Classifications

• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
  • D02G3/48—Tyre cords
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
  • D07B1/0606—Reinforcing cords for rubber or plastic articles
  • D07B1/062—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
  • D07B1/0606—Reinforcing cords for rubber or plastic articles
  • D07B1/0613—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the rope configuration
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
  • D07B1/0606—Reinforcing cords for rubber or plastic articles
  • D07B1/062—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration
  • D07B1/0626—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration the reinforcing cords consisting of three core wires or filaments and at least one layer of outer wires or filaments, i.e. a 3+N configuration
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2015—Strands
  • D07B2201/2023—Strands with core
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2015—Strands
  • D07B2201/2024—Strands twisted
  • D07B2201/2027—Compact winding
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2015—Strands
  • D07B2201/2036—Strands characterised by the use of different wires or filaments
  • D07B2201/2037—Strands characterised by the use of different wires or filaments regarding the dimension of the wires or filaments
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2015—Strands
  • D07B2201/2046—Strands comprising fillers
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2047—Cores
  • D07B2201/2052—Cores characterised by their structure
  • D07B2201/2059—Cores characterised by their structure comprising wires
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2047—Cores
  • D07B2201/2052—Cores characterised by their structure
  • D07B2201/2059—Cores characterised by their structure comprising wires
  • D07B2201/2061—Cores characterised by their structure comprising wires resulting in a twisted structure
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2047—Cores
  • D07B2201/2052—Cores characterised by their structure
  • D07B2201/2059—Cores characterised by their structure comprising wires
  • D07B2201/2062—Cores characterised by their structure comprising wires comprising fillers
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2047—Cores
  • D07B2201/2052—Cores characterised by their structure
  • D07B2201/2065—Cores characterised by their structure comprising a coating
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2201/00—Ropes or cables
  • D07B2201/20—Rope or cable components
  • D07B2201/2075—Fillers
  • D07B2201/2082—Fillers characterised by the materials used
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2205/00—Rope or cable materials
  • D07B2205/20—Organic high polymers
  • D07B2205/2003—Thermoplastics
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2205/00—Rope or cable materials
  • D07B2205/20—Organic high polymers
  • D07B2205/2017—Polystyrenes
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2205/00—Rope or cable materials
  • D07B2205/20—Organic high polymers
  • D07B2205/2075—Rubbers, i.e. elastomers
  • D07B2205/2082—Rubbers, i.e. elastomers being of synthetic nature, e.g. chloroprene
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2207/00—Rope or cable making machines
  • D07B2207/20—Type of machine
  • D07B2207/204—Double twist winding
  • D07B2207/205—Double twist winding comprising flyer
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2207/00—Rope or cable making machines
  • D07B2207/40—Machine components
  • D07B2207/4072—Means for mechanically reducing serpentining or mechanically killing of rope
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2401/00—Aspects related to the problem to be solved or advantage
  • D07B2401/20—Aspects related to the problem to be solved or advantage related to ropes or cables
  • D07B2401/208—Enabling filler penetration
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2501/00—Application field
  • D07B2501/20—Application field related to ropes or cables
  • D07B2501/2046—Tire cords
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B5/00—Making ropes or cables from special materials or of particular form
  • D07B5/12—Making ropes or cables from special materials or of particular form of low twist or low tension by processes comprising setting or straightening treatments
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B7/00—Details of, or auxiliary devices incorporated in, rope- or cable-making machines; Auxiliary apparatus associated with such machines
  • D07B7/02—Machine details; Auxiliary devices
  • D07B7/14—Machine details; Auxiliary devices for coating or wrapping ropes, cables, or component strands thereof
  • D07B7/145—Coating or filling-up interstices

Definitions

• the present invention relates to concentric two-layer metal cables, of M + N construction, formed of a first central layer, internal M wire (s) surrounded by a second outer layer of N son, used in particular for the reinforcement rubber articles, more particularly relative to two-layer metal cables of the type "gummed in situ", that is to say gummed from the inside, during their manufacture, by rubber or a rubber composition.
• a radial tire comprises in known manner a tread, two inextensible beads, two flanks connecting the beads to the tread and a belt circumferentially disposed between the carcass reinforcement and the tread.
• the carcass reinforcement consists of at least one ply (or “layer”) of rubber reinforced by reinforcing elements (or “reinforcements”) such as cords or monofllaments, generally of the metal type in the case of tires for industrial vehicles carrying heavy loads.
• the belt consists of various plies or layers of rubber reinforced or not by reinforcements such as cords or monofllaments, including metal type. It generally comprises at least two superimposed belt plies, sometimes called “working plies” or “crossed plies”, whose metal reinforcing cables are arranged parallel to each other inside a ply, but crossed with one another. a ply to the other, that is to say, inclined, symmetrically or otherwise, with respect to the median circumferential plane, an angle which is generally between 10 ° and 45 ° depending on the type of tire considered.
