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WO2020096027A1 - Article, en particulier un pneu - Google Patents

Article, en particulier un pneu Download PDF

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Publication number
WO2020096027A1
WO2020096027A1 PCT/JP2019/043795 JP2019043795W WO2020096027A1 WO 2020096027 A1 WO2020096027 A1 WO 2020096027A1 JP 2019043795 W JP2019043795 W JP 2019043795W WO 2020096027 A1 WO2020096027 A1 WO 2020096027A1
Authority
WO
WIPO (PCT)
Prior art keywords
article according
article
fiber
thermoplastic resin
tire
Prior art date
Application number
PCT/JP2019/043795
Other languages
English (en)
Inventor
Yasufumi Nakashima
Guillaume Cantagrel
Original Assignee
Compagnie Generale Des Etablissements Michelin
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Compagnie Generale Des Etablissements Michelin filed Critical Compagnie Generale Des Etablissements Michelin
Publication of WO2020096027A1 publication Critical patent/WO2020096027A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/10—Footwear characterised by the material made of rubber
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D29/00—Producing belts or bands
    • B29D29/08—Toothed driving belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
    • B29D30/66—Moulding treads on to tyre casings, e.g. non-skid treads with spikes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/122—Soles
    • 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
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • 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
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
    • B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
    • 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
    • B60C9/0042—Reinforcements made of synthetic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
    • B29D30/66—Moulding treads on to tyre casings, e.g. non-skid treads with spikes
    • B29D2030/665—Treads containing inserts other than spikes, e.g. fibers or hard granules, providing antiskid properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles

Definitions

  • the field of the invention is that of articles, for example, tires, shoes, conveyors or caterpillar tracks, in particular for tire treads, and that of production methods of the articles.
  • Articles, for example tires comprise external portions, for example tire treads made of rubber compositions, and the external portions are provided with an incisions, slits, holes or combinations thereof in order to adjust the rigidities of the external portions and to improve performances of the articles as the following patent literature 1 discloses.
  • the articles having the external portions provide with the holes are industrially produced for example using methods described in the patent literature 2.
  • the holes are formed using special tools such as needles or fingers which penetrate the portion on faces thereof during curing of the article.
  • the form of the holes depends on that of the special tools, and there is some risk that the holes, the external portions other than the holes or both suffer damage from the special tools when the special tools remove from the external portions.
  • an article for a rubber article, in particular a tire, a shoe, a conveyor or a caterpillar track tread, in more particular a tire and a specific production method of the article, which allows excellently producing an article comprising a portion provided with a hole(s) externally opening, without using the above special tools such as needles or fingers.
  • elastomer matrix is understood to mean, in a given composition, all of the elastomers present in said rubber composition.
  • each Tg DSC glass transition temperature
  • DSC Densilic Acid
  • any interval of values denoted by the expression “between a and b” represents the range of values of more than “a” and of less than “b” (i.e. the limits a and b excluded) whereas any interval of values denoted by the expression “from a to b” means the range of values going from “a” to “b” (i.e. including the strict limits a and b).
  • composition comprising the mixture(s), the product of the reaction of the various constituents used or both, some of the constituents being able or intended to react together, at least partly, during the various manufacturing phases of the composition, in particular during the vulcanization (curing).
  • a tire has a geometry of revolution about an axis of rotation
  • the geometry of the tire is generally described in a meridian plane containing the axis of rotation of the tire, and the following definitions of directions of the tire are understood in the present application: - A radial direction is a direction perpendicular to the axis of rotation of the tire; - An axial direction is a direction parallel to the axis of rotation of the tire; - A circumferential direction is a direction perpendicular to the meridian plane.
  • a plane being perpendicular to the axis of rotation of the tire and passing through the middle of a tread surface of the tire is referred to as an equatorial plane of the tire.
  • expressions “radially”, “axially” and “circumferentially” respectively mean “in the radial direction”, “in the axial direction” and “in the circumferential direction”.
  • Expressions “radially on the inside (radially inner or radially internal), or respectively radially on the outside (radially outer or radially external)” mean “closer or, respectively, further away, from the axis of rotation of the tire, in the radial direction, than”.
  • Expressions “axially on the inside (axially inner or axially interior) or respectively axially on the outside (axially outer or axially exterior)” mean “closer or, respectively further away, from the equatorial plane, in the axial direction, than”.
  • Respective dimensions of a given element in the radial, axial and circumferential directions will also be denoted “radial thickness or height”, “axial width” and “circumferential length” of this element.
  • Expression “laterally” means “in the circumferential or axial direction”.
  • X extending substantially perpendicularly to Y means the angle from the extending direction of X (or X) to Y is from 80 to 100 degrees, preferably from 85 to 95 degree.
  • X extending substantially parallelly to Y means the angle from the extending direction of X to Y is from -10 to 10 degrees, preferably from -5 to 5 degree.
