend comme cela va de soi le produit de la réaction entre le lignosulfonate et le durcisseur époxy, ce qui ne comprend pas les éventuels additifs qui pourraient entrer dans la composition finale. Without wishing to be bound by theory, it is believed that the lignosulfonate salt and the epoxy hardener of that salt, by definition, react together to give a reaction product when they are mixed together and whether or not subjected to heat, such as a heat treatment which will be applied to the textile once coated and / or impregnated with the adhesion composition. -The lignosulfonate salt is expected to react with the epoxy hardener in a crosslinking reaction by adding the reactive units of lignosulfonate to the epoxy rings and opening this ring, when the compounds are subjected to heat. This heat can be applied during a heat treatment such as the heat treatment applied to a textile after coating and / or impregnation of the adhesion composition. Since the epoxy hardener contains at least 2 epoxy units, a crosslinking reaction is expected, and therefore formation of a polymer or a resin. In a favorable mode, this reaction is expected to be favored by the presence of a basic medium. This reaction state has been studied and described in more detail in part I of the examples. However, the possibility of one or more reaction mechanisms between the lignosulfonate salt and the epoxy cannot be excluded during preparation or storage. The term “reaction product” is understood to mean, as goes without saying, the product of the reaction between the lignosulfonate and the epoxy hardener, which does not include any additives which could enter into the final composition.
Cette composition peut notamment être obtenue par un procédé, également objet de l’invention, selon lequel on mélange les trois ingrédients sous agitation. This composition can in particular be obtained by a process, also subject of the invention, according to which the three ingredients are mixed with stirring.
Comme illustré dans les exemples, selon un premier mode de réalisation, on peut solubiliser le sel de lignosulfonate dans l’eau, avant de mélanger la solution obtenue au latex et à l’époxy. On peut faciliter cette solubilisation en travaillant en milieu basique, par l’ajout d’un agent type soude et/ou ammoniaque. Suivant une modalité, on mélange d’abord la solution de sel de lignosulfonate et le latex, puis seulement ensuite on ajoute l’époxy. Suivant une autre modalité, on mélange d’abord la solution de sel de lignosulfonate et le durcisseur époxy, puis seulement ensuite on ajoute le latex, ceci constituant donc deux modalités. A noter que, sauf indication contraire, par le terme « ajout », il peut s’agir d’ajouter le premier produit au deuxième, ou l’inverse. As illustrated in the examples, according to a first embodiment, the lignosulfonate salt can be dissolved in water, before mixing the solution obtained with the latex and the epoxy. This solubilization can be facilitated by working in a basic medium, by adding a soda and / or ammonia type agent. According to one method, the lignosulfonate salt solution and the latex are mixed first, and only then is the epoxy added. According to another modality, we first mix the solution of lignosulfonate salt and the epoxy hardener, then only then is the latex added, thus constituting two modalities. Note that, unless otherwise indicated, by the term "addition", it can mean adding the first product to the second, or vice versa.
Dans un mode de réalisation du procédé de préparation, on peut dissoudre le sel de lignosulfonate dans de l’eau sous agitation et en présence de l’agent permettant d’être à pH basique, on agite jusqu’à solubilisation, de préférence totale, on l’ajoute ensuite, tout en agitant, au latex, avant d’incorporer, toujours sous agitation, le durcisseur (de préférence celui-ci est préalablement dissout ou dispersé dans de l’eau, e.g. sous forte agitation). Selon une modalité pratique, le mélange sel de lignosulfonate et le latex est ajouté dans la solution ou dispersion de durcisseur époxy. Le mélange au durcisseur époxy peut être réalisé dans la suite de la préparation du mélange lignosulfonate et latex, ou ultérieurement, comme dans le cas du kit ou set objet de l’invention. La composition est utilisable comme composition d’adhérisage prête à l’emploi ou pouvant être diluée à façon. In one embodiment of the preparation process, the lignosulfonate salt can be dissolved in water with stirring and in the presence of the agent allowing the pH to be basic, the mixture is stirred until solubilization, preferably complete, it is then added, while stirring, to the latex, before incorporating, still with stirring, the hardener (the hardener is preferably dissolved or dispersed beforehand in water, eg with vigorous stirring). According to a practical modality, the mixture of lignosulfonate salt and the latex is added to the solution or dispersion of epoxy hardener. The mixture with the epoxy hardener can be carried out following the preparation of the lignosulfonate and latex mixture, or subsequently, as in the case of the kit or set which is the subject of the invention. The composition can be used as a ready-to-use adhesive composition or which can be custom-diluted.
Selon un autre mode de réalisation du procédé, on peut mélanger une solution aqueuse de lignosulfonate et de durcisseur époxy, avant d’ajouter le mélange sous agitation
à une dispersion aqueuse de latex. Selon une modalité pratique, le mélange sel de lignosulfonate et durcisseur époxy est ajouté dans le latex. Avantageusement, le pH de la solution de lignosulfonate ou de lignosulfonate et de durcisseur est ajusté pour être basique, par exemple par ajout de soude et/ou d’ammoniaque, avant incorporation du latex. La composition est utilisable comme composition d’adhérisage prête à l’emploi ou pouvant être diluée à façon. According to another embodiment of the process, it is possible to mix an aqueous solution of lignosulfonate and of epoxy hardener, before adding the mixture with stirring. to an aqueous dispersion of latex. According to a practical modality, the mixture of lignosulfonate salt and epoxy hardener is added to the latex. Advantageously, the pH of the solution of lignosulfonate or of lignosulfonate and of hardener is adjusted to be basic, for example by adding sodium hydroxide and / or ammonia, before incorporation of the latex. The composition can be used as a ready-to-use adhesive composition or which can be diluted on demand.
Les caractéristiques qui suivent s’appliquent aux différents objets de l’invention.The following characteristics apply to the various objects of the invention.
Le latex est de préférence une dispersion aqueuse basique du/des polymère(s) et/ou élastomère(s). On peut aussi travailler selon l’invention à pH neutre. Les valeurs de pH de travail peuvent notamment être celles mentionnées plus loin à propos du pH de la composition. The latex is preferably a basic aqueous dispersion of the polymer (s) and / or elastomer (s). It is also possible to work according to the invention at neutral pH. The working pH values can in particular be those mentioned below with regard to the pH of the composition.
Par « élastomère », on entend, notamment, une chaîne polymère ou copolymère dont la température de transition vitreuse (Tv) est inférieure à environ 25°C. Les élastomères sont présents dans le caoutchouc à adhériser et dans le latex de la composition d’adhérisation. Un « latex d’élastomère » est une dispersion aqueuse colloïdale d’élastomère. The term “elastomer” is understood to mean, in particular, a polymer or copolymer chain whose glass transition temperature (T v ) is less than approximately 25 ° C. The elastomers are present in the rubber to be adhered and in the latex of the adhesion composition. An "elastomer latex" is a colloidal aqueous dispersion of elastomer.
Par « caoutchouc » (en anglais « rubber ») ou « matériau élastomère », on entend ici le produit vulcanisé ou réticulé préparé à partir d’élastomère ou de gomme élastomère, synthétique ou naturel, d’un ou plusieurs types, de charge(s) renforçante(s) (noirs de carbone, silice, kaolins...), de plastifiant(s), d’agent(s) de vulcanisation (soufre, peroxyde, oxydes métalliques et les accélérateurs nécessaires), d’éventuels autres additifs usuels pour l’application considérée (par exemple pour faciliter la mise en oeuvre, pour la protection contre le dioxygène, l'ozone, la chaleur, la flamme, les UV). L’invention s’intéresse aussi bien aux caoutchoucs synthétiques qu’au caoutchouc naturel. Les caoutchoucs, formulés à base d’élastomères, sont des matériaux dont la Tv obtenue est inférieure à la température de service, de fonctionnement ou d’utilisation des pièces mécaniques ou assemblages formés avec le ou les caoutchoucs. By "rubber" (in English "rubber") or "elastomeric material" is meant here the vulcanized or crosslinked product prepared from elastomer or elastomeric rubber, synthetic or natural, of one or more types, of filler ( s) reinforcing agent (s) (carbon blacks, silica, kaolins ...), plasticizer (s), vulcanizing agent (s) (sulfur, peroxide, metal oxides and the necessary accelerators), any other usual additives for the application in question (for example to facilitate processing, for protection against oxygen, ozone, heat, flame, UV rays). The invention relates to both synthetic rubbers and natural rubber. Rubbers, formulated on the basis of elastomers, are materials whose Tg obtained is lower than the service, operating or use temperature of the mechanical parts or assemblies formed with the rubber (s).
Les lignosulfonates sont des sous-produits issus de la transformation du bois, notamment du traitement du bois pour la fabrication de pâte à papier selon le procédé dit « procédé de cuisson acide au bisulfite ». Ce procédé, qui met en oeuvre un bisulfite, permet selon la nature du contre-ion employé d’obtenir les sels de lignosulfonate correspondants. Ces lignosulfonates peuvent aussi être issus d’une filière destinée à les produire à partir du bois. Lignosulphonates are by-products resulting from the transformation of wood, in particular from the treatment of wood for the manufacture of paper pulp according to the process known as “acidic bisulphite cooking process”. This process, which uses a bisulfite, makes it possible, depending on the nature of the counterion used, to obtain the corresponding lignosulfonate salts. These lignosulfonates can also come from a process intended to produce them from wood.
De préférence, dans la composition d’adhérisation, le sel de lignosulfonate peut être un sel de sodium, de potassium, de magnésium, d’ammonium ou de calcium.
Dans un exemple de réalisation, on utilise des lignosulfonates préparés par le procédé bisulfite à partir de pin maritime, par exemple provenant des Landes (France). Preferably, in the adhesion composition, the lignosulfonate salt can be a sodium, potassium, magnesium, ammonium or calcium salt. In an exemplary embodiment, use is made of lignosulfonates prepared by the bisulfite process from maritime pine, for example from the Landes (France).
De préférence, les compositions d’adhérisation ne comprennent pas de formaldéhyde ou de formol. De préférence, les compositions d’adhérisation ne comprennent pas de résorcinol. De préférence, les compositions d’adhérisation ne comprennent ni formaldéhyde ou formol, ni résorcinol. De préférence, les compositions d’adhérisation ne comprennent pas de solvant organique. Elles utilisent de l’eau en tant que solvant, dont le pH peut être ajusté en fonction des besoins. Preferably, the adhesion compositions do not include formaldehyde or formalin. Preferably, the adhesion compositions do not include resorcinol. Preferably, the adhesion compositions do not include formaldehyde or formalin, or resorcinol. Preferably, the adhesion compositions do not include an organic solvent. They use water as a solvent, the pH of which can be adjusted as needed.
Le durcisseur époxy selon l’invention est un composé polyépoxydique, comprenant au moins 2 groupes ou motifs époxydes ou époxy. On peut citer en particulier ceux qui comportent en moyenne plus d'un radical glycidyle ou -méthyl-glycidyle porté par un hétéro- atome, de préférence un atome d'oxygène ou d'azote, plus particulièrement atome d’oxygène, ou ceux qui renferment en moyenne plus d'un groupement époxy-cyclo-hexyle. Il est possible d’utiliser plusieurs composés différents des listes qui suivent. The epoxy hardener according to the invention is a polyepoxy compound comprising at least 2 epoxy or epoxy groups or units. Mention may in particular be made of those which contain on average more than one glycidyl or -methyl-glycidyl radical carried by a heteroatom, preferably an oxygen or nitrogen atom, more particularly an oxygen atom, or those which contain on average more than one epoxy-cyclo-hexyl group. It is possible to use several different compounds from the following lists.