• crossed plies can be supplemented by various other plies or layers of auxiliary rubber, of varying widths depending on the case, with or without reinforcements; examples of so-called “protection” plies responsible for protecting the rest of the belt from external aggressions, perforations, or so-called “hooping” plies comprising reinforcements oriented substantially in the circumferential direction (so-called plies). "At zero degrees").
• a tire belt must satisfy many known requirements, often contradictory, including: be as rigid as possible with low deformation, because it contributes in a substantial way to stiffen the crown of the tire;
• the third requirement is particularly strong for tire casings for industrial vehicles such as heavy-duty vehicles, designed to be retreadable once or more when their treads reach a critical degree of wear after prolonged rolling. .
• a first object of the invention is a metal cable with two concentric layers (Ci, Ce) of M + N construction, comprising a first inner layer or core (Ci) consisting of M fIl (s) of diameter di, M ranging from 1 to 4, core around which are surrounded together in a helix, in a second outer layer (Ce), N son of diameter d 2 , wherein at least a portion of the interstices between the son of the different layers contain rubber or a rubber composition, which cable is characterized in that said rubber is an unsaturated thermoplastic elastomer.
• This two-layer cable of the invention no longer poses a problem of parasitic tights in the event of an overflow outside the cable after its manufacture.
• the unsaturated and therefore (co) vulcanizable nature of this thermoplastic elastomer offers the cable thus prepared excellent compatibility with the matrices of diene rubbers usually used. as a calendering rubber in metal fabrics for reinforcing tires.
• thermoplastic elastomer above is by definition heat fusible, therefore easier to implement than a diene-type elastomer; thus, its quantity can be more easily controlled, it is possible, by adjusting the application temperature, to evenly distribute the thermoplastic elastomer inside each of the interstices of the cable, giving the latter optimal impermeability according to its longitudinal axis, without even fearing a possible overflow at the periphery of the cable.
• the invention also relates to the use of a cable according to the invention for reinforcing finished articles or semi-finished rubber products, for example webs, pipes, belts, conveyor belts, tires. .
• the cable of the invention is particularly intended to be used as reinforcing member of a carcass reinforcement or vertex tires of industrial vehicles (heavy load carriers) selected from vans and vehicles called "truck-heavy" c ' that is, metro vehicles, buses, road transport vehicles such as trucks, tractors, trailers, or off-the-road vehicles, agricultural or civil engineering machinery, and any other type of transport or handling vehicle.
• the invention further relates to these finished articles or semi-finished rubber products themselves when reinforced by a cable according to the invention, in particular tires for industrial vehicles such as vans or heavy goods vehicles.
• FIGS. 1 to 6 relating to these examples which schematize, respectively: in cross-section, a construction cable +9 according to the invention, gummed in situ, of the compact type (FIG 1);
• FIG. 6 an example of a twisting and in situ scrubbing installation that can be used for manufacturing cylindrical type cables, in accordance with the invention (FIG. in radial section, a heavy-duty pneumatic tire with a radial carcass reinforcement, conforming or not to the invention in this general representation (FIG 6).
• Fm maximum load in N
• Rm tensile strength in MPa
• At total elongation in %
• the modulus measurements are carried out in tension, unless otherwise indicated according to the ASTM D 412 standard of 1998 (test piece “C”): one measures in second elongation (that is to say after a cycle of accommodation) the secant modulus "true” (that is to say, brought back to the real section of the specimen) at 10% elongation, denoted E10 and expressed in MPa (normal conditions of temperature and hygrometry according to ASTM D 1349 of 1999).
• This test makes it possible to determine the longitudinal permeability to the air of the cables tested, by measuring the volume of air passing through a specimen under constant pressure for a given time.
• the principle of such a test is to demonstrate the effectiveness of the treatment of a cable to make it impermeable to air; it has been described for example in ASTM D2692-98.
• the test is here performed either on cables extracted from tires or rubber sheets that they reinforce, so already coated from the outside by the rubber in the fired state, or on raw cables manufacturing.
• the raw cables must be previously coated from the outside by a so-called coating gum.
• a series of 10 cables arranged in parallel (inter-cable distance: 20 mm) is placed between two layers or "skims" (two rectangles of 80 x 200 mm) of a diene rubber composition in the green state, each skim having a thickness of 3.5 mm; the whole is then locked in a mold, each of the cables being kept under a sufficient tension (for example 2 daN) to ensure its straightness during the establishment in the mold, using clamping modules; then the vulcanization (cooking) is carried out for 40 minutes at a temperature of 140 ° C. and under a pressure of 15 bar (rectangular piston of 80 x 200 mm).
• sulfur (7 phr), accelerator is used as a coating rubber.
• the test is carried out on 2 cm of cable length, thus coated by its surrounding rubber composition (or coating gum) in the fired state, as follows: air is sent to the cable inlet at a pressure of 1 bar, and the volume of air at the outlet is measured using a flow meter (calibrated for example from 0 to 500 cm 3 / min).
• a flow meter calibrated for example from 0 to 500 cm 3 / min.