  • a first aspect of the invention is an article comprising a portion (10) comprising a rubber composition cured or intended to be cured, preferably a cured rubber composition, at a curing temperature; the portion (10) provided with at least one external face (12) and at least one fiber (11) passing through the portion (10); the fiber (11) comprising a thermoplastic resin exhibiting a melting point higher than the curing temperature; and the fiber (11) having a cross section area (s) on the external face (12).
  • the curing temperature is between 110°C and 190°C.
  • the curing time is between 5 and 90 min.
  • external face (12) means a face which is in contact either with the air or with an inflating gas.
  • thermoplastic is a plastic material, a polymer or a copolymer, that becomes pliable or moldable above a specific temperature and solidifies upon cooling.
  • the melting point is a well-known basic physical constant (available, for example, in “Handbook of Chemistry and Physics”) of organic or inorganic compounds; it can be monitored by any known method, for example by the Thiele method, the Kofler bench method or else by DSC analysis.
  • the fiber (11) has the cross sectional area on the external face (12) of the portion (10) of the article according to the first aspect, that is, the tip part of the fiber on the external face (12) is in contact either with the air or with an inflating gas.
  • the fiber (11) predominately comprises the thermoplastic resin, that is, the fiber (11) comprises more than 50% by weight of the thermoplastic resin per 100% by weight of the fiber (11), preferably the fiber (11) comprises more than 60%, more preferably more than 70%, still more preferably more than 80%, particularly more than 90%, by weight of the thermoplastic resin per 100% of the fiber (11).
  • the cross section of the fiber (11) on the external face (12) is polygonal, elliptical or circular.
  • the specific portion (10) (in particular, a tire tread, a shoe sole, a conveyor belt or a caterpillar track tread, in more particular a tire tread) of the article according to the invention and the specific production method according to the invention allow excellently producing an article comprising a portion (10) provided with a hole(s) (13) externally opening, without using the above special tools such as needles or fingers.
  • a second aspect of the invention is the article according to the first aspect, wherein the cross sectional area (s) of the fiber (11) on the external face (12) is more than 1.0 mm 2 (for example, between 1.0 and 100.0 mm 2 ), preferably more than 1.5 mm 2 (for example, between 1.5 and 60.0 mm 2 ), more preferably more than 1.5 mm 2 (between 2.0 and 20 mm 2 ), which can allow not only excellently, but also efficiently producing an article comprising a portion (10) provided with a hole(s) (13) externally opening, without using the above special tools such as needles or fingers.
  • the cross sectional area (s) of the fiber (11) on the external face (12) is more than 1.0 mm 2 (for example, between 1.0 and 100.0 mm 2 ), preferably more than 1.5 mm 2 (for example, between 1.5 and 60.0 mm 2 ), more preferably more than 1.5 mm 2 (between 2.0 and 20 mm 2 ), which can allow not only excellently, but also efficiently producing an article comprising a portion (10)
  • a third aspect of the invention is the article according to the first aspect or the second aspect, wherein the section of the fiber (11) on the external face (12) is substantially circular and wherein its diameter is more than 1.5 mm, preferably between 1.5 and 10.0 mm, more preferably between 1.5 and 5.0 mm.
  • each diameter of the fiber (11) is different from the average diameter of the fiber (11) by less than 10%, preferably at most 5%, by length per 100% by length of the average diameter.
  • a fourth aspect of the invention is the article according to any one of the first to the third aspects, wherein a difference between the curing temperature and the melting point of the thermoplastic resin is more than 10°C, preferably more than 20°C, more preferably more than 30°C, still more preferably at least 40°C.
  • a fifth aspect of the invention is the article according to any one of the first to the fourth aspects, wherein the thermoplastic resin exhibits a melting point of between 170 and 270 °C, preferably between 180 and 260 °C, more preferably between 190 and 250 °C, still more preferably from 195 to 245 °C.
  • thermoplastic resin is a thermoplastic resin dissolvable in a solvent.
  • thermoplastic resin dissolvable in the solvent means the solubility of the thermoplastic resin in the solvent at 23 °C under a pressure equal to 1 atm is higher than 1 g/100ml, more preferably higher than 5 g/100ml, still more preferably higher than 10 g/100ml.
  • the solvent may be water, an organic solvent(s) (for example, alcohol, acetone and hexane), or combinations thereof, preferably, water, an alcohol(s) (for example, methanol, ethanol and n-propanol) or combinations thereof.
  • an organic solvent(s) for example, alcohol, acetone and hexane
  • an alcohol(s) for example, methanol, ethanol and n-propanol
  • thermoplastic resin is a water soluble thermoplastic resin.
  • thermoplastic resin is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyvinylidene chloride, nylon 6, nylon 66, nylon 12, polyacetal, polyetherimide, polysulfone, polyvinyl alcohol and combinations thereof.
  • thermoplastic resin is polyvinyl alcohol, preferably poly butenediol-vinyl alcohol.