On peut citer comme durcisseur notamment : As hardener, the following can be mentioned in particular:
- des éthers diglycidyliques ou polyglycidlyliques de polyols aliphatiques, - diglycidyl or polyglycidlyl ethers of aliphatic polyols,
- des éthers diglycidyliques ou polyglycidyliques de phénols polyfonctionnels,- diglycidyl or polyglycidyl ethers of polyfunctional phenols,
- des éthers polyglycidyliques de produits de condensation de phénols avec le formaldéhyde obtenus dans des conditions acides, - polyglycidyl ethers of condensation products of phenols with formaldehyde obtained under acidic conditions,
- des esters di- ou polyglycidyliques d'acides polycarboxyliques aliphatique ou aromatique, - di- or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids,
- des composés à groupements époxycyclohexyles, - compounds containing epoxycyclohexyl groups,
- des composés polyépoxydes résultant de l’époxydation d’un composé oléfiniquement insaturé - polyepoxy compounds resulting from the epoxidation of an olefinically unsaturated compound
On peut mentionner notamment : We can mention in particular:
- des éthers diglycidyliques ou polyglycidlyliques de polyols aliphatiques comme le butane-diol-1 ,4, le hexane-diol-1 ,6, le 1 ,2,6-hexane-triol, le glycérol, le néopentylglycol, l’éthylèneglycol, le triéthylèneglyycol, 1 ,2 propyléneglycol ou des polyalkylène-glycols tels que des polypropylène-glycols, ou dérivés des polyalkylène-glycols, par exemple des polypropylène-glycols ; - diglycidyl or polyglycidlyl ethers of aliphatic polyols such as butanediol-1, 4, hexane-diol-1, 6, 1, 2,6-hexane-triol, glycerol, neopentylglycol, ethylene glycol, triethyleneglyycol, 1, 2 propylene glycols or polyalkylene glycols such as polypropylene glycols, or derivatives of polyalkylene glycols, for example polypropylene glycols;
- des éthers diglycidyliques ou polyglycidyliques de phénols polyfonctionnels comme le 2,2-bis(4-hydroxyphényl)propane (ou BPA), le 2,2-bis(4-
hydroxyphényl)hexafluoropropane (ou BPA-F), 1 ,1-bis(4-hydroxyphényl)-1-phényl- éthane (ou BPA-P), 2,2-bis(4-hydroxyphényl)butane, (BPB), le bis-(4- hydroxyphényl)diphénylméthane (ou BPBP), le 2,2-bis(3-méthyl-4- hydroxyphényl)propane (ou BPC), le bis(4-hydroxyphényl)-2,2-dichloréthylène (ou BPCII), le bis(4-hydroxyphényl)méthane (ou BPF), le 4,4'-(9/-/-fluorén-9- ylidène)bisphénol (ou BPFL), le 2,2-bis(4-hydroxy-3-isopropylphényl)propane (ou BPG), 1 ,3-bis(2-(4-hydroxyphényl)-2-propyl)benzène (ou BPM), le 1 ,1 -bis(4- hydroxyphényl)cyclohexane (BPZ) et similaire ; - diglycidyl or polyglycidyl ethers of polyfunctional phenols such as 2,2-bis (4-hydroxyphenyl) propane (or BPA), 2,2-bis (4- hydroxyphenyl) hexafluoropropane (or BPA-F), 1, 1-bis (4-hydroxyphenyl) -1-phenyl-ethane (or BPA-P), 2,2-bis (4-hydroxyphenyl) butane, (BPB), bis- (4- hydroxyphenyl) diphenylmethane (or BPBP), 2,2-bis (3-methyl-4- hydroxyphenyl) propane (or BPC), bis (4-hydroxyphenyl) -2,2-dichlorethylene (or BPCII ), bis (4-hydroxyphenyl) methane (or BPF), 4,4 '- (9 / - / - fluoren-9-ylidene) bisphenol (or BPFL), 2,2-bis (4-hydroxy- 3-isopropylphenyl) propane (or BPG), 1, 3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene (or BPM), 1, 1 -bis (4-hydroxyphenyl) cyclohexane (BPZ) and similar;
- des éthers polyglycidyliques de produits de condensation de phénols avec le formaldéhyde obtenus dans des conditions acides: des novolaques du phénol et des novolaques de crésols et similaire ; - polyglycidyl ethers of condensation products of phenols with formaldehyde obtained under acidic conditions: novolacs of phenol and novolacs of cresols and the like;
- des éthers de composés à groupements époxycyclohexyles tels que le 3,4- époxycyclohexylméthyl 3,4 époxycyclohexanecarboxylate, l'époxy-8,9 (époxy-3,4 cyclohexyl)-3 di-oxa-2,4 spiro 5.5 undécane et l'adipate de bis-(époxy-3,4 cyclohexylméthyle), et similaire ; - ethers of compounds containing epoxycyclohexyl groups such as 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate, epoxy-8,9 (epoxy-3,4 cyclohexyl) -3-di-oxa-2,4 spiro 5.5 undecane and l bis- (3,4-epoxy cyclohexylmethyl) adipate, and the like;
- des esters di- ou polyglycidyliques d'acides polycarboxyliques tels que l'acide phtalique, l'acide téréphtalique, l'acide A -tétrahydrophtalique, l'acide hexahydrophtalique, l'acide triméllitique, l’acide oxalique, l’acide succinique, l’acide glutarique, l’acide linolénique dimérisé et similaires. - di- or polyglycidyl esters of polycarboxylic acids such as phthalic acid, terephthalic acid, A -tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, oxalic acid, succinic acid, glutaric acid, dimerized linolenic acid and the like.
Le durcisseur époxy pourra notamment être choisi parmi les composés ci-dessous, étant entendu que la composition pourra incorporer l’un d’entre eux ou plusieurs d’entre eux, notamment 2 d’entre eux : The epoxy hardener can in particular be chosen from the compounds below, it being understood that the composition can incorporate one of them or more of them, in particular 2 of them:
1 ,4 butanediol diglycidyl éther (Éthers diglycidyliques de polyols aliphatiques) 2,2-bis(4-hydroxyphényl) propane diglycidyl éther (Éthers diglycidyliques de phénols polyfonctionnels) 1, 4 butanediol diglycidyl ether (Diglycidyl ethers of aliphatic polyols) 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether (Diglycidyl ethers of polyfunctional phenols)
- Diglycidyl 1 ,2-cyclohexanedicarboxylate (Esters di- ou polyglycidyliques d'acides polycarboxyliques) - Diglycidyl 1, 2-cyclohexanedicarboxylate (Di- or polyglycidyl esters of polycarboxylic acids)
- 3,4-époxycyclohexylméthyl 3,4 époxycyclohexanecarboxylate (Composés à groupements époxycyclohexyles) - 3,4-epoxycyclohexylmethyl 3,4 epoxycyclohexanecarboxylate (Compounds containing epoxycyclohexyl groups)
1 ,6 hexanediol diglycidyl éther (Éthers diglycidyliques de polyols aliphatiques)1, 6 hexanediol diglycidyl ether (Diglycidyl ethers of aliphatic polyols)
- Glycérol diglycidyl éther (Éthers diglycidyliques de polyols aliphatiques) - Glycerol diglycidyl ether (Diglycidyl ethers of aliphatic polyols)
- Glycérol triglycidyl éther (Éthers polyglycidlyliques de polyols aliphatiques) - Glycerol triglycidyl ether (Polyglycidlyl ethers of aliphatic polyols)
- Mélange de glycérol diglycidyl éther et glycérol triglycidyl éther, e.g. commercialisé par la Société Raschig sous la référence GE100 (Éthers diglycidyliques de polyols aliphatiques)
- Résines époxyde de type novolaque, e.g. comercialisées par la Société HUNTSMAN sous la référence Araldite PZ 323 (Éthers polyglycidyliques de produits de condensation de phénols avec le formaldéhyde) - Mixture of glycerol diglycidyl ether and glycerol triglycidyl ether, eg marketed by the company Raschig under the reference GE100 (Diglycidyl ethers of aliphatic polyols) - Novolak type epoxy resins, eg marketed by the company HUNTSMAN under the reference Araldite PZ 323 (Polyglycidyl ethers of condensation products of phenols with formaldehyde)
Le durcisseur époxy peut aussi être choisi parmi des dérivés N-glycidyliques d'amines, d'amides et de bases azotées hétérocycliques, par exemple : - la N,N-diglycidyl-aniline, - la N,N-diglycidyl-toluidine, - le N, N, N', N' tétrakis-glycidyl bis-(amino-4 phényl)-méthane, - le dérivé triglycidylique de l'hydroxy-4 aniline, - l'isocyanurate de triglycidyle, - la N,N'- diglycidyl-éthylène-urée, - la N,N'-diglycidyl diméthyl-5,5 hydantoine, - la N,N'-diglycidyl isopropyl-5 hydantoine et - le N,N'diglycidyl diméthyl-5,5 isopropyl-6 dlhydro-5,6 uracile. The epoxy hardener can also be chosen from N-glycidyl derivatives of heterocyclic amines, amides and nitrogenous bases, for example: - N, N-diglycidyl-aniline, - N, N-diglycidyl-toluidine, - N, N, N ', N' tetrakis-glycidyl bis- (4-amino phenyl) -methane, - the triglycidyl derivative of 4-hydroxy aniline, - triglycidyl isocyanurate, - N, N'- diglycidyl-ethylene-urea, - N, N'-diglycidyl-5,5-dimethyl hydantoin, - N, N'-diglycidyl isopropyl-5 hydantoin and - N, N'diglycidyl-5,5-dimethyl-isopropyl-6 dlhydro -5.6 uracil.
Le latex peut avantageusement être un latex de copolymère acrylonitrile/butadiène carboxylé (XNBR), un latex d'acrylonitrile/butadiène hydrogéné (HNBR), un latex de polyéthylène chlorosulfoné (CSM), un latex de copolymère styrène-butadiène-vinylpyridine (VPSBR), un latex de copolymère styrène/butadiène (SBR), un latex de copolymère acrylonitrile/butadiène (NBR), un latex de polybutadiène (BR), un latex de chlorobutadiène (CR), un latex de caoutchouc naturel (NR), un latex de polyuréthane, ou un mélange d’au moins deux d’entre eux. The latex can advantageously be a latex of acrylonitrile / carboxylated butadiene copolymer (XNBR), a latex of acrylonitrile / hydrogenated butadiene (HNBR), a latex of chlorosulfonated polyethylene (CSM), a latex of styrene-butadiene-vinylpyridine copolymer (VPSBR) , a styrene / butadiene copolymer latex (SBR), an acrylonitrile / butadiene copolymer latex (NBR), a polybutadiene latex (BR), a chlorobutadiene latex (CR), a natural rubber latex (NR), a latex polyurethane, or a mixture of at least two of them.
Le taux massique de matière sèche de la composition peut être compris notamment entre environ 2 et environ 38%, en particulier entre environ 4 et environ 30%, plus particulièrement entre environ 7 et environ 25%. The dry matter content of the composition by weight can be in particular between approximately 2 and approximately 38%, in particular between approximately 4 and approximately 30%, more particularly between approximately 7 and approximately 25%.
La composition selon l’invention peut notamment comprendre d’environ 40 à environ 95 %, de préférence d’environ 55 à environ 90% ou d’environ 40 à environ 60, 70, 80 ou 90 % en masse d’élastomère par rapport à la composition. The composition according to the invention may in particular comprise from about 40 to about 95%, preferably from about 55 to about 90% or from about 40 to about 60, 70, 80 or 90% by weight of elastomer relative to to the composition.
Sauf indication contraire, la composition est donnée en matière sèche.Unless otherwise indicated, the composition is given as a dry matter.
Dans la composition, le ratio massique durcisseur / sel de lianosulfonate peut être compris notamment entre environ 0,01 et environ 5, plus particulièrement entre environ 0,03 et environ 1 , typiquement entre environ 0,05 et environ 0,5. Des valeurs inférieures ou supérieures pourront s’avérer possible selon les couples durcisseur et sel de lignosulfonate choisis et ce paramètre est déterminable par l’homme du métier sur la base de cette description. In the composition, the hardener / lianosulfonate salt mass ratio can be in particular between approximately 0.01 and approximately 5, more particularly between approximately 0.03 and approximately 1, typically between approximately 0.05 and approximately 0.5. Lower or higher values may prove to be possible depending on the hardener and lignosulfonate salt pairs chosen and this parameter can be determined by a person skilled in the art on the basis of this description.
Dans la composition, le ratio massique [durcisseur + sel de liqnosulfonatel / latex peut être compris notamment entre environ 0,05 et environ 0,6 plus particulièrement entre environ 0,15 et environ 0,5. Des valeurs inférieures ou supérieures pourront s’avérer
possible selon les composés choisis en combinaison et ce paramètre est déterminable par l’homme du métier sur la base de cette description. In the composition, the mass ratio [hardener + liqnosulfonatel salt / latex can be in particular between approximately 0.05 and approximately 0.6, more particularly between approximately 0.15 and approximately 0.5. Lower or higher values may prove to be possible according to the compounds chosen in combination and this parameter can be determined by a person skilled in the art on the basis of this description.
Suivant une caractéristique avantageuse, la composition a un pH neutre ou basique, notamment un pH compris entre environ 7 et environ 13, en particulier entre environ 9 et environ 13. La composition peut comprendre à cet effet un additif permettant d’ajuster le pH, par exemple de la soude. According to an advantageous characteristic, the composition has a neutral or basic pH, in particular a pH of between approximately 7 and approximately 13, in particular between approximately 9 and approximately 13. The composition can comprise for this purpose an additive making it possible to adjust the pH, eg soda.
La composition comprend l’eau du latex d’élastomère. De l’eau peut encore être ajoutée, afin de rendre la composition applicable suffisamment fluide pour une application classique, par exemple par imprégnation. The composition includes the water of the elastomer latex. Water can still be added, in order to make the applicable composition sufficiently fluid for a conventional application, for example by impregnation.
La composition peut encore comprendre des additifs à une teneur notamment comprise entre environ 0,01 ou 0,1 et environ 50% en masse sèche. La composition peut notamment comprendre un promoteur d’adhésion ou d’adhérence soluble en milieu aqueux (par exemple, silane, isocyanate bloqué), un tensioactif, un dispersant, un agent anti mousse, une cire (par exemple cire hydrocarbonée microcristalline en émulsion), une charge (par exemple noir de carbone, silice), un colorant, un oxyde métallique (par exemple oxyde de zinc ZnO), un réticulant d’élastomère, un agent anti-UV, un agent anti-ozone, un agent thermo-protecteur. Ces agents sont des additifs classiquement utilisés dans les formulations RFL. Ils sont compatibles avec l’adhésif objet de l’invention. The composition may also comprise additives at a content in particular of between approximately 0.01 or 0.1 and approximately 50% by dry mass. The composition can in particular comprise an adhesion promoter or adhesion soluble in aqueous medium (for example, silane, blocked isocyanate), a surfactant, a dispersant, an antifoaming agent, a wax (for example microcrystalline hydrocarbon wax in emulsion) , a filler (eg carbon black, silica), a colorant, a metal oxide (eg zinc oxide ZnO), an elastomer crosslinker, an anti-UV agent, an anti-ozone agent, a thermo-agent. protective. These agents are additives conventionally used in RFL formulations. They are compatible with the adhesive that is the subject of the invention.