• the cable sample is locked in a compressed seal (eg a dense foam or rubber seal) in such a way that only the amount of air passing through the cable from one end to the other, along its longitudinal axis, is taken into account by the measure; the tightness of the seal itself is checked beforehand with the aid of a solid rubber specimen, that is to say without cable.
• a compressed seal eg a dense foam or rubber seal
• the average air flow measured (average of the 10 specimens) is even lower than the longitudinal imperviousness of the cable is high.
• the measured values less than or equal to 0.2 cm 3 / min are considered as zero; they correspond to a cable that can be described as airtight (totally airtight) along its axis (ie, in its longitudinal direction).
• the amount of filling compound is measured by the difference between the weight of the initial cable (thus erased in situ) and the weight of the cable (thus that of its threads) whose filling compound has been eliminated by a treatment in a suitable extraction solvent.
• the procedure is as follows. A sample of cable of a given length (for example one meter), coiled on itself to reduce its bulk, is placed in a sealed bottle containing one liter of toluene. Then the flask is stirred (125 rounds per minute) for 24 hours at room temperature (20 ° C.), using a "Ping-Pong 400" agitator from the company. Fischer Scientific); after removal of the solvent, the operation is repeated once. The thus treated cable is recovered and the residual solvent evaporated under vacuum for 1 hour at 60 ° C. Then the cable thus freed of its filling rubber is weighed. From the calculation, the filling rate in the cable, expressed in mg (milligram) of filling rubber per g (gram) of initial cable, is calculated and averaged over 10 measurements (i.e. total cable meters).
• any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range from a to b (i.e., including the strict limits a and b).
• the metal cable of the invention therefore comprises two concentric layers:
• a first central layer or inner layer consisting of M f (d) of diameter di, wound together in a helix, in a pitch pi, when M is greater than 1;
• a second layer or outer layer (Ce) comprising N wires of diameter d 2 wound together in a helix, in a pitch p 2 , around the first layer (Ci).
• the first layer (Ci) is also called the core or core of the cable.
• M is greater than 1, it must of course be understood that the diameter noted d ; the core (Ci) then represents the diameter of the cylinder of imaginary revolution (or diameter of space) which surrounds the M (2, 3 or 4) central son of diameter di.
• This cable of the invention can be described as gummed cable in situ, that is to say that it is erased from within, during its manufacture itself, by rubber or a rubber composition referred to in the present application "filling rubber”.
• cable in the raw state of manufacture means a cable which has not yet been brought into contact with a diene rubber matrix (eg natural rubber) of a semi-finished product or an article rubber finish such as a tire, that said cable of the invention would be intended to reinforce later.
• a diene rubber matrix eg natural rubber
• This specific rubber is an unsaturated thermoplastic elastomer, used alone or with any additives (that is to say in this case in the form of an unsaturated thermoplastic elastomer composition) to form the filling rubber.
• thermoplastic elastomers are thermoplastic elastomers in the form of block copolymers based on thermoplastic blocks.
• thermoplastic polymers and elastomers consist in known manner of rigid thermoplastic blocks, in particular polystyrene linked by flexible elastomer blocks, for example polybutadiene or polyisoprene for unsaturated TPE or poly (ethylene / butylene) for saturated TPEs.
• the above TPE block copolymers are generally characterized by the presence of two glass transition peaks, the first peak (lowest temperature, generally negative) being relative to the elastomer sequence of the TPE copolymer, the second peak (highest temperature, positive, typically greater than 80 ° C for preferred elastomers TPS type) being relative to the thermoplastic part (eg styrene blocks) of the TPE copolymer.
• TPE elastomers are often triblock elastomers with two rigid segments connected by a flexible segment.
• the rigid and flexible segments can be arranged linearly, star or connected.
• These TPE elastomers may also be diblock elastomers with a single rigid segment connected to a flexible segment.
• each of these segments or blocks contains at least more than 5, usually more than 10 base units (e.g., styrene units and isoprene units for a styrene / isoprene / styrene block copolymer).
• an essential characteristic of the TPE elastomer used in the composite reinforcement of the invention is that it is unsaturated.
• unsaturated TPE elastomer is meant by definition and well known manner a TPE elastomer which is provided with ethylenic unsaturations, that is to say which has carbon-carbon double bonds (conjugated or not); reciprocally, a saturated TPE elastomer is of course a TPE elastomer which is free of such double bonds.
• the unsaturated nature of the unsaturated TPE elastomer causes the latter to be (co) crosslinkable, (co) vulcanizable with sulfur, which makes it advantageously compatible with matrices of unsaturated diene rubbers such as those based on natural rubber, which are usually used as a calendering rubber in metal fabrics for reinforcing tires.
• any overflow of the filling rubber outside the cable, during the manufacture of the latter will not be detrimental to its subsequent adhesion to the calendering gum of said metal fabric, this defect being indeed susceptible of be corrected during the final firing of the tire by the possible co-crosslinking between the unsaturated TPE elastomer and the diene elastomer of the calendering gum.