  • a tenth aspect of the invention is the article according to any one of the first to the ninth aspects, wherein the fiber (11) is made of monofilament, multifilament or combinations thereof, preferably monofilament or multifilament, more preferably monofilament.
  • An eleventh aspect of the invention is the article according to any one of the first to the tenth aspects, wherein the fiber (11) has an average length by number of less than 50 mm (for example, between 0 and 50 mm), preferably less than 40 mm (for example, between 1 and 40 mm).
  • the average length by number may be measured in accordance with JIS L 1015: 2010.
  • a twelfth aspect of the invention is the article according to any one of the first to the eleventh aspects, wherein the portion (10) is provided with a plurality of the fibers (11).
  • each of the fibers (11) has a cross sectional area on the external face (12), and each of the cross sectional areas is more than 1.0 mm 2 (for example, between 1.0 and 100.0 mm 2 ), preferably more than 1.5 mm 2 (for example, between 1.5 and 60.0 mm 2 ), more preferably more than 1.5 mm 2 (between 2.0 and 20.0 mm 2 ).
  • a thirteenth aspect of the invention is the article according to the twelfth aspect, wherein the fibers (11) are arranged in substantially parallel to each other.
  • a fourteenth aspect of the invention is the article according to the twelfth aspect or the thirteenth aspect, wherein the fibers (11) are substantially uniformly distributed over the external face (12), that is, the cross sections of the fibers (11) are substantially uniformly distributed over the external face (12).
  • a fifteenth aspect of the invention is the article according to any of the first to the fourteenth aspects, wherein the article after curing is intended to come into contact with the ground.
  • a sixteenth aspect of the invention is the article according to the fifteenth aspect, wherein the external face (12) forms an angle other than 0 degree with the surface of the ground, preferably the angle is from 10 to 90 degree, more preferably from 20 to 90 degree, still more preferably from 30 to 90 degree, particularly from 40 to 90 degree, more particularly from 50 to 90 degree, still more particularly from 60 to 90 degree, advantageously from 70 to 90 degree.
  • the external face (12) is substantially perpendicular to the surface of the ground.
  • a seventeenth aspect of the invention is the article according to the fifteenth aspect or the sixteenth aspect, wherein the fiber(s) (11) extends substantially parallelly to the surface of the ground.
  • An eighteenth aspect of the invention is the article according to any one of the fifteenth to the seventeenth aspects, wherein the portion (10) is not intended to come into contact with the ground during the service life of the article.
  • the article is a tire (1), and the portion (10) is an under-tread(s) of the tire (1).
  • a nineteenth aspect of the invention is the article according to any one of the fifteenth to the seventeenth aspects, wherein the portion (10) is not intended to come into contact with the ground during the service life of the article.
  • the article is a tire (1), and the portion (10) is a tread block(s), a tread rib(s) or the both of the tire (1).
  • the article is a tire (1)
  • the portion (10) is a cap-tread(s), a sub-tread(s) or the both of the tire (1), preferably a sub-tread(s) of the tire (1).
  • the sub-tread(s) is positioned radially inner than the cap-tread(s) in the tire (1).
  • a twentieth aspect of the invention is the article according to the nineteenth aspect, wherein the portion (10) is that the rubber composition adjacent to the fiber(s) (11) is not intended to come into contact with the ground during the service life of the article.
  • the service life means the duration to use the tire (1) (for example, the term from the new state to the final state of the tire, the final state means a state on reaching the wear indicator bar(s) in the tread (2) of tire (1)).
  • a twenty first aspect of the invention is the article according to any one of the first to the twentieth aspects, wherein the article is a tire (1), a shoe, a conveyor or a caterpillar track.
  • the article is a shoe, preferably, the portion (10) is comprised of a shoe sole.
  • the article is a conveyor, preferably, the portion (10) is comprised of a conveyor belt.
  • the article is a caterpillar track, preferably the portion (10) is comprised of a caterpillar track tread.
  • a twenty second aspect of the invention is the article according to the twenty first aspect, wherein the article is a tire (1).
  • the tire (1) is particularly intended to be equipped to passenger motor vehicles, including 4 ⁇ 4 (four-wheel drive) vehicles and SUV (Sport Utility Vehicles) vehicles, and also industrial vehicles in particular chosen from vans and heavy duty vehicles (i.e., bus or heavy road transport vehicles (lorries, tractors, trailers)).
  • passenger motor vehicles including 4 ⁇ 4 (four-wheel drive) vehicles and SUV (Sport Utility Vehicles) vehicles
  • SUV Sport Utility Vehicles
  • industrial vehicles in particular chosen from vans and heavy duty vehicles (i.e., bus or heavy road transport vehicles (lorries, tractors, trailers)).
  • the portion (10) is a tread (2), a sidewall(s), an inner layer or combinations thereof, preferably a tread (2), a sidewall(s) or combinations thereof.