Dans un mode de réalisation, la composition d’adhérisation pour textile est constituée essentiellement d’un sel de lignosulfonate, d’un durcisseur époxy ce sel, et d’un latex d’élastomère, et peut comprendre un ou plusieurs additifs, notamment un ou plusieurs des additifs mentionnés au paragraphe précédent. Avantageusement, les compositions selon l’invention ne comprennent pas de durcisseur ou catalyseur classique des composés à groupe ou motif époxy, comme la triéthylènetriamine (TETA) et la triéthylamine (TEA). In one embodiment, the textile adhesion composition consists essentially of a lignosulfonate salt, an epoxy hardener this salt, and an elastomer latex, and may comprise one or more additives, in particular a or more of the additives mentioned in the previous paragraph. Advantageously, the compositions according to the invention do not comprise a hardener or conventional catalyst for compounds containing an epoxy group or unit, such as triethylenetriamine (TETA) and triethylamine (TEA).
La viscosité de la composition d’adhérisation est mesurée à 23°C à l’aide d’un viscosimètre Brookfield, par exemple équipé d’un module ULA adapté aux basses viscosités. Comme cela est détaillé dans les exemples, la viscosité peut être ajustée en jouant notamment sur la teneur en eau. La viscosité peut être ajustée de manière à obtenir le niveau souhaité pour permettre une bonne application sur le textile dans le procédé d’enduction ou d’imprégnation utilisé. Dans le cas d’une imprégnation par trempage, cette viscosité peut notamment être comprise entre environ 1 et environ 10, typiquement entre environ 1 et environ 5 Cp ou mPa.s. The viscosity of the adhesion composition is measured at 23 ° C using a Brookfield viscometer, for example equipped with a ULA module suitable for low viscosities. As is detailed in the examples, the viscosity can be adjusted by adjusting in particular the water content. The viscosity can be adjusted to achieve the desired level to allow good application to the textile in the coating or impregnation process used. In the case of impregnation by soaking, this viscosity can in particular be between approximately 1 and approximately 10, typically between approximately 1 and approximately 5 Cp or mPa.s.
La composition selon l’invention peut être appliquée sur tout textile. Par « textile » au sens de l’invention, on entend : fil continu monofilamentaire, fil continu multifilamentaire, fil ou fibre coupé (en anglais « staple fiber »), tout assemblage de fils continus monofilamentaires et/ou multifilamentaires ou de fil coupé, notamment une mèche, un câblé
formé de tels fils par les techniques classiques de retordage et une « structure textile » formée de l’assemblage de fils, retors ou câblés, sous la forme notamment de tissu, de grille, etc. Les textiles de l’invention, ayant été traités par la composition selon l’invention, sont désignés par l’expression « textiles de renfort ». The composition according to the invention can be applied to any textile. By “textile” within the meaning of the invention, is meant: continuous monofilament yarn, continuous multifilament yarn, staple fiber, any assembly of monofilament and / or multifilament continuous yarns or chopped yarn, including a wick, a cable formed from such yarns by conventional twisting techniques and a "textile structure" formed from the assembly of yarns, twisted or cabled, in particular in the form of fabric, grid, and the like. The textiles of the invention, having been treated with the composition according to the invention, are designated by the expression “reinforcing textiles”.
Le textile peut être de nature organique ou inorganique. Comme nature de textile, on peut citer notamment le verre (notamment verre E ou verre haut module), le basalte, le carbone, l'aramide (meta ou para), les alcools polyvinylique, la cellulose, les polyéthylènes haute densité (PEHD), les polyester (notamment les polytéréphtalates d’éthylène, PET), les polyamides (PA, notamment les PA 4.6, PA 6.6, PA 6), les acryliques, les hybrides (fil en aramide + fil en nylon, câblés ensemble ; acrylique + verre + cuivre, câblés ensemble), etc. Lorsque le textile est un câblé ou une structure textile de plusieurs fils, les fils peuvent être tous de nature organique ou inorganique, ou le câblé ou la structure textile peut comporter les deux types de fils, organique et inorganique. The textile can be organic or inorganic in nature. As the type of textile, mention may in particular be made of glass (in particular E glass or high modulus glass), basalt, carbon, aramid (meta or para), polyvinyl alcohols, cellulose, high density polyethylenes (HDPE). , polyester (in particular polyethylene terephthalates, PET), polyamides (PA, in particular PA 4.6, PA 6.6, PA 6), acrylics, hybrids (aramid yarn + nylon yarn, cabled together; acrylic + glass + copper, wired together), etc. When the textile is a cord or a textile structure of several threads, the threads can all be organic or inorganic in nature, or the cord or the textile structure can comprise both types of threads, organic and inorganic.
L’invention a aussi pour objet un procédé d’application, ou l’utilisation, d’une composition d’adhérisation selon l’invention, pour conférer des propriétés d’adhésion à un tel textile, notamment vis-à-vis d’un matériau élastomère. Cette utilisation peut se décliner en termes de procédé d’adhérisage d’un textile selon l’invention. Cette utilisation ou ce procédé comprend l’application de ladite composition sur le textile (fil, câblé, structure textile), puis son séchage. Cette application peut être réalisée par les méthodes en usage dans l’industrie, pour l’enduction, notamment par imprégnation, comme décrit infra. Le choix du latex, donc de l’élastomère constitutif, se porte avantageusement vers une formule similaire à la nature de l’élastomère constitutif du caoutchouc à traiter. A subject of the invention is also a process for applying, or using, an adhesion composition according to the invention, to impart adhesion properties to such a textile, in particular with respect to an elastomeric material. This use can be broken down in terms of the method of adhering a textile according to the invention. This use or method comprises applying said composition to the textile (yarn, cord, textile structure), then drying it. This application can be carried out by the methods in use in industry, for coating, in particular by impregnation, as described below. The choice of latex, and therefore of the constituent elastomer, advantageously leans towards a formula similar to the nature of the constituent elastomer of the rubber to be treated.
Dans un mode de réalisation, l’imprégnation des textiles est réalisée par trempage (« dipping ») dans des bacs contenant les préparations adhésives. In one embodiment, the impregnation of the textiles is carried out by soaking ("dipping") in trays containing the adhesive preparations.
Les fils, cordes et câbles peuvent notamment subir soit un trempage direct dans un bac, soit une imprégnation par un rouleau lécheur, pour l’application de la composition d’adhérisation. Après trempage ou imprégnation, l’excès de préparation humide est de préférence éliminé par exemple par pressage (foulardage), filière, aspiration ou par compression physique entre des supports poreux tels que des mousses. Après trempage ou imprégnation, et éventuellement élimination de l’excès, on procède ensuite au séchage et à la thermofixation de la composition d’adhérisation. Le textile imprégné enduit peut ainsi subir un passage dans un four pour permettre le séchage et la réticulation de la composition d’adhérisation. Après sortie d’un four, le textile peut à nouveau subir une étape d’imprégnation (par trempage ou imprégnation par rouleau lécheur), puis de passage dans
un four, ces étapes pouvant être répétées, notamment jusqu’à un total de 4 imprégnations (2, 3 ou 4). The wires, cords and cables can in particular undergo either a direct soaking in a tank, or an impregnation by a lick roller, for the application of the adhesion composition. After soaking or impregnation, the excess of wet preparation is preferably removed, for example by pressing (padding), die, suction or by physical compression between porous supports such as foams. After soaking or impregnation, and optionally removal of the excess, the drying and heat-setting of the adhesion composition are then carried out. The coated impregnated textile can thus be passed through an oven to allow drying and crosslinking of the adhesion composition. After leaving an oven, the textile can again undergo an impregnation step (by soaking or impregnation by a lick roller), then passing through an oven, these steps being repeatable, in particular up to a total of 4 impregnations (2, 3 or 4).
Dans un autre mode d’imprégnation, particulièrement adapté aux fibres minérales (verre, basalte, carbone...), un système de dérompage composé de peigne et/ou de « queues de cochons » peut être utilisé avant l’imprégnation d’un fil multifilamentaire. Il permet une ouverture maximale du fil multifilamentaire, pour favoriser une forte imprégnation. Après trempage ou imprégnation au rouleau lécheur comme ci-dessus, l’excès de préparation humide est de préférence éliminé par exemple par pressage (foulardage), aspiration ou par compression physique entre des supports poreux tels que des mousses. Après trempage ou imprégnation, et éventuellement élimination de l’excès, on procède ensuite au séchage et à la thermofixation de la composition d’adhérisation. Le fil imprégné enduit peut ainsi subir un passage dans un four pour permettre le séchage et la réticulation de la composition d’adhérisation. Après sortie d’un four, le fil peut à nouveau subir une étape d’imprégnation (par trempage ou imprégnation par rouleau lécheur), puis de passage dans un four, ces étapes pouvant être répétées, notamment jusqu’à un total de 4 imprégnations (2, 3 ou 4). In another mode of impregnation, particularly suitable for mineral fibers (glass, basalt, carbon, etc.), a derivation system made up of a comb and / or "pig tails" can be used before the impregnation of a multifilament yarn. It allows maximum opening of the multifilament yarn, to promote strong impregnation. After soaking or impregnation with a wet roller as above, the excess wet preparation is preferably removed, for example by pressing (padding), suction or by physical compression between porous supports such as foams. After soaking or impregnation, and optionally removing the excess, the adhesive composition is then dried and heat-set. The coated impregnated yarn can thus be passed through an oven to allow drying and crosslinking of the adhesion composition. After leaving an oven, the yarn can again undergo an impregnation step (by dipping or impregnation by licker roll), then passing through an oven, these steps can be repeated, in particular up to a total of 4 impregnations. (2, 3 or 4).
Après les étapes d’imprégnation et de séchage et thermofixation d’un fil, le fil est alors retordu en ligne. Le câblage est effectué de préférence sur un fil déjà traité, mais on peut aussi effectuer le câblage et effectuer ensuite les étapes d’imprégnation et de séchage et thermofixation. Dans les différents procédés, les vitesses peuvent aller de 1 m/min à 150m/min, les températures des fours de 30°C à 350°C, plus spécifiquement de 100 à 300°C, et encore plus spécifiquement de 140 à 220°C. Une tension mécanique peut également être appliquée sur le textile tout au long du procédé. After the steps of impregnation and drying and heat-setting of a yarn, the yarn is then twisted in line. The wiring is preferably carried out on an already treated wire, but it is also possible to perform the wiring and then perform the steps of impregnation and drying and heat setting. In the different processes, the speeds can range from 1 m / min to 150 m / min, the temperatures of the furnaces from 30 ° C to 350 ° C, more specifically from 100 to 300 ° C, and even more specifically from 140 to 220 ° vs. Mechanical tension can also be applied to the textile throughout the process.
Un mode de réalisation concerne la production d’un renfort textile pour incorporation dans des assemblages tels que courroies de transmission ou bandes transporteuses. Pour cela, un câblé, par exemple en polyamide tel que le PA 4-6 est construit par retordage, puis câblage. Le câblé obtenu peut éventuellement et avantageusement être traité par une première imprégnation à cœur destinée à bloquer les filaments entre eux et conférer au fil une résistance à l’effilochage, rendant aussi le fil raide (« stiff ») ; ceci peut être réalisé avec une solution de méthylène diphényl diisocyanate dans du toluène ; le câblé imprégné est alors soumis à séchage et thermofixation dans un four. Le câblé est ensuite imprégné dans un bac contenant une composition d’adhérisage de l’invention, puis séché et thermofixé au four. One embodiment relates to the production of a textile reinforcement for incorporation into assemblies such as transmission belts or conveyor belts. For this, a cord, for example made of polyamide such as PA 4-6, is constructed by twisting, then cabling. The cord obtained can optionally and advantageously be treated by a first core impregnation intended to block the filaments between them and give the yarn resistance to fraying, also making the yarn stiff ("stiff"); this can be done with a solution of methylene diphenyl diisocyanate in toluene; the impregnated cord is then subjected to drying and heat setting in an oven. The cord is then impregnated in a tank containing an adhesive composition of the invention, then dried and heat set in the oven.
Un autre mode de réalisation concerne la production d’un renfort textile pour incorporation dans des profilés et joints, tels que joints de fenêtre ou de porte. De tels renforts peuvent notamment être réalisés à partir de fil de verre contenant un ensimage
avec lequel la composition adhésive doit être compatible. On peut procéder à partir de fils de verre (notamment verre E), on leur fait subir un dérompage (voir ci-dessus) et une imprégnation dans le bac contenant une composition d’adhérisation de l’invention. Les fils imprégnés ont été soumis à séchage et thermofixation dans un four. A la sortie du four, les fils subissent une opération de retordage. Une pluralité, par exemple trois, retors imprégnés peuvent ensuite être câblés entre eux. Another embodiment relates to the production of a textile reinforcement for incorporation into profiles and seals, such as window or door seals. Such reinforcements can in particular be made from glass yarn containing a sizing with which the adhesive composition is to be compatible. It is possible to proceed from glass strands (in particular E-glass), they are subjected to a derompage (see above) and to an impregnation in the tank containing an adhesion composition of the invention. The impregnated yarns were subjected to drying and heat setting in an oven. On leaving the oven, the yarns undergo a twisting operation. A plurality, for example three, impregnated twists can then be cabled together.
Un autre mode de réalisation concerne la production d’un renfort textile pour servir de renfort, tressé, spiralé, guipé ou tricoté dans un tuyau de frein. On peut partir d’un fil en matière organique, par exemple en polyéthylène-téréphtalate (PET), en Polyéthylène haute densité (PEHD), ou en Polyamide. On lui applique une torsion de préférence. Le fil, de préférence retordu, est traité par une imprégnation dans une composition d’adhérisation de l’invention, puis par séchage et thermofixation dans un four. Another embodiment relates to the production of a textile reinforcement to serve as a reinforcement, braided, coiled, wrapped or knitted in a brake pipe. It is possible to start from a yarn made of organic material, for example polyethylene terephthalate (PET), high density polyethylene (HDPE), or polyamide. It is preferably applied a twist. The yarn, preferably twisted, is treated by impregnation in an adhesion composition of the invention, then by drying and heat setting in an oven.