• the unsaturated TPE elastomer is a styrenic thermoplastic elastomer (abbreviated as "TPS"), that is to say comprising, as thermoplastic blocks, styrene blocks (polystyrene).
• TPS thermoplastic elastomer
• the unsaturated TPS elastomer is a copolymer comprising polystyrene blocks (that is to say formed from polymerized styrene monomer) and polydiene blocks (that is to say formed from polymerized diene monomer), preferably from the latter polyisoprene blocks and / or polybutadiene blocks.
• polydiene blocks in particular polyisoprene blocks and polybutadiene blocks
• blocks of random diene copolymer in particular of isoprene or butadiene, for example blocks of styrene / isoprene random copolymer (SI) or styrene-butadiene (SB), these polydiene blocks being particularly associated with polystyrene thermoplastic blocks to form unsaturated TPS elastomers which have been previously described.
• SI styrene / isoprene random copolymer
• SB styrene-butadiene
• styrene monomer any styrene-based monomer, unsubstituted as substituted; among the substituted styrenes may be mentioned, for example, methylstyrenes (for example ⁇ -methylstyrene, m-methylstyrene or p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene or diphenylethylene), para-tert-butylstyrene, chlorostyrenes (for example o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene or 2, 4,6-trichlorostyrene), bromostyrenes (eg, o-bromostyrene, m-bromostyrene, p-bromostyrene, 2, 2,
• iene monomer should be understood to mean any monomer bearing two carbon-carbon double bonds, conjugated or otherwise, in particular any conjugated diene monomer having from 4 to 12 carbon atoms chosen in particular from the group constituted by isoprene, butadiene, 1-methylbutadiene, 2-methylbutadiene, 2,3-dimethyl-1,3-butadiene, 2,4-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3 -pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,5-dimethyl-1,3-pentadiene , 1,3-hexadiene, 2-methyl-1,3-hexadiene, 3-methyl-1,3-hexadiene, 4-methyl-1,3-hexadiene, 5-methyl-1,3-hexadiene, hexadiene,
• Such an unsaturated TPS elastomer is chosen in particular from the group consisting of styrene / butadiene block copolymers (SB), styrene / isoprene block copolymers (SI), styrene / butadiene / butylene block copolymers (SBB), styrene block copolymers / butadiene / isoprene (SBI), styrene / butadiene / styrene block copolymers (SBS), styrene / butadiene / butylene / styrene block copolymers (SBB S), styrene / isoprene / styrene block copolymers (SIS), block copolymers styrene / butadiene / isoprene / styrene (SBIS) and mixtures of these
• this unsaturated TPS elastomer is a copolymer comprising at least three blocks, this copolymer being more particularly chosen from the group consisting of styrene / butadiene / styrene block copolymers (SBS), styrene / butadiene / butylene / styrene block copolymers (SBBS), styrene / isoprene / styrene block copolymers (SIS), styrene / butadiene / isoprene / styrene block copolymers (SBIS) and mixtures of these copolymers.
• SBS styrene / butadiene / styrene block copolymers
• SBBS styrene / butadiene / butylene / styrene block copolymers
• SIS styrene
• the styrene content, in the unsaturated TPS elastomer above, is between 5 and 50%, for an optimal compromise with respect to the thermoplastic properties of one part and the (co) crosslinkable character of this elastomer on the other hand.
• the number-average molecular weight (denoted Mn) of the TPE elastomer is preferably between 5,000 and 500,000 g / mol, more preferably between
• the number average molecular weight (Mn) of the TPS elastomers is determined in known manner by size exclusion chromatography (SEC). The sample is first solubilized in tetrahydrofuran at a concentration of about 1 g / l; then the solution is filtered on 0.45 ⁇ porosity filter before injection. The equipment used is a chromatographic chain "WATERS alliance".
• the eluting solvent is tetrahydrofuran
• the flow rate is 0.7 ml / min
• the system temperature is 35 ° C. and the analysis time of 90 min.
• a set of four WATERS columns in series, of trade names "STYRAGEL"("HMW7","HMW6E” and two “HT6E") is used.
• the injected volume of the solution of the polymer sample is 100 ⁇ .
• the detector is a differential refractometer "WATERS 2410" and its associated software for the exploitation of chromatographic data is the "WATERS MILLENIUM" system.
• the calculated average molar masses relate to a calibration curve made with polystyrene standards.
• the Tg of the unsaturated TPE elastomer (in particular TPS) (as a reminder, first Tg relative to the elastomer block) is less than 0 ° C., more particularly less than - 15 ° C., this quantity being measured in a known manner by DSC (Differential Scanning Calorimetry), for example according to the ASTM D3418-82 standard.
• the Shore A hardness (measured according to ASTM D2240-86) of the unsaturated TPE elastomer (in particular TPS) is between 10 and 100, more particularly included in a range of 20 to 90.