  • a twenty third aspect of the invention is the article according to the twenty second aspect, wherein the fiber(s) (11) extends substantially parallelly to an axial direction of a tire (1).
  • a twenty fourth aspect of the invention is the article according to the twenty second aspect, wherein the fiber(s) (11) extends substantially parallelly to a circumferential direction of a tire (1).
  • a twenty fifth aspect of the invention is the article according to any one of the twenty second to the twenty fourth aspects, wherein the portion (10) is comprised of a tread (2) of a tire (1).
  • the portion (10) is comprised of a cap-tread(s), a sub-tread(s), an under-tread(s) or combinations thereof, of a tread (2) of a tire (1), preferably a sub-tread(s), an under-tread(s) or the both, of a tread (2) of a tire (1), more preferably of an under-tread(s), of a tread (2) of a tire (1).
  • Fig. 1 shows a schematic view of a cross sectional view of a portion (10) of an article according to the invention.
  • Fig. 2 shows a schematic view of a cross sectional view of a cured portion (10c) of a cured article produced by a production method according to the invention, the production method comprising at least a step of removing fibers (11) from an article shown in Fig. 1 after curing the article.
  • Fig. 3 shows a schematic view of a cross sectional view of a portion (10) of an article according to the invention.
  • FIG. 4 shows a schematic view of a cross sectional view of a cured portion (10c) of a cured article produced by a production method according to the invention, the production method comprising at least a step of removing fibers (11) from an article shown in Fig. 3 after curing the article.
  • FIG. 1 to 4 schematically (in particular not to a specific scale) represents, in the cross section of the portion (10) of the article.
  • the article is a tire (1) that comprises the portion (10) comprising a rubber composition.
  • the portion (10) is an under-tread comprised of a tread (2) of the tire (1), the portion (10) is provided with a plurality of fibers (11) and an external face (12) forming an angle other than 0 degree with the surface of the ground.
  • the fibers (11) pass through the portion (10), the fibers (11) are arranged in substantially parallel to each other, the fibers (11) extends substantially parallelly to the axial direction (A) and substantially perpendicularly to the radial direction (R) of the tire (1), each of the fibers (11) has a circular cross section having an area (s) and diameter (d) on the external face (12), and the circular cross sections of fibers (11) on the external face (12) are a distributed at a substantially equal interval (t) over the external face (12).
  • the fibers (11) can remain in the portion (10) because the fibers (11) comprise a thermoplastic resin exhibiting a melting point higher than the curing temperature.
  • the article is a cured tire (1c) that comprises the cured portion (10c) comprising a cured rubber composition.
  • the cured portion (10c) is a cured under-tread comprised of a cured tread (2) of the cured tire (1c), the cured portion (10c) is provided with a plurality of a cured external face (12c) and holes (13), instead of the fibers (11) in Fig. 1.
  • the holes (13) are formed by that the fibers (11) are removed from the tire (1) by applying an ultrasonic wave(s) to the tire (1), that is, to the fibers (11) with which the tire (1) is provided, after curing the tire (1) in Fig. 1.
  • the article is a tire (1) that comprises the portion (10) comprising a rubber composition.
  • the portion (10) is a sub-tread comprised of a tread block of a tread (2) of the tire (1), the portion (10) is provided with a plurality of fibers (11) and an external face (12) forming an angle other than 0 degree with the surface of the ground.
  • the fibers (11) pass through the portion (10), the fibers (11) are arranged in substantially parallel to each other, the fibers (11) extends substantially parallelly to the circumferential direction (C) and substantially perpendicularly to the radial direction (R) of the tire (1), each of the fibers (11) has a circular cross section having an area (s) and a diameter (d) on the external face (12), and the circular cross sections of fibers (11) on the external face (12) are distributed at a substantially equal interval (t) over the external face (12).
  • the fibers (11) can remain in the portion (10) because the fibers (11) comprise a thermoplastic resin exhibiting a melting point higher than the curing temperature.
  • the article is a cured tire (1c) that comprises the cured portion (10c) comprising a cured rubber composition.
  • the cured portion (10c) is a cured sub-tread comprised of a cured tread block of a cured tread (2c) of the cured tire (1), the cured portion (10c) is provided with a cured external face (12c) and a plurality of holes (13), instead of the fibers in Fig. 3.
  • the holes (13) are formed by that the fibers (11) are removed from the tire (1) by applying an ultrasonic wave(s) to the tire (1), that is, to the fibers (11) with which the tire (1) is provided, after curing the tire (1) in Fig. 3.
  • FIG. 1 shows, on the external face (12), a cross section of the portion (10) which forms a cuboid having a length (L: 25 mm), a width (W: 30 mm), and a thickness (T: 5 mm).
  • a twenty sixth aspect of the invention is the article according to any one of the first to twenty fifth aspects, wherein the rubber composition is based on an elastomer matrix.