En variante de ce mode de réalisation, on part de fils similaires, on construit un câblé par étapes successives de retordage, puis câblage. Le câblé obtenu est traité par une première imprégnation à cœur destinée à bloquer les filaments entre eux et conférer au fil une résistance à l’effilochage, rendant aussi le fil raide (« stiff »), par exemple à l’aide d’une solution de méthylène diphényl diisocyanate dans du toluène, puis soumis à séchage et thermofixation dans un four. Le câblé obtenu est ensuite traité par une imprégnation dans une composition d’adhérisation de l’invention, puis par séchage et thermofixation dans un four. As a variant of this embodiment, one starts from similar yarns, a cord is constructed by successive stages of twisting, then cabling. The cord obtained is treated by a first core impregnation intended to block the filaments between them and give the yarn resistance to fraying, also making the yarn stiff, for example using a solution. of methylene diphenyl diisocyanate in toluene, then subjected to drying and heat setting in an oven. The cord obtained is then treated by impregnation in an adhesion composition of the invention, then by drying and heat-setting in an oven.
D’autres caractéristiques de l’utilisation ou du procédé apparaîtront à la lecture du reste de la description. Other characteristics of the use or of the method will become apparent on reading the remainder of the description.
L’invention a aussi pour objet un textile de renfort revêtu et/ou imprégné d'une composition d’adhérisage selon l’invention. L’invention a notamment pour objet un textile de renfort revêtu et/ou imprégné d'une composition d’adhérisage susceptible d’être obtenue par la mise en œuvre des procédés décrits ici. Elle a aussi pour objet le procédé de traitement du textile pour produire le textile de renfort, par application de la composition d’adhérisage sur ledit textile. The subject of the invention is also a reinforcing textile coated and / or impregnated with a bonding composition according to the invention. The subject of the invention is in particular a reinforcing textile coated and / or impregnated with an adhesion composition capable of being obtained by implementing the methods described here. It also relates to the method of treating the textile to produce the reinforcing textile, by applying the adhesive composition to said textile.
L’invention a notamment pour objet un fil revêtu et/ou imprégné d'une composition d’adhérisage selon l’invention. Le fil peut être un fil retordu, et le retordage peut avoir lieu avant ou après application de la composition, et séchage et/ou durcissement de celle-ci. Lorsque le fil est multifilamentaire, il peut être imprégné à cœur, et ceci peut avoir été obtenu au besoin en dérompant le fil (écartement des filaments par des moyens connus de l’homme du métier) avant de l’imprégner avec la composition. Ce fil peut notamment comporter, ou être revêtu de, la composition d’adhérisation durcie (séchée et/ou réticulée).
L’invention a aussi pour objet un câblé revêtu et/ou imprégné d'une composition d’adhérisage selon l’invention. Ce câblé peut notamment comporter, ou être revêtu de, la composition d’adhérisation durcie (séchée et/ou réticulée). A subject of the invention is in particular a yarn coated and / or impregnated with an adhesion composition according to the invention. The yarn can be a twisted yarn, and the twisting can take place before or after application of the composition, and drying and / or curing thereof. When the yarn is multifilament, it can be impregnated to the core, and this can have been obtained if necessary by breaking the yarn (spacing of the filaments by means known to those skilled in the art) before impregnating it with the composition. This yarn can in particular comprise, or be coated with, the cured adhesion composition (dried and / or crosslinked). A subject of the invention is also a cord coated and / or impregnated with an adhesion composition according to the invention. This cord can in particular comprise, or be coated with, the cured adhesion composition (dried and / or crosslinked).
Le câblé peut être formé d’au moins deux fils non revêtus ou imprégnés de la composition adhésive, généralement chaque fil est retordu, puis les fils sont câblés (assemblés ensemble et retordus en sens inverse de la torsion des fils élémentaires), puis le câblé est imprégné de la composition adhésive, qui est durcie après application. The cord can be formed from at least two wires not coated or impregnated with the adhesive composition, generally each wire is twisted, then the wires are cabled (assembled together and twisted in the opposite direction of the twist of the elementary wires), then the cord is impregnated with the adhesive composition, which is cured after application.
Le câblé peut aussi être formé de l’assemblage d’au moins deux fils revêtus ou imprégnés de la composition adhésive, généralement chaque fil est retordu après solidification de la composition, et ensuite les fils sont câblés (assemblés ensemble et retordus en sens inverse de la torsion des fils élémentaires) ; on peut prévoir ensuite une enduction du câblé avec d’autres traitements (« overcoat » ou « topcoat »), et son séchage. The cord can also be formed from the assembly of at least two threads coated or impregnated with the adhesive composition, generally each thread is twisted after solidification of the composition, and then the threads are cabled (assembled together and twisted in the opposite direction of the twisting of the elementary wires); one can then provide a coating of the cord with other treatments ("overcoat" or "topcoat"), and its drying.
L’invention a aussi pour objet une structure textile formée de l’assemblage de fils par les techniques connues telles que le tissage ou encore par collage ou soudage dans le cas des grilles. Ces structures textiles sont revêtues ou imprégnées de la composition de l’invention, et l’invention couvre ces structures textiles revêtues de la composition d’adhérisage durcie. The subject of the invention is also a textile structure formed by assembling threads by known techniques such as weaving or by gluing or welding in the case of grids. These textile structures are coated or impregnated with the composition of the invention, and the invention covers such textile structures coated with the cured adhesion composition.
Les compositions d’adhérisage peuvent être appliquées sur les textiles au sens de l’invention par les méthodes utilisées pour les RFL. On retiendra en premier lieu l’imprégnation, par trempage direct (« dipping ») ou au moyen d’un rouleau lécheur. The adhesion compositions can be applied to textiles within the meaning of the invention by the methods used for RFLs. Firstly, the impregnation is retained, by direct dipping or by means of a lick roller.
L’invention a aussi pour objet un article ou pièce en caoutchouc (ou comprenant une partie en caoutchouc), comprenant au moins un textile de renfort, notamment fil, câblé et/ou structure textile, selon l’invention. Ce textile de renfort peut notamment être appliqué en surface de l’article ou pièce et/ou intégré à l’intérieur de l’article ou pièce. The subject of the invention is also an article or part made of rubber (or one comprising a part made of rubber), comprising at least one reinforcing textile, in particular thread, cord and / or textile structure, according to the invention. This reinforcing textile can in particular be applied to the surface of the article or part and / or integrated inside the article or part.
Comme il a été dit, le caoutchouc est une formulation vulcanisable à base d’élastomères naturels ou synthétiques, tels que caoutchouc naturel (NR ou polyisoprène) vulcanisé (réticulé), ou un caoutchouc synthétique, vulcanisé (réticulé). Comme exemple de caoutchouc synthétique, on peut citer les caoutchoucs de : polybutadiène (BR), polyuréthane (AU ou EU), polychloroprène (CR), silicone (VMQ, PVMQ) et fluorosilicone (FVMQ), éthylène-propylène-diène monomère (EPDM), copolymères butadiène- acrylonitrile (NBR pour nitrile butadiene rubber), copolymères butadiène-acrylonitrile hydrogénés (HNBR), copolymère styrène/butadiène (SBR), épichlorydrine (ECO ou CO), butyle (IIR), bromobutyle (BIIR), chlorobutyle (CMR), polyéthylènes chlorés (CM), polyéthylènes chlorosulfonés (CSM), nitrile butadiène acrylonitrile carboxylé (XNBR),
copolymères d’éthylène et d’acrylate de méthyle (AEM), copolymères d’éthylène et d’acétate de vinyle (EVM et EVA), polyacrylates (ACM), caoutchoucs fluorés (FKM), caoutchoucs perfluorés (FFKM). As has been said, rubber is a vulcanizable formulation based on natural or synthetic elastomers, such as vulcanized (crosslinked) natural rubber (NR or polyisoprene), or a synthetic, vulcanized (crosslinked) rubber. As examples of synthetic rubber, mention may be made of rubbers of: polybutadiene (BR), polyurethane (AU or EU), polychloroprene (CR), silicone (VMQ, PVMQ) and fluorosilicone (FVMQ), ethylene-propylene-diene monomer (EPDM ), butadiene-acrylonitrile copolymers (NBR for nitrile butadiene rubber), hydrogenated butadiene-acrylonitrile copolymers (HNBR), styrene / butadiene copolymer (SBR), epichlordrin (ECO or CO), butyl (IIR), bromobutyl (BIIR), chlorobutyl ( CMR), chlorinated polyethylenes (CM), chlorosulfonated polyethylenes (CSM), nitrile butadiene acrylonitrile carboxyl (XNBR), copolymers of ethylene and methyl acrylate (AEM), copolymers of ethylene and vinyl acetate (EVM and EVA), polyacrylates (ACM), fluorinated rubbers (FKM), perfluorinated rubbers (FFKM).
Un caoutchouc peut également être une formulation vulcanisable à base de mélanges ou coupages de telles gommes élastomères. A rubber can also be a vulcanizable formulation based on mixtures or cuts of such elastomeric gums.
Le caoutchouc peut également être une formulation à base de thermoplastiques élastomères (élastomères dits « à réticulation physique » comme par exemple le SBS, styrène-butadiène-styrène bloc). The rubber can also be a formulation based on thermoplastic elastomers (so-called “physically crosslinking” elastomers such as SBS, block styrene-butadiene-styrene, for example).
L’invention a notamment pour objet un article ou pièce en élastomère ou caoutchouc comportant, noyé dans sa masse en élastomère ou caoutchouc, ou affleurant en surface, un textile de renfort adhérisé selon l’invention, par exemple un ou plusieurs fils, individuels ou câblés ou encore assemblés en structures textiles, ou plusieurs de ces catégories. The subject of the invention is in particular an article or part made of elastomer or rubber comprising, embedded in its mass in elastomer or rubber, or flush with the surface, a reinforcing textile adhered according to the invention, for example one or more threads, individual or cabled or assembled in textile structures, or several of these categories.
Par « adhérisé », on entend notamment que le textile de renfort comporte ou est revêtu de la composition d’adhérisation durcie (séchée et/ou réticulée). By "bonded" is meant in particular that the reinforcing textile comprises or is coated with the cured (dried and / or crosslinked) adhesive composition.
L’invention a encore pour objet un article ou pièce en élastomère ou caoutchouc comportant, noyé dans sa masse en élastomère ou caoutchouc, un ou plusieurs fils, individuels ou câblés ou encore assemblés en structures textiles, ou plusieurs de ces catégories, et comportant en outre, collée ou adhérant sur au moins une surface de ce matériau élastomère ou caoutchouc, une structure textile selon l’invention, ces textiles de renfort étant adhérisés conformément à l’invention. The subject of the invention is also an article or part made of elastomer or rubber comprising, embedded in its mass in elastomer or rubber, one or more threads, individual or cabled or else assembled in textile structures, or more of these categories, and comprising in furthermore, glued or adhered to at least one surface of this elastomeric or rubber material, a textile structure according to the invention, these reinforcing textiles being adhered in accordance with the invention.
Comme articles, on peut citer, sans être exhaustif, les articles suivants, qui peuvent incorporer au moins un textile de renfort adhérisé selon l’invention, notamment fil, câblé ou structure textile traité par la composition d’adhérisation de l’invention, appliqué à la surface de l’article auquel il adhère et/ou intégré à l’intérieur du matériau élastomère de l’article : As articles, there may be mentioned, without being exhaustive, the following articles, which may incorporate at least one reinforcing textile adhered according to the invention, in particular yarn, cord or textile structure treated with the adhesion composition of the invention, applied. on the surface of the article to which it adheres and / or integrated inside the elastomeric material of the article:
- Courroies, notamment courroies de transmission, courroies synchrones, bandes transporteuses, courroies d’ascenseur, courroies trapézoïdales. Les courroies peuvent comprendre des fils ou des câblés noyés dans la masse d’élastomère ou de caoutchouc. Elles peuvent aussi comprendre, à la place ou en plus des fils et câblés, une structure textile, notamment un tissu, adhérant en surface, par exemple sur le dos dans la courroie de transmission, et sur le dos et le crantage pour la courroie de distribution - Belts, in particular transmission belts, synchronous belts, conveyor belts, elevator belts, V-belts. The belts can include wires or cords embedded in the mass of elastomer or rubber. They can also comprise, instead of or in addition to the son and cords, a textile structure, in particular a fabric, adhering on the surface, for example on the back in the transmission belt, and on the back and the notch for the belt. distribution
- T uyaux souples ou rigides, notamment tuyaux pour freins (comportant une structure textile tressée, mono ou double tresse), durites, tuyaux industriels (comportant une structure textile guipée ou spiralée, c’est-à-dire fabriquée par guipage ou par
spiralage), y compris tuyaux pour pétrole et gaz, durites (structure textile tricotée).- Flexible or rigid hoses, in particular brake hoses (comprising a braided textile structure, single or double braid), hoses, industrial hoses (comprising a wrapped or spiral textile structure, that is to say manufactured by wrapping or by spiraling), including oil and gas hoses, hoses (knitted textile structure).
Le tressage, spiralage, tricotage est généralement réalisé durant la mise en oeuvre du tuyau par extrusion. Braiding, spiraling, knitting is generally carried out during the implementation of the pipe by extrusion.