• Unsaturated TPS elastomers such as, for example, SB, SI, SBS, SIS, SBBS or SBIS are well known and commercially available, for example from Kraton under the name "Kraton D” (eg, products Dl 161, Dl 118, Dl 116, Dl 163), from Dynasol under the name "Calprene” (eg, products C405, C411, C412), from Polimeri Europa under the name "Europrene” (eg, product SOLT166), from BASF under the name "Styroflex” (eg, product 2G66), or from Asahi under the name "Tuftec” (eg, product P1500).
• Kraton D eg, products Dl 161, Dl 118, Dl 116, Dl 163
• Dynasol under the name "Calprene” (eg, products C405, C411, C412)
• Polimeri Europa under the name "Europrene”
• BASF under the name
• the unsaturated thermoplastic elastomer previously described is sufficient on its own for the filling rubber to fully fulfill its function of closing off the capillaries or interstices of the cable of the invention.
• various other additives may be added, typically in small amounts (preferably at weight ratios of less than 20 parts, more preferably less than 10 parts per 100 parts of unsaturated thermoplastic elastomer), for example plasticizers, reinforcing fillers such as carbon black or silica, non-reinforcing or inert fillers, lamellar fillers, protective agents such as antioxidants or anti-ozonants, various other stabilizers, coloring agents intended for example to color the gum filling.
• the filling rubber could also comprise, in a minority weight fraction relative to the unsaturated thermoplastic elastomer fraction, polymers or elastomers other than unsaturated thermoplastic elastomers.
• the invention relates of course to the previously described cable both in the crosslinked (or vulcanized) state and in the uncrosslinked (or uncured) state. However, it is preferred to use the cable of the invention with a filling rubber in the uncrosslinked state until it is subsequently incorporated into the semi-finished product or finished article, such as the tire for which it is intended, so as to favor the bonding. during the final crosslinking or vulcanization between the filling rubber and the surrounding rubber matrix (for example a calendering rubber).
• FIG. 1 schematizes, in section perpendicular to the axis of the cable (assumed to be rectilinear and at rest), an example of a preferential cable 3 + 9 in accordance with the invention in which the core or central layer (Cl) consists of three sons.
• This type of construction has the consequence that the inner (10) and outer (11) wires form two concentric layers which each have a substantially polygonal contour (represented in dotted lines) (triangular for the Ci, hexagonal layer for the Ce layer), and non-cylindrical as in the case of cables with cylindrical layers which will be described later.
• the filling rubber (12) fills the central capillary (13) (symbolized by a triangle) formed by the three core wires (10) by spacing them very slightly, while completely covering the inner layer Ci formed by the three wires (10). It also fills each interstice or cavity (also symbolized by a triangle) formed either by a core wire (10) and the two external wires (11) which are immediately adjacent to it, or by two core wires (10) and the outer wire (11) adjacent thereto; in total, 12 interstices or capillaries are thus present in this example of cable 3 + 9, to which is added the central capillary (13).
• the filling rubber extends in a continuous manner around the layer Ci it covers.
• Figure 2 recalls the section of a cable 3 + 9 (noted C-2) conventional (ie, not gummed in situ), also of the compact type.
• C-2 conventional (ie, not gummed in situ), also of the compact type.
• the absence of filling rubber makes practically all the son (20, 21) in contact with each other, which leads to a particularly compact structure, also very difficult to penetrate (not to say impenetrable) from the outside by rubber.
• the characteristic of this type of cable is that the three core wires (20) form a central channel or capillary (23) which is empty and closed and thus conducive, by "wicking" effect, to the propagation of corrosive media such as that water.
• Figure 3 shows another example of a preferred cable 3 + 9 according to the invention.
• this type of construction has the consequence that the wires are arranged in two adjacent and concentric, tubular layers (Ci and Ce), giving the cable (and its two layers) an outline (shown in dashed lines) of cylindrical and non-linear shape. more polygonal.
• the filling rubber (32) fills the central capillary (33) (symbolized by a triangle) formed by the three core wires (30) slightly apart, while completely covering the inner layer Ci formed by the three wires ( 30). It also fulfills, at least in part (here, in this example, totally) each interstice or cavity formed either by a core wire (30) and the two outer wires (31) which are immediately adjacent thereto (the closest) either by two core wires (30) and the adjacent outer wire (31).
• Figure 4 recalls the section of a cable 3 + 9 (noted C-4) conventional (not gummed in situ), also of the type with two cylindrical layers.
• C-4 conventional (not gummed in situ), also of the type with two cylindrical layers.
• the absence of filling rubber causes the three wires (40) of the inner layer (Ci) to come into close contact with each other, which leads to a central, empty and closed capillary 43, which is impenetrable. outside by rubber and thus conducive to the propagation of corrosive media.
• the unsaturated TPS elastomer is present in each of the capillaries situated between the core (Ci) and the N wires of the second layer ( This) as well as between the core threads themselves when M is greater than 1.