  • Elastomer (or loosely “rubber”, the two terms being regarded as synonyms) of the “diene” type is to be understood in a known manner as an (meaning one or more) elastomer derived at least partly (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or not).
  • diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
  • essentially unsaturated is understood to mean a diene elastomer resulting at least in part from conjugated diene monomers having a content of units of diene origin (conjugated dienes) which is greater than 15% (mol %); thus it is that diene elastomers such as butyl rubbers or diene/ ⁇ -olefin copolymers of the EPDM type do not fall under the preceding definition and may especially be described as “essentially saturated” diene elastomers (low or very low content of units of diene origin, always less than 15%).
  • the expression “highly unsaturated” diene elastomer is understood to mean in particular a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
  • diene elastomer capable of being used in the compositions in accordance with the invention is understood in particular to mean: (a) - any homopolymer obtained by polymerization of a conjugated diene monomer, preferably having from 4 to 12 carbon atoms; (b) - any copolymer obtained by copolymerization of one or more conjugated dienes with one another or with one or more vinyl aromatic compounds preferably having from 8 to 20 carbon atoms.
  • conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1 ,3-butadiene or 2-methyl-3-isopropyl-1 ,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene or 2,4-hexadiene.
  • 1,3-butadiene 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1 ,3-
  • vinylaromatic compounds styrene, ortho-, meta- or para-methylstyrene, the“vinyltoluene” commercial mixture, para-(tert-butyl) styrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene or vinylnaphthalene.
  • a twenty seventh aspect of the invention is the article according to the twenty sixth aspect, wherein the elastomer matrix comprises at least one diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), butadiene copolymers, isoprene copolymers and combinations thereof; such copolymers are preferably selected from the group consisting of butadiene copolymers combinations thereof, more preferably selected from the group consisting of styrene-butadiene copolymers (SBR), butadiene-isoprene copolymers (BIR), styrene-isoprene copolymers (SIR), styrene-butadiene-isoprene copolymers (SBIR) and combinations thereof, still more preferably selected from the group consisting of styrene-butadiene copolymers (SBR) and combinations thereof.
  • SBR sty
  • the diene elastomer may have any microstructure which depends on the polymerization conditions used, in particular on the presence or absence of a modifying agent, randomizing agent, or both and on the amounts of modifying agent, randomizing agent, or both employed.
  • This elastomer may, for example, be a block, statistical, sequential or micro sequential elastomer and may be prepared in dispersion or in solution.
  • This elastomer may be coupled, star-branched, or both; or else functionalized with a coupling, star-branching, or both; or functionalizing agent.
  • the elastomer matrix comprises more than 50 phr (for example, more than 50 phr and up to 100 phr) of a first diene elastomer which is a styrene-butadiene copolymer, advantageously a solution styrene-butadiene copolymer, and optionally comprising less than 50 phr (for example, 0 phr to less than 50 phr) of a second diene elastomer which is different from the first diene elastomer.
  • the styrene-butadiene copolymer exhibits a styrene unit of less than 30% by weight (for example, between 3 and 30% by weight) per 100% by weight of the styrene-butadiene copolymer, preferably less than 27% by weight (for example, between 5 and 27% by weight), more preferably less than 23% by weight (for example, between 7 and 23% by weight), still more preferably less than 20% by weight (for example, between 10 and 20% by weight), particularly at most 18% by weight (for example, from 12 to 18%).
  • the styrene unit can be determined by 1H NMR method in accordance with ISO 21561.
  • the styrene-butadiene copolymer exhibits a glass transition temperature of less than -40°C (for example, between -40°C and -110°C), preferably less than -45°C (for example, between -45°C and -105°C), more preferably less than -50°C (for example, between -50°C and -100°C), still more preferably less than -55°C (for example, between -55°C and -95°C), particularly at most -60°C (for example, -60°C to -90°C).
  • a glass transition temperature of less than -40°C (for example, between -40°C and -110°C), preferably less than -45°C (for example, between -45°C and -105°C), more preferably less than -50°C (for example, between -50°C and -100°C), still more preferably less than -55°C (for example, between -55°C and -95°
  • a twenty eighth aspect of the invention is the article according to any one of the first to the twenty seventh aspects, wherein the rubber composition is based on a reinforcing filler.
  • the reinforcing filler may comprise a reinforcing organic filler (for example, carbon black), a reinforcing inorganic filler (for instance, silica) or combinations thereof.
  • a reinforcing organic filler for example, carbon black
  • a reinforcing inorganic filler for instance, silica
  • a twenty ninth aspect of the invention is the article according to the twenty eighth aspect, wherein the amount of reinforcing filler is more than 50 phr (for example, between 50 and 300 phr), preferably more than 60 phr (for example, between 60 and 280 phr), more preferably more than 70 phr (for example, between 70 and 260 phr), still more preferably more than 80 phr (for example, between 80 and 240 phr), particularly more than 90 phr (for example, between 90 and 220 phr), more particularly more than 100 phr (for example, between 100 and 200 phr), still more particularly more than 110 phr (for example, between 110 and 180 phr).