- Articles de spécialité : ressorts pneumatiques (« air-springs »), disques d’accouplement cinétique, obturateurs de tuyaux, joints de compensation. - Specialty items: pneumatic springs ("air-springs"), kinetic coupling discs, pipe plugs, compensation joints.
- Pneumatiques : notamment poids-lourds et course. - Tires: in particular heavy goods vehicles and racing.
A titre d’exemples de composition de caoutchouc pour ces articles : courroie transmission : à base d’EPDM ou de CR ; courroies synchrones : à base d’HNBR et de CR ; T uyaux : à base de SBR, ou d’EPDM, ou d’un coupage NBR/PVC, ou d’épichlorydrine, ou de butyle ; Airspring : à base de CR ; disques cinétiques : à base de CR ou de NR ; pneus : pièce épaisse comprenant plusieurs mélanges, à base de NR, de BR ou de SBR As examples of rubber composition for these articles: transmission belt: based on EPDM or CR; synchronous belts: based on HNBR and CR; Pipes: based on SBR, or EPDM, or an NBR / PVC blend, or epichlorohydrin, or butyl; Airspring: based on CR; kinetic discs: based on CR or NR; tires: thick part comprising several mixtures, based on NR, BR or SBR
L’invention a l’avantage de s’intégrer dans la valorisation de matière première renouvelable non alimentaire. Elle permet la valorisation de la lignine, actuellement un déchet de l’industrie du bois et du papier. Ce composé est parfaitement inoffensif, a un coût bas, de hautes performances. Son utilisation n’entre pas en compétition avec le marché alimentaire, il n’est pas soumis à la réglementation sur les produits chimiques. Il s’agit d’une agro-ressource. The invention has the advantage of being integrated into the recovery of renewable non-food raw materials. It enables the recovery of lignin, currently a waste from the wood and paper industry. This compound is perfectly harmless, has a low cost, high performance. Its use does not compete with the food market, it is not subject to regulations on chemicals. This is an agro-resource.
L’invention va maintenant être décrite plus en détail à l’aide de modes de réalisation pris à titre d’exemples non limitatifs. The invention will now be described in more detail with the aid of embodiments taken by way of non-limiting examples.
Partie I Préparation de formule comprenant un sel de lignosulfonate et un durcisseur époxy (exemple bi-composant). Part I Preparation of formula comprising a lignosulfonate salt and an epoxy hardener (two-component example).
Le phénomène de réticulation ou « cuisson » d’un matériau thermodurcissable, c’est-à-dire la formation d’un réseau tri-dimensionnel covalent aboutissant à un produit de réaction, est accompagné d’un dégagement de chaleur. Ainsi, le calorimètre différentiel à balayage (DSC) est classiquement utilisé pour caractériser la réticulation d'un matériau thermodurcissable. Ceci est accompli en soumettant un matériau thermodurcissable non cuit à une rampe de température contrôlée suivi de l'analyse de la localisation, la taille et forme du pic d’exothermie résultant. The phenomenon of crosslinking or "baking" of a thermosetting material, that is to say the formation of a three-dimensional covalent network resulting in a reaction product, is accompanied by the release of heat. Thus, the differential scanning calorimeter (DSC) is conventionally used to characterize the crosslinking of a thermosetting material. This is accomplished by subjecting an unbaked thermosetting material to a controlled temperature ramp followed by analysis of the location, size and shape of the resulting exothermic peak.
Quelques grammes de la lignosulfonate de sodium (Arbo N18 ; Tembec N18) et un durcisseur époxy (1 ,4 butanediol diglycidyl éther) sont homogénéisé pendant 2 minutes dans une coupelle d’aluminium sous hotte à température ambiante. Le ratio massique sel de lignosulfonate / durcisseur époxy est précisément de 1 . Ensuite quelques milligrammes de cette composition sont scellés dans un creuset d’aluminium de diamètre de 43 mm et une profondeur de 12 mm. L’échantillon est ensuite placé dans un équipement DSC 3+
STARe SYSTEM de METTLER TOLEDO et soumis à une rampe en température de 25 à 300°C, à 10°C par minute, sous flux d’azote à 80 ml par minute. La variation totale d'enthalpie que subit l'échantillon est enregistrée en intégrant la surface sous le pic exothermique à l’aide du logiciel STAR SW 14.00, puis normalisée en J. g-1. La température de cuisson en °C, où la cinétique de réticulation est la plus forte, est mesurée au pic maximum (peakmax) du pic d’exothermie avec une précision de +/- 1°C. A few grams of sodium lignosulfonate (Arbo N18; Tembec N18) and an epoxy hardener (1, 4 butanediol diglycidyl ether) are homogenized for 2 minutes in an aluminum dish under a hood at room temperature. The lignosulfonate salt / epoxy hardener mass ratio is precisely 1. Then a few milligrams of this composition are sealed in an aluminum crucible with a diameter of 43 mm and a depth of 12 mm. The sample is then placed in DSC 3+ equipment STAR e SYSTEM from METTLER TOLEDO and subjected to a temperature ramp from 25 to 300 ° C, at 10 ° C per minute, under a flow of nitrogen at 80 ml per minute. The total enthalpy variation to which the sample is subjected is recorded by integrating the surface under the exothermic peak using the STAR SW 14.00 software, then normalized in J. g -1 . The firing temperature in ° C, where the crosslinking kinetics are the strongest, is measured at the maximum peak (peakmax) of the exothermic peak with an accuracy of +/- 1 ° C.
Le même procédé est appliqué pour produire d’autres composition contenant du 2,2-bis(4-hydroxyphényl) propane diglycidyl éther ; diglycidyl 1 ,2- cyclohexanedicarboxylate ; 3,4-époxycyclohexylméthyl 3,4 époxycyclohexanecarboxylate ; 1 ,6 hexanediol diglycidyl éther ; glycérol diglycidyl éther ; glycérol triglycidyl éther ; mélange de glycérol diglycidyl éther et glycérol triglycidyl éther commercialisé par la Société Raschig sous la référence GE100; résine époxyde de type novolaque comercialisés par la SociétéThe same process is applied to produce other compositions containing 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether; diglycidyl 1, 2-cyclohexanedicarboxylate; 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; 1, 6 hexanediol diglycidyl ether; glycerol diglycidyl ether; glycerol triglycidyl ether; mixture of glycerol diglycidyl ether and glycerol triglycidyl ether sold by the company Raschig under the reference GE100; novolac type epoxy resin marketed by the Company
HUNTSMAN sous la référence Araldite® PZ 323. HUNTSMAN under the reference Araldite ® PZ 323.
Le même procédé est appliqué pour produire d’autres échantillons contenants uniquement de la lignosulfonate de sodium. The same process is applied to produce other samples containing only sodium lignosulfonate.
Le même procédé est appliqué pour produire d’autres échantillons contenants uniquement le durcisseur époxy. The same process is applied to produce other samples containing only the epoxy hardener.
[Table 1]
[Table 1]
La variation d’énergie exothermique mesurée pour l’échantillon témoin contenant uniquement de la lignosulfonate est normalisé à 100%. The change in exothermic energy measured for the control sample containing only lignosulfonate is normalized to 100%.
Les compositions contenant uniquement un durcisseur époxy (ratio massique sel de lignosulfonate / durcisseur de 0) présentent des variations d’exothermie nul ou faible, entre 0 et 33 % par rapport au témoin sel de lignosulfonate. The compositions containing only an epoxy hardener (lignosulphonate salt / hardener mass ratio of 0) exhibit zero or low exothermic variations, between 0 and 33% relative to the lignosulphonate salt control.
Les compositions contenant de la lignosulfonate de sodium et un durcisseur époxy (ratio massique sel de lignosulfonate / durcisseur de 1 ) présentent des variations d’énergies exothermiques comprises entre 595 et 1199 % par rapport au témoin sel de lignosulfonate. Cette forte variation d’exothermie par rapport au témoin est caractéristique du phénomène de réticulation ou « cuisson » d’un matériau thermodurcissable. Le rôle du durcisseur époxy sur la lignosulfonate est ici clairement apparent. The compositions containing sodium lignosulphonate and an epoxy hardener (lignosulphonate salt / hardener mass ratio of 1) exhibit exothermic energy variations of between 595 and 1199% relative to the lignosulphonate salt control. This strong variation in exothermic relative to the control is characteristic of the phenomenon of crosslinking or "baking" of a thermosetting material. The role of the epoxy hardener on the lignosulfonate is clearly apparent here.
Exemples II : Partie Exemples de préparation de formule adhésive Examples II: Part Examples of preparation of adhesive formula
Les définitions et méthodes de mesure ou de contrôle décrites dans cette partie s’appliquent de manière générale à la demande, sauf indication contraire. The definitions and methods of measurement or control described in this part are generally applicable on request, unless otherwise indicated.
L’extrait sec (ou concentration massique) des préparations est défini comme étant le pourcentage de matière sèche résiduelle après évaporation des matières volatiles (eau, solvant) selon un mode de séchage défini. L’analyse est réalisée à l’aide d’une balance dessicatrice, sur un échantillon humide prélevé de masse me h= entre 2 et 5 grammes. L’échantillon est déposé dans une coupelle en aluminium préalablement tarée contenant un filtre en fibre de verre sans liant, de densité surfacique 52 g.nr2 et de seuil 1 ,6 pm.The dry extract (or mass concentration) of the preparations is defined as being the percentage of residual dry matter after evaporation of the volatile materials (water, solvent) according to a defined drying method. The analysis is carried out using a desiccator balance, on a wet sample taken with a mass m e h = between 2 and 5 grams. The sample is placed in a pre-tared aluminum cup containing a fiberglass filter without binder, with a surface density of 52 g.nr 2 and threshold 1, 6 μm.
L’ensemble est ensuite soumis à une température de 120 °C jusqu’à stabilisation totale de la masse. Le résultat est exprimé en %. The whole is then subjected to a temperature of 120 ° C until total stabilization of the mass. The result is expressed in%.
La viscosité de la préparation est mesurée à 23°C à l’aide d’un viscosimètre Brookfield. Sauf mention contraire, la mesure est réalisée à l’aide d’un module ULA (Ultra Low Viscosity Adaptator) et d’un mobile n°1 (système basse viscosité) à une vitesse de 60 rpm (révolutions par minute). The viscosity of the preparation is measured at 23 ° C using a Brookfield viscometer. Unless otherwise specified, the measurement is carried out using a ULA (Ultra Low Viscosity Adaptator) module and a mobile n ° 1 (low viscosity system) at a speed of 60 rpm (revolutions per minute).
Le pH des préparations aqueuses est mesuré à l’aide d’un pH-mètre METLER 340, étalonné pour des mesures en milieu basique à l’aide de solutions tampons. Une électrode de verre et un électrolyte KCI 3M sont utilisés. The pH of aqueous preparations is measured using a METLER 340 pH meter, calibrated for measurements in a basic medium using buffer solutions. A glass electrode and 3M KCI electrolyte are used.
Sauf mention contraire, l’eau utilisée pour la réalisation des préparations est de l’eau de qualité osmosée, de conductivité résiduelle inférieure à 70pS/cm.
Exemple C.II-1 : Préparation d’un adhésif à base de lignosulfonate de sodium et d’un durcisseur époxy Unless otherwise stated, the water used for the preparation of the preparations is water of reverse osmosis quality, with a residual conductivity of less than 70 pS / cm. Example C.II-1: Preparation of an adhesive based on sodium lignosulfonate and an epoxy hardener
Dans un premier mode de réalisation de l’invention, 64,2g de lignosulfonate de sodium (Arbo N18 ; Tembec) sont dissouts sous agitation dans 1184g d’eau. 2,5g d’une solution de soude à 10% massique sont ensuite ajoutés à la solution, qui est maintenue 10 minutes sous agitation pour permettre une solubilisation totale. Cette solution est ajoutée sous agitation à 983g d’un latex de copolymère styrène-butadiène-vinylpyridine (VPSBR). L’ensemble est maintenu sous agitation (150 rpm) durant la phase de préparation du durcisseur. In a first embodiment of the invention, 64.2g of sodium lignosulfonate (Arbo N18; Tembec) are dissolved with stirring in 1184g of water. 2.5 g of a 10% by mass sodium hydroxide solution are then added to the solution, which is kept stirring for 10 minutes to allow complete solubilization. This solution is added with stirring to 983 g of a styrene-butadiene-vinylpyridine copolymer latex (VPSBR). The whole is kept under agitation (150 rpm) during the hardener preparation phase.
35g de GE100 sont mis sous vive agitation (300rpm) avec 230 grammes d’eau. Cette solution est ajoutée à la préparation de lignosulfonate et de latex. L’agitation est maintenue quelques minutes jusqu’à homogénéisation totale. 35g of GE100 are stirred vigorously (300rpm) with 230 grams of water. This solution is added to the preparation of lignosulfonate and latex. Stirring is maintained for a few minutes until complete homogenization.
La préparation présente un pH de 10,8 un extrait sec de 19,43% et une viscosité de 2,45 mPa.s. The preparation has a pH of 10.8, a dry extract of 19.43% and a viscosity of 2.45 mPa.s.
Le même procédé a été appliqué pour produire 2 autres compositions en faisant varier les paramètres suivants : The same process was applied to produce 2 other compositions by varying the following parameters:
Ratio massique durcisseur / sel de lignosulfonate : de 56% à 116 % Hardener / lignosulfonate salt mass ratio: from 56% to 116%
Ratio massique [sel de lignosulfonate + durcisseur] / latex : de 18% à 21% Mass ratio [lignosulfonate salt + hardener] / latex: from 18% to 21%
% massique de latex sec dans la composition : de 80 à 84%. % by mass of dry latex in the composition: from 80 to 84%.