• the level of filling rubber in the cable of the invention is between 5 and 40 mg of gum per g of cable. Below the indicated minimum, it is more difficult to guarantee that the filling compound is present, at least in part, in each of the interstices or capillaries of the cable, whereas beyond the maximum indicated, it is exposed to possible overflow of the filling rubber at the periphery of the cable. For all these reasons, it is preferred that the level of filling gum be between 5 and 35 mg, especially between 5 and 30 mg.
• each capillary or interstice of the cable of the invention comprises at least one rubber stopper which obstructs this capillary or interstice in such a way that, at air permeability test according to section 1-2, this cable of the invention has a flow rate average air less than 2 cm 3 / min, more preferably less than 0.2 cm 3 / min or at most equal to 0.2 cm 3 / min.
• N is in a range from 5 to 15.
• the core (Ci) of the cable of the invention preferably consists of a single unitary wire or at most 2 or 3 wires, the latter being for example parallel or on the contrary twisted together. More preferably still, when M is equal to 1, N is in a range from 5 to 7, and when M is equal to 2 or 3, N is in a range from 6 to 11; When M is 4, N is preferably in the range of 8 to 12.
• the pitch "p" represents the length, measured parallel to the axis of the cable, at the end of which a wire having this pitch performs a complete revolution about said axis of the cable.
• the M son are preferably assembled, in particular twisted, according to a pitch pi which is more preferably in a range from 3 to 30 mm , in particular in a range of 3 to 20 mm.
• the pitches pi and p 2 are equal. This is particularly the case for cables of the compact type of layer as schematized for example in Figure 1, in which the two layers Ci and Ce have the other characteristic of being wound in the same direction of torsion (S / S or Z / Z). In such cables with so-called compact layers, the compactness is very high, such that the cross section of these cables has a contour which is polygonal and non-cylindrical, as illustrated by way of example in FIG. 1 (compact cable 3 + 9 according to the invention) or in Figure 2 (compact cable 3 + 9 control, that is to say, not gummed in situ). According to another preferred embodiment, the pitches pi and p 2 are different.
• the outer layer Ce has the preferential characteristic of being a saturated layer, that is to say that, by definition, there is not enough room in this layer to add a additional wire of diameter d 2 , in other words at least one (N max + 1) th wire diameter d 2 , N max representing the maximum number of windable son in a layer around the central layer (Ci).
• This construction has the notable advantage of offering, for a given diameter of the cable, a higher resistance.
• the number N of wires can vary to a very large extent according to the particular embodiment of the invention, it being understood that the maximum number of wires N will be increased if their diameter d 2 is reduced compared to the diameter di of the wires of the layer, in order to preferentially keep the outer layer in a saturated state.
• the cables of the invention have for their preferred constructions 1 + 6, 2 + 7, 2 + 8, 3 + 8, 3 + 9, 4 + 9 and 4 + 10.
• the cable of the invention can be of two types, namely of the compact-layer type or of the cylindrical-layer type.
• the layer Ci in the case where M is greater than 1 and the layer Ce are wound in the same direction of torsion, that is to say either in the direction S ("S / S" arrangement), or in the Z direction (“Z / Z” layout). Coiling in the same direction of these layers advantageously allows to minimize the friction between these two layers and therefore the wear of the son that constitute them.
• the two layers are wound in the same direction of torsion and at a different pitch (ie pi ⁇ p 2 ), to obtain a cable of the cylindrical type as represented for example in Figure 3.
• Wire rope means by definition in the present application a cable formed of son constituted mainly (that is to say for more than 50% by number of these son) or integrally (per 100 % of the wires) of a metallic material.
• the M or the wire (s) of the core (Ci) and the N son of the second external (Ce) are preferably made of steel, more preferably carbon steel. But it is of course possible to use other steels, for example a stainless steel, or other alloys.
• carbon steel When a carbon steel is used, its carbon content (% by weight of steel) is preferably between 0.2% and 1.2%, especially between 0.5% and 1.1%; these levels represent a good compromise between the mechanical properties required for the tire and the feasibility of the wires. It should be noted that a carbon content of between 0.5% and 0.6% makes such steels ultimately less expensive because easier to draw.
• Another advantageous embodiment of the invention may also consist, depending on the applications concerned, of using steels with a low carbon content, for example between 0.2% and 0.5%, in particular because of a cost lower and easier to draw.
• the metal or steel used may itself be coated with a metal layer improving, for example, the properties of implementation of the wire rope and / or its constituent elements, or the properties of use of the cable and / or the tire themselves, such as adhesion properties, corrosion resistance or resistance to aging.
• the steel used is covered with a layer of brass (Zn-Cu alloy) or zinc; it is recalled that during the wire manufacturing process, the coating of brass or zinc facilitates the drawing of the wire, as well as the bonding of the wire with the rubber.
• the son could be covered with a thin metal layer other than brass or zinc, for example having the function of improving the resistance to corrosion of these son and / or their adhesion to rubber, for example a thin layer of Co, Ni, Al, an alloy of two or more compounds Cu, Zn, Al, Ni, Co, Sn.