  • the amount of reinforcing filler is more than 50 phr (for example, between 50 and 300 phr), preferably more than 60 phr (for example, between 60 and 280 phr), more preferably more than 70 phr (
  • Use may be made of any type of reinforcing filler known for its capabilities of reinforcing a rubber composition which can be used for the manufacture of tires, for example a reinforcing organic filler, such as carbon black, or a reinforcing inorganic filler, such as silica, with which a coupling agent is combined in a known way.
  • a reinforcing organic filler such as carbon black
  • a reinforcing inorganic filler such as silica
  • carbon blacks all carbon blacks conventionally used in tires (“tire-grade” blacks) are suitable, such as for example reinforcing carbon blacks of the 100, 200 or 300 series in ASTM grades (such as for example, the N115, N134, N234, N326, N330, N339, N347 or N375 blacks), or carbon blacks higher series, the 500, 600, 700 or 800 series in ASTM grades (such as for example the N550, N660, N683, N772, N774 blacks).
  • the carbon blacks might for example be already incorporated in an elastomer matrix, for instance, a diene elastomer, in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
  • filler should be understood here to mean any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also referred to as “white filler”, “clear filler” or even “non-black filler”, in contrast to carbon black, capable of reinforcing by itself alone, without means other than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words capable of replacing, in its reinforcing role, a conventional tire-grade carbon black; such a filler is generally characterized, in a known manner, by the presence of hydroxyl (-OH) groups at its surface.
  • -OH hydroxyl
  • this filler is unimportant, whether it is in the form of powder, granules, beads or any other suitable densified form.
  • the reinforcing inorganic filler of the mixtures of various reinforcing inorganic fillers preferably of highly dispersible siliceous filler(s), aluminous filler(s), or both is described hereafter.
  • Mineral fillers of the siliceous type preferably silica (SiO 2 )
  • the aluminous type preferably alumina (Al 2 O 3 )
  • the reinforcing inorganic fillers are suitable in particular as the reinforcing inorganic fillers.
  • a thirtieth aspect of the invention is the article according to the twenty eighth aspect or the twenty ninth aspect, wherein the reinforcing filler predominately comprises a reinforcing inorganic filler, that is, the reinforcing filler comprises more than 50% by weight of the reinforcing inorganic filler per 100% of the reinforcing filler, preferably the reinforcing filler comprises more than 60%, more preferably more than 70%, still more preferably more than 80%, particularly more than 90%, by weight of the reinforcing inorganic filler per 100% of the reinforcing filler.
  • a thirty first aspect of the invention is the article according to the thirtieth aspect, wherein the reinforcing inorganic filler predominately comprises silica, that is, the reinforcing inorganic filler comprises more than 50% by weight of silica per 100% of the reinforcing inorganic filler, preferably the reinforcing inorganic filler comprises more than 60%, more preferably more than 70%, still more preferably more than 80%, particularly more than 90%, more particularly 100%, by weight of silica per 100% of the reinforcing inorganic filler.
  • the silica may be a type of silica or a blend of several silicas.
  • the silica used may be any reinforcing silica known to a person skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface area and a CTAB specific surface area that are both less than 450 m 2 /g, preferably from 20 to 400 m 2 /g, more preferably 50 to 350 m 2 /g, still more preferably 100 to 300 m 2 /g, particularly between 150 and 250 m 2 /g, wherein the BET surface area is measured according to a known method, that is, by gas adsorption using the Brunauer-Emmett-Teller method described in “The Journal of the American Chemical Society”, Vol.
  • HDSs highly dispersible precipitated silicas
  • pyrogenic silicas for example, of “CAB-O-SIL S-17D” from Cabot, “HDK T40” from Wacker, “Aeroperl 300/30”, “Aerosil 380”, “Aerosil 150” or “Aerosil 90” from Evonik.
  • Such silica may be covered, for example, “CAB-O-SIL TS-530” covered with hexamethyldiasilazene or “CAB-O-SIL TS-622” covered with dimethyldichlorosilane from Cabot.
  • a reinforcing filler of another nature, in particular organic nature, such as carbon black might be used as filler equivalent to the reinforcing inorganic filler described in the present section, provided that this reinforcing filler is covered with an inorganic layer, such as silica, or else comprises, at its surface, functional sites, in particular hydroxyls, requiring the use of a coupling agent in order to form the connection between the filler and the elastomer.
  • an inorganic layer such as silica
  • a thirty second aspect of the invention is the article according to any one of the twenty eighth to the thirty first aspects, wherein the reinforcing filler comprises less than 50 phr (for example, between 0 and 50 phr), preferably less than 40 phr (for example, between 0 and 40 phr), more preferably less than 30 phr (for example, between 0 and 30 phr), still more preferably less than 20 phr (for example, between 0 and 30 phr), particularly less than 15 phr (for example, between 1 and 15 phr), more particularly less than 10 phr (for example, between 2 and 10 phr), of carbon black.