Au total, 3 compositions ont été réalisées. In total, 3 compositions were produced.
Exemple C.II-2 : Deuxième mode de préparation d’un adhésif de lignosulfonate de sodium et un durcisseur époxy Example C.II-2: Second method of preparing a sodium lignosulfonate adhesive and an epoxy hardener
Dans un deuxième mode de réalisation de l’invention, 34,8g de lignosulfonate de sodium sont introduits dans un récipient et 782g d’eau sont ajoutés progressivement. La solution est mise sous agitation à 200rpm. 20g d’une solution de soude à 10% massique et 100,7g d’ammoniaque à 20% massique sont ensuite successivement ajoutés sous agitation à la préparation. Le mélange est agité à 200rpm durant 10 minutes. In a second embodiment of the invention, 34.8g of sodium lignosulfonate are introduced into a container and 782g of water are added gradually. The solution is stirred at 200rpm. 20g of a 10% by mass sodium hydroxide solution and 100.7g of 20% by mass ammonia are then successively added with stirring to the preparation. The mixture is stirred at 200rpm for 10 minutes.
La solution basique de lignosulfonate de sodium est ajoutée sous agitation à une préparation de latex d’un copolymère styrène-butadiène (latex humide SBR; 946g) et à 157g d’eau préalablement homogénéisée. The basic sodium lignosulfonate solution is added with stirring to a latex preparation of a styrene-butadiene copolymer (SBR wet latex; 946g) and to 157g of previously homogenized water.
75,5g de GE100 sont mis sous vive agitation (300rpm) et 383,75 grammes d’eau y sont ajoutés. Cette émulsion est immédiatement ajoutée sous agitation à la préparation de lignosulfonate et de latex. L’agitation est maintenue quelques minutes jusqu’à homogénéisation totale.
La préparation présente un pH de 12,2, un extrait sec de 19,9% et une viscosité de 2,7 mPa.s. 75.5g of GE100 are stirred vigorously (300rpm) and 383.75 grams of water are added thereto. This emulsion is immediately added with stirring to the preparation of lignosulfonate and latex. Stirring is maintained for a few minutes until complete homogenization. The preparation has a pH of 12.2, a dry extract of 19.9% and a viscosity of 2.7 mPa.s.
Le même procédé a été appliqué pour produire une autre composition en faisant varier les paramètres suivants : The same process was applied to produce another composition by varying the following parameters:
Ratio massique durcisseur / sel de lignosulfonate : de 217% à 218%. Hardener / lignosulfonate salt mass ratio: from 217% to 218%.
Ratio massique [sel de lignosulfonate + durcisseur] / latex : de 21% à 29%. Mass ratio [lignosulfonate salt + hardener] / latex: from 21% to 29%.
% massique de latex sec dans la composition : de 78% à 82%. % by mass of dry latex in the composition: from 78% to 82%.
Au total, 2 compositions ont été réalisées. In total, 2 compositions were produced.
Exemple C.II-3 : Troisième mode de préparation d’un adhésif à base de lignosulfonate de sodium et d’un durcisseur époxy Example C.II-3: Third method of preparing an adhesive based on sodium lignosulfonate and an epoxy hardener
Dans un troisième mode de préparation de l’invention, une solution basique de lignosulfonate de sodium est préparée par dissolution sous agitation de 19g de lignosulfonate de sodium dans 955g d’eau et ajout de 19g d’une solution de soude à 10% massique. La préparation est laissée sous agitation à 200rpm durant 10 minutes afin de permettre une solubilisation totale. In a third method of preparation of the invention, a basic solution of sodium lignosulfonate is prepared by dissolving 19 g of sodium lignosulfonate in 955 g of water and stirring with stirring and adding 19 g of a sodium hydroxide solution at 10% by mass. The preparation is left under stirring at 200rpm for 10 minutes in order to allow total solubilization.
Une dispersion basique de latex est préparée en introduisant 167g d’eau dans un récipient, qui est ensuite mis sous agitation à 200rpm. 1049g d’un latex de copolymère styrène-butadiène (SBR), puis 25g d’une solution d’ammoniac à 20% massique sont ensuite introduits successivement. La solution basique de lignosulfonate est ensuite ajoutée sous agitation à la dispersion de latex. A basic latex dispersion is prepared by introducing 167g of water into a container, which is then stirred at 200rpm. 1049g of a styrene-butadiene copolymer latex (SBR), then 25g of an ammonia solution at 20% by mass are then introduced successively. The basic lignosulfonate solution is then added with stirring to the latex dispersion.
49g de GE100 sont mis sous vive agitation (300rpm) et 216 grammes d’eau y sont ajoutés. Cette solution est immédiatement ajoutée sous agitation à la préparation de lignosulfonate et de latex. L’agitation est maintenue quelques minutes jusqu’à homogénéisation totale. 49g of GE100 are stirred vigorously (300rpm) and 216 grams of water are added. This solution is immediately added with stirring to the preparation of lignosulphonate and latex. Stirring is maintained for a few minutes until complete homogenization.
La préparation présente un pH de 12,25 un extrait sec de 18,33% et une viscosité de 2,25 mPa.s. The preparation has a pH of 12.25, a dry extract of 18.33% and a viscosity of 2.25 mPa.s.
Le même procédé a été appliqué pour produire 2 autres compositions en faisant varier les paramètres suivants : The same process was applied to produce 2 other compositions by varying the following parameters:
Ratio massique durcisseur / sel de lignosulfonate : de 255% à 516% Hardener / lignosulfonate salt mass ratio: from 255% to 516%
Ratio massique [sel de lignosulfonate + durcisseur] / latex : de 16% à 46% Mass ratio [lignosulfonate salt + hardener] / latex: from 16% to 46%
% massique de latex sec dans la composition : de 68% à 86%. % by mass of dry latex in the composition: from 68% to 86%.
Au total, 3 compositions ont été réalisées.
Exemple C.II-4 : Quatrième mode de préparation d’un adhésif à base de lignosulfonate de potassium et d’un durcisseur époxy. In total, 3 compositions were produced. Example C.II-4: Fourth method of preparing an adhesive based on potassium lignosulfonate and an epoxy hardener.
Dans ce mode de préparation, 94,5g d’une solution aqueuse de lignosulfonate de potassium et 63,7g de GE100 sont mélangés. 1794,8g d’eau sont ensuite versés sur le mélange sous vive agitation. 33g d’une solution de soude à 10% massique et 166,6g d’une solution d’ammoniac à 20% massique sont ensuite successivement ajoutés à la préparation sous agitation. Le mélange est laissé sous agitation durant 10 minutes, puis ajouté sous agitation à un latex de chloroprène (latex humide CR ; 1004g) dans de l’eau (176g). In this method of preparation, 94.5g of an aqueous solution of potassium lignosulfonate and 63.7g of GE100 are mixed. 1794.8g of water are then poured over the mixture with vigorous stirring. 33g of a 10% by mass sodium hydroxide solution and 166.6g of a 20% by mass ammonia solution are then successively added to the preparation with stirring. The mixture is left under stirring for 10 minutes, then added with stirring to a chloroprene latex (wet latex CR; 1004g) in water (176g).
La préparation présente un pH de 12,69, un extrait sec de 19,58% et une viscosité de 2,45 mPa.s. The preparation has a pH of 12.69, a solids content of 19.58% and a viscosity of 2.45 mPa.s.
Le même procédé a été appliqué pour produire 2 autres compositions en faisant varier les paramètres suivants : The same process was applied to produce 2 other compositions by varying the following parameters:
Ratio massique durcisseur / sel de lignosulfonate : de 33% à 134% Hardener / lignosulfonate salt mass ratio: 33% to 134%
Ratio massique [sel de lignosulfonate + durcisseur / latex] : de 20% à 47% Mass ratio [lignosulfonate salt + hardener / latex]: from 20% to 47%
% massique de latex sec dans la composition : de 65% à 79%. % by mass of dry latex in the composition: from 65% to 79%.
Au total, 3 compositions ont été réalisées. In total, 3 compositions were produced.
Exemple C.II-5 : Cinquième mode de préparation d’un adhésif à base de lignosulfonate de potassium et d’un durcisseur époxy Example C.II-5: Fifth method of preparing an adhesive based on potassium lignosulfonate and an epoxy hardener
Dans ce mode de préparation, 94,5g d’une solution aqueuse de lignosulfonate de potassium et 63,7g de GE100 sont mélangés. 1794,8g d’eau sont ensuite versés sur le mélange sous vive agitation. 33g d’une solution de soude à 10% massique et 166,6g d’une solution d’ammoniac à 20% massique sont ensuite successivement ajoutés à la préparation sous agitation. Le mélange est laissé sous agitation durant 10 minutes, puis ajouté sous agitation à une dispersion de latex de chloroprène (latex humide CR ; 1004g) dans de l’eau (176g). In this method of preparation, 94.5g of an aqueous solution of potassium lignosulfonate and 63.7g of GE100 are mixed. 1794.8g of water are then poured over the mixture with vigorous stirring. 33g of a 10% by mass sodium hydroxide solution and 166.6g of a 20% by mass ammonia solution are then successively added to the preparation with stirring. The mixture is left under stirring for 10 minutes, then added with stirring to a dispersion of chloroprene latex (wet latex CR; 1004g) in water (176g).
1306g de cette préparation sont prélevés et dilués sous agitation dans 996g d’eau. 36g d’une dispersion aqueuse d’oxyde de zinc à 55% massique, 78g d’une dispersion aqueuse de noir de carbone à 35% massique et 83g d’un promoteur d’adhérence (isocyanate bloqué) sont ensuite successivement ajoutés sous agitation moyenne. 1306g of this preparation are taken and diluted with stirring in 996g of water. 36g of an aqueous dispersion of zinc oxide at 55% by mass, 78g of an aqueous dispersion of carbon black at 35% by mass and 83g of an adhesion promoter (blocked isocyanate) are then successively added with moderate stirring .
La préparation présente un pH de 12,32 un extrait sec de 14,1% et une viscosité de 1 ,95 mPa.s. The preparation has a pH of 12.32, a solids content of 14.1% and a viscosity of 1.95 mPa.s.
Le même procédé a été appliqué pour produire 2 autres compositions en faisant varier les paramètres suivants : The same process was applied to produce 2 other compositions by varying the following parameters:
Ratio massique durcisseur / sel de lignosulfonate : de 33% à 135% Hardener / lignosulfonate salt mass ratio: 33% to 135%
Ratio massique [sel de lignosulfonate + durcisseur] / latex : de 20% à 47%
% massique de latex sec dans la composition : de 48% à 59% Mass ratio [lignosulfonate salt + hardener] / latex: from 20% to 47% % by mass of dry latex in the composition: from 48% to 59%
Au total, 3 compositions ont été réalisées. In total, 3 compositions were produced.
Les compositions de ces exemples sont utilisées dans la partie traitement du textile de renfort. The compositions of these examples are used in the treatment part of the reinforcing textile.
Partie III- Traitement du textile de renfort Part III- Treatment of the reinforcing textile
Les définitions et méthodes de mesure ou de contrôle décrites dans cette partie s’appliquent de manière générale à la demande, sauf indication contraire. Les caractéristiques mécaniques des textiles traités, telles que résistance à la rupture en traction (« tensile strengh »), allongement à la rupture en traction (« élongation at break »), retrait (« shrinkage »), retrait en température, embuvage (« contraction »), force de contraction en température (« shrinkage force »), masse linéique (« linear weight »), taux d’emport (« Dip pick-up » ; DPU), raideur (« stiffness »), etc., sont mesurées selon les normes en vigueur dans l’industrie textile. Dans le cadre de la présente invention, il a été vérifié que les nouveaux traitements n’entraînaient pas de modification de ces propriétés, par rapport au RFL standard. The definitions and methods of measurement or control described in this part are generally applicable on request, unless otherwise indicated. The mechanical characteristics of the treated textiles, such as tensile strength at break ("tensile strengh"), tensile elongation at break ("elongation at break"), shrinkage, temperature shrinkage, steaming (" contraction "), temperature contraction force (" shrinkage force "), linear mass (" linear weight "), load rate (" Dip pick-up "; DPU), stiffness, etc., are measured according to the standards in force in the textile industry. In the context of the present invention, it has been verified that the new treatments do not lead to any modification of these properties, compared to the standard RFL.
Les préparations adhésives de l’invention font l’objet d’une évaluation de leurs performances d’adhésion. Après enduction du textile, celui-ci est déposé au sein d’une matrice de caoutchouc non-vulcanisée, de façon que la surface du textile en contact avec le caoutchouc reste vierge de toute pollution. La matrice contenant le textile est ensuite vulcanisée par compression, selon des conditions de température, de temps et de pression propres à chaque caoutchouc. L’ensemble textile + matrice vulcanisée forme une éprouvette d’adhésion. The adhesive preparations of the invention are evaluated for their adhesion performance. After coating the textile, it is deposited in an unvulcanized rubber matrix, so that the surface of the textile in contact with the rubber remains free of any pollution. The matrix containing the textile is then vulcanized by compression, according to temperature, time and pressure conditions specific to each rubber. The textile + vulcanized matrix assembly forms an adhesion test tube.