• a thin metal layer other than brass or zinc for example having the function of improving the resistance to corrosion of these son and / or their adhesion to rubber, for example a thin layer of Co, Ni, Al, an alloy of two or more compounds Cu, Zn, Al, Ni, Co, Sn.
• the cables of the invention are preferably carbon steel and have a tensile strength (Rm) preferably greater than 2500 MPa.
• the total elongation at break ( ⁇ t) of the cable, the sum of its structural, elastic and plastic elongations, is preferably greater than 2.0%.
• the two-layer cable (Ci, Ce) of the invention described above may be manufactured according to a method comprising at least the following steps:
• the tension stress exerted on each wire of the inner layer is preferably between 10 and 25% of its breaking force.
• the so-called filling gum is thus introduced in situ into the cable during manufacture, by sheathing the inner layer, said cladding being operated in known manner, for example by passing through at least one head of the extrusion delivering the filling rubber in the molten state.
• the extrusion head is brought to a suitable temperature, easily adjustable according to the specific nature of the TPE elastomer used and its thermal properties.
• the extrusion temperature of the unsaturated TPE elastomer is between 100 ° C and 250 ° C, more preferably between 150 ° C and 200 ° C.
• the extrusion head defines a cladding zone having for example the shape of a cylinder of revolution whose diameter is preferably between 0.15 mm and 1.2 mm, more preferably between 0.20 and 1, 0 mm, and whose length is preferably between 1 and 10 mm.
• the melt unsaturated TPE elastomer thus covers the core by means of the cladding head, at a running speed typically of a few meters to a few tens of m / min, for an extrusion pump flow typically of several cm 3 / min to several tens of cm 3 / min.
• the core is advantageously preheated before passing through the extrusion head, for example by passing through an HF generator or through a heating tunnel.
• all the steps described above are operated online and continuously, regardless of the type of cable manufactured (compact cable as cable with cylindrical layers), all this at high speed.
• the above method can be implemented at a speed (running speed of the cable on the production line) greater than 50 m / min, preferably greater than 70 m / min, especially greater than 100 m / min.
• the cable of the invention batchwise, for example by prior sheathing of the central layer (Ci), solidification of the filling rubber and winding and storage of the latter before the final operation of assembly of the outer layer (Ce); the solidification of the elastomeric sheath is easy, it can be conducted by any suitable cooling means, for example by cooling in air or water, followed in the latter case by a drying operation. At this stage, the manufacture of the cable of the invention is complete.
• Torsion balancing here means, in a known manner, the cancellation of the residual torsional torques (or of the elastic recoil of detorsion) acting on the cable.
• Torsion balancing tools are well known to those skilled in the art of twisting; they may consist for example of trainers and / or twisters and / or twister-trainers consisting of either pulleys for twisters, or small diameter rollers for trainers, pulleys and / or rollers through which the cable runs.
• the thickness of filling rubber between two adjacent wires of the cable, whatever they are, varies from 1 to 10 ⁇ .
• This cable can be wound on a receiving reel, for storage, before being processed, for example, through a calendering installation, for preparing a metal-rubber composite fabric that can be used, for example, as a carcass reinforcement, or even as a reinforcement. of tire crown.
• the method described above makes it possible to manufacture cables which, in a particularly preferred embodiment, may have no or almost no filling rubber at their periphery; by such an expression, it is meant that no particle of filling compound is visible, with the naked eye, at the periphery of the cable, that is to say that the person skilled in the art does not make any difference at the output of the manufacturing process, with the naked eye and at a distance of three meters or more, between a cable reel according to the invention and a conventional cable reel not gummed in situ.
• the invention applies to compact type cables (for recall and by definition, those whose layers Ci (if M is greater than 1) and Ce are wound at the same pitch and in the same direction) as well as Cylindrical layer type cables (for recall and by definition, those whose layers Ci (if M is greater than 1) and Ce are wound either in different steps (whatever their torsion directions, identical or not), or in opposite directions (whatever their steps, identical or different)).
• An assembly and scrubbing device preferably used for the implementation of this method is a device comprising from upstream to downstream, according to the direction of advancement of a cable being formed: feed means of a part of the M or M thread (s) of the inner layer (Ci), on the other hand N son of the outer layer (Ce);
• assembly means by twisting the M core yarns, for forming the inner layer (Ci) at an assembly point;
• extrusion means delivering the thermoplastic elastomer in the molten state, for sheathing the inner layer Ci (or single wire constituting this inner layer when M is equal to 1, or all of the M son twisted together when M is different from 1);
• FIG. 5 shows an exemplary twisting assembly device (50) of the rotary feed and rotary receiving type (symbolized by two arrows of the same direction), usable for the manufacture of a layer-type cable.
• cylindrical here, pi ⁇ p 2 and same direction of torsion of the layers Ci and Ce
• supply means (510) deliver three core wires (51 ) through a distribution grid (52) (axisymmetrical splitter), coupled or not to an assembly line (53), beyond which converge the three core wires at an assembly point (54), for formation of the inner layer (Ci).