  • the reinforcing filler comprises less than 50 phr (for example, between 0 and 50 phr), preferably less than 40 phr (for example, between 0 and 40 phr), more preferably less than 30 phr (for example, between 0 and 30 phr), still more
  • silane polysulfides referred to as “symmetrical” or “asymmetrical” depending on their particular structure, as described, for example, in applications WO 03/002648, WO 03/002649 and WO 2004/033548.
  • silane polysulfides correspond to the following general formula (I): (I) Z - A - Sx - A - Z , in which: - x is an integer from 2 to 8 (preferably from 2 to 5); - A is a divalent hydrocarbon radical (preferably, C 1 -C 18 alkylene groups or C 6 -C 12 arylene groups, more particularly C 1 -C 10 , in particular C 1 -C 4 , alkylenes, especially propylene); - Z corresponds to one of the formulae below: in which: - the R 1 radicals which are unsubstituted or substituted and identical to or different from one another, represent a C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl group (preferably, C 1 -C 6 alkyl, cyclohexyl or phenyl groups, in particular C 1 -C 4 alkyl groups, more particularly methyl, ethyl
  • the mean value of the "x" indices is a fractional number preferably of between 2 and 5, more preferably of approximately 4.
  • silane polysulfides of bis((C 1 -C 4 )alkoxyl(C 1 -C 4 )alkylsilyl(C 1 -C 4 )alkyl)polysulfides (in particular disulfides, trisulfides or tetrasulfides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl)polysulfides.
  • TESPT bis(3-triethoxysilylpropyl)tetrasulfide
  • TESPD bis(3-triethoxysilylpropyl)disulfide
  • silanes bearing at least one thiol (-SH) function referred to as mercaptosilanes
  • at least one blocked thiol function or both such as described, for example, in patents or patent applications US 6 849 754, WO 99/09036, WO 2006/023815, WO 2007/098080, WO 2008/055986 and WO 2010/072685.
  • the content of coupling agent may be from 0.5 to 15% by weight per 100% by weight of the reinforcing inorganic filler, preferably silica.
  • the amount of coupling agent may be less than 30 phr (for example, between 0.1 and 30 phr), preferably less than 25 phr (for example, between 0.5 and 25 phr), more preferably less than 20 phr (for example, between 1 and 20 phr).
  • the rubber composition of the portion (10) of the article according to the invention may be based on all or a part(s) of the usual additives generally used in the elastomer compositions for articles (for example, tires, shoes, conveyor or caterpillar tracks), such as, for example, protection agents, such as antiozone waxes, chemical antiozonants, antioxidants, plasticizing agents, tackifying resins, methylene acceptors (for example phenolic novolak resin) or methylene donors (for example HMT or H3M hexamethylenetetramine (HMT) or hexamethoxymethylmelamine (H3M)), a crosslinking system based either on sulfur, or on donors of sulfur, or peroxide, or bismaleimides or combination thereof, vulcanization accelerators, or vulcanization activators.
  • protection agents such as antiozone waxes, chemical antiozonants, antioxidants, plasticizing agents, tackifying resins, methylene acceptors (for example phenolic novolak
  • the rubber composition can be also based on coupling activators when a coupling agent is used, agents for covering the reinforcing inorganic filler or more generally processing aids capable, in a known way, by virtue of an improvement in the dispersion of the filler in the rubber matrix and of a lowering of the viscosity of the compositions, of improving their property of processing in the raw state; these agents are, for example, hydrolysable silanes, such as alkylalkoxysilanes, polyols, polyethers, amines, or hydroxylated or hydrolysable polyorganosiloxanes.
  • hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, amines, or hydroxylated or hydrolysable polyorganosiloxanes.
  • a thirty third aspect of the invention is the article according to any one of the first to the thirty second aspects, wherein the rubber composition is based on no blowing agent or based on less than 5 phr, preferably less than 2 phr, more preferably less than 1 phr, still more preferably less than 0.5 phr, particularly less than 0.1 phr, of a blowing agent.
  • the blowing agent is a compound which can decompose thermally and which is intended to release, during thermal activation, for example during the vulcanization of the article (for example a tire), a large amount of gas and to thus result in the formation of bubbles.
  • the blowing agent is preferably selected from a group of compounds consisting of: azo, nitroso, hydrazine, carbazide, semicarbazide, tetrazole, carbonate, citrate, and combinations thereof.
  • the rubber composition of the portion (10) of the article according to the invention may be manufactured in appropriate mixers using two successive preparation phases well known to a person skilled in the art: a first phase of thermomechanical working or kneading (referred to as “non-productive” phase) at high temperature, up to a maximum temperature of between 110°C and 190°C, preferably between 130°C and 180°C, followed by a second phase of mechanical working (referred to as “productive” phase) at a lower temperature, typically of less than 110°C, for example between 40°C and 100°C, finishing phase during which the crosslinking or vulcanization system is incorporated.