Les éprouvettes d’adhésion peuvent prendre plusieurs formes, décrites dans différentes normes internationales, comme par exemple la norme ISO 36:2017. Les éprouvettes, et par extension l’essai réalisé pour déterminer l’adhésion, sont couramment connues par l’homme du métier sous des noms tels que Test-T (« pull-out test », ASTM D2229-04), Test-H (selon la norme NF ISO 4647 ou ASTM D4776-04), pelage (peel-test), etc. Le test est ensuite réalisé par sollicitation de l’éprouvette jusqu’à destruction de la zone de contact interfaciale, de l’arrachement du textile, ou du déchirement de la matrice caoutchouc. L’adhésion est alors évaluée selon des critères tels que l’aspect du textile à la rupture, la force maximale d’adhésion, la force moyenne d’arrachement, éventuellement ramenées à l’épaisseur de l’éprouvette. Adhesion specimens can take several forms, described in various international standards, such as ISO 36: 2017. The test pieces, and by extension the test carried out to determine the adhesion, are commonly known to those skilled in the art under names such as Test-T (“pull-out test”, ASTM D2229-04), Test-H (according to standard NF ISO 4647 or ASTM D4776-04), peeling (peel-test), etc. The test is then carried out by stressing the specimen until destruction of the interfacial contact zone, tearing of the textile, or tearing of the rubber matrix. The adhesion is then evaluated according to criteria such as the appearance of the textile at break, the maximum adhesion force, the average tear-off force, possibly reduced to the thickness of the test piece.
Généralités sur les procédés d’imprégnation
D’une manière générale, le procédé d’imprégnation des textiles est réalisé par trempage (« dipping ») dans des bacs contenant les préparations adhésives. Un schéma d’un tel procédé est illustré dans Gomes A., Nabih N., Kramer T, Adhesion activation of tire textiles by resorcinol formaldéhyde free coatings, Rubber World, Mars 2016. General information on impregnation processes In general, the textile impregnation process is carried out by soaking (“dipping”) in trays containing the adhesive preparations. A diagram of such a process is illustrated in Gomes A., Nabih N., Kramer T, Adhesion activation of tire textiles by resorcinol formaldehyde free coatings, Rubber World, March 2016.
La ou les bobines de fils, cordes et câblés non traités, peuvent être positionnées sur un cantre en entrée de ligne. Un système accumulateur peut éventuellement être utilisé. Les fils, cordes et câbles peuvent subir soit un trempage direct dans un bac, soit une imprégnation par un rouleau lécheur, pour l’application de la composition d’adhérisation. Après trempage ou imprégnation, l’excès de préparation humide est de préférence éliminé par exemple par pressage (foulardage), aspiration ou par des mousses The coil (s) of untreated wires, cords and cables can be positioned on a creel at the line entry. An accumulator system can optionally be used. The wires, ropes and cables can be either directly dipped in a tub or impregnated by a lick roller, for the application of the adhesion composition. After soaking or impregnation, the excess of wet preparation is preferably removed, for example by pressing (padding), suction or by foams
On procède ensuite au séchage et/ou la réticulation de la composition d’adhérisation. Le textile imprégné enduit peut ainsi subir un passage dans un four pour permettre le séchage et la réticulation de la composition d’adhérisation. Après sortie d’un four, le textile peut à nouveau subir une étape d’imprégnation, puis de passage dans un four, ces étapes pouvant être répétées, notamment jusqu’à un total de 4 imprégnations (2, 3 ou 4). En sortie de ligne, les fils, cordes ou câblés peuvent être réceptionnés sur des bobinoirs. Drying and / or crosslinking of the adhesion composition is then carried out. The coated impregnated textile can thus be passed through an oven to allow drying and crosslinking of the adhesion composition. After removal from an oven, the textile can again undergo an impregnation step, then passage through an oven, these steps being able to be repeated, in particular up to a total of 4 impregnations (2, 3 or 4). At the output of the line, the wires, cords or cables can be received on winders.
Dans un autre mode d’imprégnation, particulièrement adapté aux fibres minérales (verre, basalte, carbone...), un système de dérompage composé de peigne et/ou de « queues de cochons » peut être utilisé en sortie de cantre. Il permet une ouverture maximale du fil multifilamentaire, pour favoriser une forte imprégnation. Après les étapes d’imprégnation et de séchage et/ou réticulation, le fil est alors retordu en ligne. Le câblage est effectué de préférence sur un fil déjà traité. Des traitements additionnels peuvent être effectués sur les câblés ainsi formés. In another method of impregnation, particularly suitable for mineral fibers (glass, basalt, carbon, etc.), a derivation system made up of a comb and / or "pig tails" can be used at the creel outlet. It allows maximum opening of the multifilament yarn, to promote strong impregnation. After the impregnation and drying and / or crosslinking steps, the yarn is then twisted in line. The wiring is preferably carried out on an already treated wire. Additional treatments can be carried out on the cords thus formed.
Dans les différents procédés, les vitesses peuvent aller de 1 m/min à 150m/min, les températures des fours de 30°C à 350°C, plus spécifiquement de 100 à 300°C, et encore plus spécifiquement de 140 à 220°C. Une tension mécanique peut également être appliquée sur le textile. Sauf mention contraire, dans les exemples suivants, les textiles ont été traités avec les compositions d’adhérisation objet de l’invention dans des conditions identiques à celles appliquées lors d’un traitement avec un RFL. In the different processes, the speeds can range from 1 m / min to 150 m / min, the temperatures of the furnaces from 30 ° C to 350 ° C, more specifically from 100 to 300 ° C, and even more specifically from 140 to 220 ° vs. Mechanical tension can also be applied to the textile. Unless otherwise indicated, in the following examples, the textiles were treated with the adhesion compositions object of the invention under conditions identical to those applied during a treatment with an RFL.
Exemple III-1 : Renfort polyamide 4-6 traité pour courroies. Example III-1: Polyamide 4-6 reinforcement treated for belts.
Dans un exemple de préparation de l’invention, les inventeurs se sont attachés à présenter une solution pouvant être utilisée en tant que renfort dans des assemblages tels que courroies de transmission ou bandes transporteuses.
Pour cela, un câblé en PA 4-6 de construction 470/5x3 dtex (100/125) a été construit par étapes successives de retordage, puis de câblage. Le câblé obtenu a été traité par une première imprégnation dans une solution de méthylène diphényl diisocyanate dans du toluène, puis soumis à séchage et thermofixation dans un four. Le câblé a ensuite été imprégné dans un bac contenant la composition d’adhérisation (l’adhésif) de l’invention, à une concentration massique en matière sèche de 20%, en lieu et place du traitement RFL habituellement appliqué. Les différents fils imprégnés des différents adhésifs obtenus ont été évalués en adhésion sur un mélange à base d’EPDM (éthylène-propylène-diène monomère) accéléré au peroxyde. Les éprouvettes ont été réalisées par un moulage en compression. Un fil imprégné de RFL, réalisé dans les mêmes conditions, a permis d’obtenir les valeurs d’adhérence témoins. Les valeurs d’adhésion obtenues sont présentées dans le tableau 2, et exprimées en % d’adhésion par rapport à l’adhésion obtenue avec le fil RFL témoin. In an example of preparation of the invention, the inventors set out to present a solution which can be used as a reinforcement in assemblies such as transmission belts or conveyor belts. For this, a cable in PA 4-6 of construction 470 / 5x3 dtex (100/125) was built by successive stages of twisting, then cabling. The cord obtained was treated by a first impregnation in a solution of methylene diphenyl diisocyanate in toluene, then subjected to drying and heat setting in an oven. The cord was then impregnated in a tank containing the adhesion composition (the adhesive) of the invention, at a concentration by mass of dry matter of 20%, instead of the RFL treatment usually applied. The various threads impregnated with the various adhesives obtained were evaluated for adhesion to a mixture based on EPDM (ethylene-propylene-diene monomer) accelerated with peroxide. The test pieces were produced by compression molding. A yarn impregnated with RFL, produced under the same conditions, made it possible to obtain the control adhesion values. The adhesion values obtained are presented in Table 2, and expressed as% adhesion relative to the adhesion obtained with the control RFL yarn.
Exemple III-2 : Renfort Verre traité pour profilés. Example III-2: Reinforcement Treated glass for profiles.
Dans un exemple de préparation de l’invention, les inventeurs se sont attachés à présenter une invention pouvant être utilisée en tant que renfort dans des profilés et joints, tels que joints de fenêtre ou de porte. De tels renforts sont réalisés à partir de fil de verre contenant un ensimage avec lequel la composition adhésive doit être compatible. In an example of preparation of the invention, the inventors set out to present an invention which can be used as a reinforcement in profiles and seals, such as window or door seals. Such reinforcements are made from glass yarn containing a size with which the adhesive composition must be compatible.
Pour cela, plusieurs fils de verre E de titre 136tex ont subi un dérompage et une imprégnation dans le bac contenant la composition d’adhérisation (l’adhésif) de l’invention, en lieu et place du RFL. Dans cet exemple, des adhésifs d’une concentration massique de 20% ont été évalués. Les fils imprégnés ont été soumis à séchage et thermofixation dans un four. A la sortie du four, les fils ont subi une opération de retordage leur conférant une torsion de 135 tours/mètre en sens Z. Trois retors imprégnés sont ensuite câblés entre eux selon un sens et un niveau 135 S. Les différents fils imprégnés des différents adhésifs obtenus ont été évalués en adhésion sur un mélange caoutchouc EPDM classiquement mis-en-œuvre par extrusion. Les éprouvettes ont été réalisées par un moulage en compression. Un fil imprégné de RFL, réalisé dans les mêmes conditions, a permis d’obtenir les valeurs d’adhérence témoins. Les valeurs d’adhésion obtenues sont présentées dans le tableau 2, et exprimées en % d’adhésion par rapport à l’adhésion obtenue avec le fil RFL témoin. To do this, several E-glass yarns with a strength of 136tex underwent a derompage and an impregnation in the tank containing the adhesion composition (the adhesive) of the invention, in place of the RFL. In this example, adhesives with a mass concentration of 20% were evaluated. The impregnated yarns were subjected to drying and heat setting in an oven. On leaving the oven, the yarns have undergone a twisting operation giving them a twist of 135 turns / meter in the Z direction. Three impregnated twists are then cabled together in one direction and at a 135 S level. adhesives obtained were evaluated for adhesion on an EPDM rubber mixture conventionally implemented by extrusion. The test pieces were produced by compression molding. A yarn impregnated with RFL, carried out under the same conditions, made it possible to obtain the control adhesion values. The adhesion values obtained are presented in Table 2, and expressed as% adhesion relative to the adhesion obtained with the control RFL yarn.
Exemple IM-3 : Renfort polvéthylène-téréphtalate traité pour tuyaux.
Dans un autre exemple de préparation de l’invention, les inventeurs se sont attachés à présenter une solution pouvant être utilisée en tant que renfort, tressé, spiralé, guipé ou tricoté dans un tuyau de frein. Example IM-3: Treated polyethylene terephthalate reinforcement for pipes. In another example of preparation of the invention, the inventors set out to present a solution which can be used as a reinforcement, braided, spiral, wrapped or knitted in a brake pipe.
Exemple 111-3 (a) : Pour cela, une torsion 90 Z a été appliquée à un fil de polyéthylène-téréphtalate (PET) de titre 1100 dtex. Le fil obtenu a été traité par une imprégnation dans la composition d’adhérisation (l’adhésif) objet de l’invention, puis par une thermofixation dans un four. Les adhésifs utilisés dans cet exemple ont une concentration en matières sèche de 20%. Les différents fils imprégnés de l’adhésif ont été évalués en adhésion sur un mélange caoutchouc EPDM accéléré au peroxyde classiquement utilisé dans les tuyaux de frein. Les éprouvettes ont été réalisées par un moulage en compression. Un fil imprégné de RFL, réalisé dans les mêmes conditions, a permis d’obtenir les valeurs d’adhérence témoins. Les valeurs obtenues sont présentées dans le tableau 2, et exprimé en % d’adhésion par rapport à l’adhésion obtenue avec le fil RFL témoin. Exemple 111-3 (b) : Dans un autre exemple, un câblé de construction 830/2x3 dtex a été construit par étapes successives de retordage, puis câblage. Le câblé obtenu a été traité par une première imprégnation dans une solution de méthylène diphényl diisocyanate dans du toluène, puis soumis à séchage et thermofixation dans un four. Les compositions d’adhérisation (adhésifs) utilisés dans cet exemple ont une concentration en matières sèche de 20%. Les différents fils imprégnés de l’adhésif ont été évalués en adhésion sur un mélanges caoutchouc à base de CR. Les éprouvettes ont été réalisées par un moulage en compression. Un fil imprégné de RFL, réalisé dans les mêmes conditions, a permis d’obtenir les valeurs d’adhérence témoins. Les valeurs obtenues sont présentées dans le tableau 2, et exprimé en % d’adhésion par rapport à l’adhésion obtenue avec le fil RFL témoin. Example 111-3 (a): For this, a 90 Z twist was applied to a polyethylene terephthalate (PET) yarn with a titre of 1100 dtex. The yarn obtained was treated by an impregnation in the adhesion composition (the adhesive) object of the invention, then by heat setting in an oven. The adhesives used in this example have a solids concentration of 20%. The different threads impregnated with the adhesive were evaluated for adhesion to an EPDM rubber compound accelerated with peroxide conventionally used in brake pipes. The test pieces were produced by compression molding. A yarn impregnated with RFL, carried out under the same conditions, made it possible to obtain the control adhesion values. The values obtained are presented in Table 2, and expressed as% adhesion relative to the adhesion obtained with the control RFL yarn. Example 111-3 (b): In another example, a cord of construction 830 / 2x3 dtex was constructed by successive stages of twisting, then cabling. The cord obtained was treated by a first impregnation in a solution of methylene diphenyl diisocyanate in toluene, then subjected to drying and heat setting in an oven. The adhesion compositions (adhesives) used in this example have a solids concentration of 20%. The different threads impregnated with the adhesive were evaluated for adhesion on a rubber mixes based on CR. The test pieces were produced by compression molding. A yarn impregnated with RFL, produced under the same conditions, obtained the control adhesion values. The values obtained are presented in Table 2, and expressed as% adhesion relative to the adhesion obtained with the control RFL yarn.