• the inner layer Ci once formed, then passes through a cladding zone consisting for example of a single extrusion head (55) through which is intended to circulate the inner layer.
• the distance between the point of convergence (54) and the sheathing point (55) is for example between 50 cm and 1 m.
• the final cable 3 + N thus formed is finally collected on a rotary reception (59) after passing through the torsion balancing means (58) consisting for example of a twister-trainer.
• the cable of the invention is particularly intended for a carcass reinforcement or a tire crown reinforcement (belt) for industrial vehicles such as heavy goods vehicles.
• FIG. 6 schematically represents a radial section of a pneumatic metal crown reinforcement tire which may or may not conform to the invention, in this general representation.
• This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a rod 5.
• the crown 2 is surmounted by a tread not shown in this schematic figure.
• a carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1 which is shown here mounted on its rim 9.
• the carcass reinforcement 7 is in known manner constituted by at least one sheet reinforced by so-called "radial” cables, that is to say that these cables are arranged substantially parallel to each other and extend from a bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located halfway between the two beads 4 and passes through the middle of the crown frame 6).
• the tire according to the invention is for example characterized in that its carcass 7 and / or its belt 6 comprises (s) at least one metal cable with two layers according to the invention.
• the cables of the invention may for example strengthen all or part of the so-called working belt plies.
• the two-layer cables of the invention compared with the two-layer cables of the prior art gummed in situ with a conventional diene rubber (non-hot melt), have the notable advantage that their filling gum is devoid of parasitic tack in the green state (ie, uncrosslinked).
• they may furthermore comprise a reduced and controlled quantity of filling compound, which guarantees them excellent compactness, this gum being preferentially distributed uniformly inside the cable, particular inside each of its capillaries, thus conferring on them an optimal longitudinal impermeability.
• the carbon steel wires are prepared in a known manner, for example starting from machine wires (diameter 5 to 6 mm) which are first cold-rolled, by rolling and / or drawing, to a neighboring intermediate diameter. of 1 mm.
• the steel used is a carbon steel of the standard (NT type for "Normal Tensile") whose carbon content is about 0.7%, the rest being made of iron and the usual unavoidable impurities related to the manufacturing process. steel.
• the intermediate diameter son undergo a degreasing treatment and / or pickling, before further processing.
• the steel wires thus drawn have the following diameter and mechanical properties:
• the cable of the invention 3 + 9 (C-3), as schematized in FIG. 3, is formed of 12 wires in total, all of diameter 0.23 mm, which have been wound to two different pitch (pi ⁇ p 2 ) and in the same direction of twist (S) to obtain a cable of the type with cylindrical layers.
• the rate of filling rubber, measured according to the method indicated previously in paragraph 1-3, is 23 mg per g of cable.
• This filling gum fills the channel or central capillary formed by the three core wires slightly apart, while completely covering the inner layer Ci formed by the three son. It also fulfills, at least in part, if not preferably completely, each of the other interstices or capillaries formed by the yarns of the two layers (Ci, Ce).
• unsaturated TPS elastomer in this case an SBS elastomer of Shore A hardness equal to about 70
• the cable according to the invention has an optimal penetration rate by the unsaturated thermoplastic elastomer, with a controlled amount of filling rubber, which guarantees the presence of internal partitions (continuous or discontinuous in the axis of the cable) or gum plugs in the capillaries or interstices in a sufficient number; thus, the cable of the invention becomes impervious to the propagation, along the cable, of any corrosive fluid such as water or oxygen in the air, thereby eliminating the wicking effect described in the introduction to this memo .
• thermoplastic elastomer used does not pose a problem of parasitic tights in case of a slight overflow outside the cable after manufacture; in case of overflow its unsaturated character and therefore (co) vulcanizable makes it compatible with a surrounding matrix of unsaturated diene elastomer such as natural rubber.
• the invention is not limited to the previously described embodiments.
• a (at least one) linear wire of one of the two layers (Ci and / or Ce) could be replaced by a preformed or deformed wire, or more generally by a wire of section different from that of other wires of diameter di and / or d 2 , for example to further improve the penetrability of the cable by rubber or any other material, the overall size of this replacement wire may be less than, equal to or greater than the diameter (di and / or d 2 ) other constituent son of the layer (Ci and / or Ce) concerned.
• part of the son constituting the cable according to the invention could be replaced by son other than son steel, metal or not, including son mineral or organic material to high mechanical strength, for example monofilaments organic polymers liquid crystal.
• the invention also relates to any multi-strand steel cable ("multistrand rope”) whose structure incorporates at least, as elementary strand, a layered cable according to the invention.
• multitoron cables in accordance with the invention which can be used, for example, in tires for industrial vehicles of the civil engineering type, in particular in their carcass or crown reinforcement, mention may be made of multi-structure cables of general construction known per se. (M being equal to 1, 2, 3 or 4, N ranging from 5 to 15):
• Such multi-layered steel cables with two layers for example of the type:

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• 2011
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