[Table 2]
[Table 2]
Le câblé de Polyamide 4-6 de l’exemple II 1-1 traité avec les différents adhésifs de l’exemple C.11-1 a montré des niveaux d’adhésions satisfaisant vis-à-vis de l’EPDM en comparaison du fil témoin imprégné RFL. Les niveaux d’adhésion obtenus, ainsi que l’observation des faciès de rupture montrent que les adhésifs évalués sont compatibles avec la première imprégnation appliquée au textile. The Polyamide 4-6 cord of Example II 1-1 treated with the different adhesives of Example C.11-1 showed satisfactory levels of adhesions with respect to EPDM compared to the yarn. RFL impregnated witness. The adhesion levels obtained, as well as the observation of the fracture patterns show that the adhesives evaluated are compatible with the first impregnation applied to the textile.
Le câblé de verre E de l’exemple III-2 traité avec les différents adhésifs de l’exemples C.II-2 a montré des niveaux d’adhésion satisfaisants vis-à-vis de l’EPDM en comparaison du fil témoin imprégné RFL. Bien que ceux-ci soient inférieurs à ceux obtenus avec le RFL, ils sont suffisamment élevés pour garantir les performances de l’application. Les niveaux d’adhésion obtenus, ainsi que l’observation des faciès de rupture montrent que les adhésifs évalués sont compatibles avec l’ensimage du verre. En outre, les fils de verre ainsi traités n’ont montré aucun endommagement visuel, ni provoqué d’encrassement excessif sur les lignes de traitement. Cela montre la capacité des adhésifs évalués à conférer des propriétés identiques au RFL, y compris des propriétés de protection mécanique. The glass cord E of Example III-2 treated with the different adhesives of Examples C.II-2 showed satisfactory levels of adhesion to EPDM compared to the RFL impregnated control yarn. . Although these are lower than those obtained with RFL, they are high enough to guarantee the performance of the application. The adhesion levels obtained, as well as the observation of the fracture patterns show that the adhesives evaluated are compatible with the sizing of the glass. In addition, the glass strands thus treated showed no visual damage or caused excessive fouling on the processing lines. This shows the ability of the adhesives evaluated to impart identical properties to RFL, including mechanical protection properties.
Le fil PET de l’exemple III-3 (a), traité avec les différents adhésifs de chacun de l’exemple C. II-3 a montré des niveaux d’adhésion vis-à-vis de l’EPDM supérieur par rapport
au fil témoin imprégné RFL. Le fil PET de l’exemple 111-3 (b), traité avec les différents adhésifs de chacun de l’exemple C. 11-4 a montré des niveaux d’adhésion satisfaisant vis- à-vis du mélange CR par rapport au fil témoin imprégné RFL. The PET yarn of Example III-3 (a), treated with the different adhesives of each of Example C. II-3 showed higher levels of adhesion to EPDM compared to the RFL impregnated control wire. The PET yarn of Example 111-3 (b), treated with the different adhesives of each of Example C. 11-4 showed satisfactory levels of adhesion with respect to the CR mixture with respect to the yarn. RFL impregnated witness.
En conclusion, les résultats de ces différents essais démontrent clairement que les compositions adhésives selon l’invention constituent une alternative fort intéressante à l’emploi des solutions d’adhérisation RFL conventionnelles contenant du formaldéhyde et du résorcinol.
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 adhesion solutions containing formaldehyde and resorcinol.
Claims
1. Composition d’adhérisation pour textile, comprenant un sel de lignosulfonate, un durcisseur époxy de ce sel, comprenant au moins deux motifs époxydes, et un latex d’élastomère. 1. An adhesion composition for textiles, comprising a salt of lignosulfonate, an epoxy hardener thereof, comprising at least two epoxy units, and an elastomer latex.
2. Composition selon la revendication 1 , dans laquelle le sel de lignosulfonate est un lignosulfonate de sodium, de potassium, de magnésium, d’ammonium ou de calcium. 2. The composition of claim 1, wherein the lignosulfonate salt is sodium, potassium, magnesium, ammonium or calcium lignosulfonate.
3. Composition selon la revendication 1 ou 2, dans laquelle le durcisseur est choisi parmi les éthers diglycidyliques ou polyglycidlyliques de polyols aliphatiques, les éthers diglycidyliques ou polyglycidyliques de phénols polyfonctionnels, les éthers polyglycidyliques de produits de condensation de phénols avec le formaldéhyde obtenus dans des conditions acides, les esters di- ou polyglycidyliques d'acides polycarboxyliques aliphatique ou aromatique, les composés à groupements époxycyclohexyles, les composés polyépoxydes résultant de l’époxydation d’un composé oléfiniquement insaturé, et leurs mélanges. 3. Composition according to claim 1 or 2, in which the hardener is chosen from diglycidyl or polyglycidlyl ethers of aliphatic polyols, diglycidyl or polyglycidyl ethers of polyfunctional phenols, polyglycidyl ethers of condensation products of phenols with formaldehyde obtained in acidic conditions, di- or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids, compounds containing epoxycyclohexyl groups, polyepoxy compounds resulting from the epoxidation of an olefinically unsaturated compound, and mixtures thereof.
4. Composition selon la revendication 3, dans laquelle le durcisseur est choisi parmi les composés suivants : 1 ,4 butanediol diglycidyl éther, 2,2-bis(4- hydroxyphényl) propane diglycidyl éther, Diglycidyl 1 ,2-cyclohexanedicarboxylate, 3,4- époxycyclohexylméthyl 3,4 époxycyclohexanecarboxylate, 1 ,6 hexanediol diglycidyl éther, Glycérol diglycidyl éther, Glycérol triglycidyl éther, mélange de glycérol diglycidyl éther et glycérol triglycidyl éther, résines époxyde de type novolaque, et leurs mélanges. 4. Composition according to claim 3, wherein the hardener is chosen from the following compounds: 1, 4 butanediol diglycidyl ether, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, Diglycidyl 1, 2-cyclohexanedicarboxylate, 3,4 - 3,4 epoxycyclohexylmethyl epoxycyclohexanecarboxylate, 1, 6 hexanediol diglycidyl ether, Glycerol diglycidyl ether, Glycerol triglycidyl ether, mixture of glycerol diglycidyl ether and glycerol triglycidyl ether, epoxy resins of the novolak type, and mixtures thereof.
5. Composition selon l’une quelconque des revendications 1 à 4, comprenant un latex de copolymère acrylonitrile/butadiène carboxylé (XNBR), un latex d'acrylonitrile/butadiène hydrogéné (HNBR), un latex de polyéthylène chlorosulfoné (CSM), un latex de copolymère styrène-butadiène-vinylpyridine (VPSBR), un latex de copolymère styrène/butadiène (SBR), un latex de copolymère acrylonitrile/butadiène (NBR), un latex de polybutadiène (BR), un latex de chlorobutadiène (CR), un latex de caoutchouc naturel (NR), un latex de polyuréthane, ou un mélange d’au moins deux d’entre eux. 5. Composition according to any one of claims 1 to 4, comprising a latex of acrylonitrile / carboxylated butadiene copolymer (XNBR), a latex of acrylonitrile / hydrogenated butadiene (HNBR), a latex of chlorosulfonated polyethylene (CSM), a latex. of styrene-butadiene-vinylpyridine copolymer (VPSBR), a latex of styrene / butadiene copolymer (SBR), an acrylonitrile / butadiene copolymer latex (NBR), a polybutadiene (BR) latex, a chlorobutadiene (CR) latex, a natural rubber latex (NR), a polyurethane latex, or a mixture of at least two of them.
6. Composition selon l’une quelconque des revendications 1 à 5, dans laquelle le taux massique de matière sèche de la composition peut être compris notamment entre environ 2 et environ 38%, en particulier entre environ 4 et environ 30%, plus particulièrement entre environ 7 et environ 25%. 6. Composition according to any one of claims 1 to 5, in which the percentage by mass of dry matter of the composition can be in particular between approximately 2 and approximately 38%, in particular between approximately 4 and approximately 30%, more particularly between approximately 2 and approximately 38%, in particular between approximately 4 and approximately 30%. about 7 and about 25%.
7. Composition selon l’une quelconque des revendications 1 à 6, comprenant d’environ 40 à environ 95 %, de préférence d’environ 55 à environ 90% en masse d’élastomère par rapport à la composition.
7. Composition according to any one of claims 1 to 6, comprising from about 40 to about 95%, preferably from about 55 to about 90% by weight of elastomer relative to the composition.
8. Composition selon l’une quelconque des revendications 1 à 7, dans laquelle le ratio massique durcisseur / sel de lianosulfonate est compris entre environ 0,01 et environ 5, plus particulièrement entre environ 0,03 et environ 1 , typiquement entre environ 0,05 et environ 0,5. 8. Composition according to any one of claims 1 to 7, in which the hardener / lianosulfonate salt mass ratio is between approximately 0.01 and approximately 5, more particularly between approximately 0.03 and approximately 1, typically between approximately 0. , 05 and about 0.5.
9. Composition selon l’une quelconque des revendications 1 à 8, dans laquelle le ratio massique [durcisseur + sel de lianosulfonatel / latex est compris entre environ 0,05 et environ 0,6 ; plus particulièrement entre environ 0,15 et environ 0,5. 9. A composition according to any one of claims 1 to 8, wherein the mass ratio [hardener + lianosulfonatel salt / latex is between about 0.05 and about 0.6; more particularly between about 0.15 and about 0.5.
10. Composition selon l’une quelconque des revendications 1 à 9, ayant un pH neutre ou basique, notamment un pH compris entre environ 7 et environ 13, en particulier entre environ 9 et environ 13. 10. A composition according to any one of claims 1 to 9, having a neutral or basic pH, in particular a pH of between about 7 and about 13, in particular between about 9 and about 13.
11. Kit destiné à produire une composition d’adhérisation selon l’une quelconque des revendications 1 à 10, comprenant une première composition comprenant un sel de lignosulfonate et un latex d’élastomère, et une deuxième composition comprenant un durcisseur époxy du sel de lignosulfonate, comprenant au moins deux motifs époxydes. 11. Kit for producing an adhesion composition according to any one of claims 1 to 10, comprising a first composition comprising a lignosulfonate salt and an elastomer latex, and a second composition comprising an epoxy hardener of the lignosulfonate salt. , comprising at least two epoxy units.
12. Utilisation d’une composition ou d’un kit selon l’une quelconque des revendications précédentes, pour conférer des propriétés d’adhésion à un textile de renfort, vis-à-vis d’un caoutchouc. 12. Use of a composition or a kit according to any one of the preceding claims, for imparting adhesion properties to a reinforcing textile, vis-à-vis a rubber.
13. Textile de renfort, notamment fil, câblé ou structure textile, au moins partiellement revêtu et/ou imprégné d’une composition d’adhérisation selon l’une quelconque des revendications 1 à 10. 13. Reinforcing textile, in particular yarn, cord or textile structure, at least partially coated and / or impregnated with an adhesion composition according to any one of claims 1 to 10.
14. Pièce en caoutchouc ou comportant un caoutchouc, dans laquelle le caoutchouc comprend au moins un textile de renfort selon la revendication précédente, en surface et/ou intégré à l’intérieur du caoutchouc.
14. Part made of rubber or comprising a rubber, in which the rubber comprises at least one reinforcing textile according to the preceding claim, on the surface and / or integrated inside the rubber.
Applications Claiming Priority (2)
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FR1911954A FR3102486A1 (en) | 2019-10-25 | 2019-10-25 | Adhering composition for textile and related reinforcing textile |
PCT/EP2020/079918 WO2021078955A1 (en) | 2019-10-25 | 2020-10-23 | Adhesion-promoting composition for a textile material and associated reinforcing textile material |
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EP4048718A1 true EP4048718A1 (en) | 2022-08-31 |
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EP20793385.4A Pending EP4048718A1 (en) | 2019-10-25 | 2020-10-23 | Adhesion-promoting composition for a textile material and associated reinforcing textile material |
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US (1) | US20220282143A1 (en) |
EP (1) | EP4048718A1 (en) |
JP (1) | JP2022554170A (en) |
CN (1) | CN114630861A (en) |
BR (1) | BR112022007678A2 (en) |
CA (1) | CA3155401A1 (en) |
FR (1) | FR3102486A1 (en) |
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JP2001234143A (en) * | 2000-02-21 | 2001-08-28 | Toray Ind Inc | Adhesive treatment agent for rubber/fiber, and fibrous cord for reinforcing rubber and its production method |
JP2002226812A (en) * | 2001-02-02 | 2002-08-14 | Toray Ind Inc | Adhesion treatment agent for carbon fiber, carbon fiber for rubber reinforcement and method for producing the same |
CN101412898B (en) * | 2007-10-18 | 2011-08-24 | 中国科学院宁波材料技术与工程研究所 | Novel non-formaldehyde wood adhesive and preparation thereof |
EP2450389B1 (en) * | 2010-11-08 | 2015-03-18 | EMS-Patent AG | Adhesion promoter for textile reinforcing inserts and their use. |
ITUA20163396A1 (en) * | 2016-05-12 | 2017-11-12 | Bridgestone Corp | ADHESIVE MIX FOR TIRES FOR TIRES |
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BR112022007678A2 (en) | 2022-08-09 |
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WO2021078955A1 (en) | 2021-04-29 |
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