  • a first phase of thermomechanical working or kneading referred to as “non-productive” phase
  • productive phase a second phase of mechanical working
  • a process which can be used for the manufacture of such compositions comprises, for example and preferably, the following steps: - incorporating in the elastomer matrix, for instance, the diene elastomer(s), in a mixer, the reinforcing filler, during a first stage (“non productive” stage) everything being kneaded thermomechanically (for example in one or more steps) until a maximum temperature of between 110°C and 190°C is reached; - cooling the combined mixture to a temperature of less than 100°C; - subsequently incorporating, during a second stage (referred to as a "productive" stage), a crosslinking system; - kneading everything up to a maximum temperature of less than 110°C.
  • the first (non-productive) phase is carried out in a single thermomechanical stage during which all the necessary constituents may be introduced into an appropriate mixer, such as a standard internal mixer, followed, in a second step, for example after kneading for 1 to 2 minutes, by the other additives, optional additional filler-covering agents or processing aids, with the exception of the crosslinking system.
  • the total kneading time, in this non-productive phase is preferably between 1 and 15 min.
  • the crosslinking system is preferably based on sulfur and on a primary vulcanization accelerator, in particular on an accelerator of sulfenamide type.
  • a primary vulcanization accelerator in particular on an accelerator of sulfenamide type.
  • various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (in particular diphenylguanidine), and the like, incorporated during the first non-productive phase, during the productive phase or both.
  • the content of sulfur is preferably between 0.5 and 10.0 phr, more preferably between 0.5 and 3.0 phr, and that of the primary accelerator is preferably between 0.5 and 5.0 phr.
  • accelerator primary or secondary of any compound capable of acting as accelerator of the vulcanization of elastomer matrix, for instance, diene elastomers, in the presence of sulfur, in particular accelerators of the thiazoles type and their derivatives, accelerators of thiurams types, or zinc dithiocarbamates.
  • accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated to “MBTS”), N-cyclohexyl-2-benzothiazole sulfenamide (abbreviated to “CBS”), N,N-dicyclohexyl-2 benzothiazolesulfenamide (“DCBS”), N-tert-butyl-2-ben zothiazolesulfenamide (“TBBS”), N-tert-butyl-2 benzothiazolesulfenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ZBEC”), Tetrabenzylthiuram disulfide (“TBZTD”) and combinations thereof.
  • MBTS 2-mercaptobenzothiazyl disulfide
  • CBS N-cyclohexyl-2-benzothiazole sulfenamide
  • DCBS N,N-dicyclohexyl-2 benzothiazolesulf
  • the fiber(s) (11) of the portion (10) of the article according to the invention is embedded in the rubber composition obtained in the above, and the rubber composition with the fiber(s) (11) is subsequently calendered, for example in the form of a sheet or of a plaque, in particular for laboratory characterization, or else extruded in the form of a rubber profiled element which can be used directly as a part of a portion (10) of an article, for example, a tire tread (2), a shoe sole, a conveyor belt and a caterpillar track tread.
  • each of the tip(s) of the fiber(s) (11) appears on a surface of the sheet or the plaque (as the external face (12) of the portion (10) of the article according to the invention), that is, each of the fiber(s) (11) has a cross section on the surface of the sheet or the plaque.
  • the curing (or vulcanization) is carried out at a temperature lower than a melting point of a thermoplastic resin which the fiber(s) (11) comprises, in order to prevent the thermoplastic resin from melting during the vulcanization.
  • a thirty fourth aspect of the invention is a production method of a cured article, comprising at least a step of removing a fiber(s) (11) from an article according to any one of the first to thirty third aspects by an ultrasonic wave(s) after curing the article comprising a portion (10) comprising a rubber composition at a curing temperature, the portion (10) provided with at least one external face (12) and the fiber(s) (11) passing through the portion (10), the fiber (11) comprising a thermoplastic resin exhibiting a melting point higher than the curing temperature, and the fiber(s) (11) having a cross sectional area on the external face (12).
  • thermoplastic resin comprised of the fiber(s) (11) with which the article is provided can be melted by applying the ultrasonic wave(s) to the article.
  • thermoplastic resin is a thermoplastic resin dissolvable in a solvent.
  • a thirty sixth aspect of the invention is the production method according to the thirty fifth aspect, wherein the step of removing the fiber(s) (11) from the article by the ultrasonic wave(s) occurs in the solvent.
  • thermoplastic resin can be dissolved in the solvent, and it can flow out from the cross section on the external face (12).
  • a thirty seventh aspect of the invention is the production method according to the thirty fifth aspect or the thirty sixth aspect, wherein the solvent is water, methanol, ethanol n-propanol or combinations thereof, preferably water.
  • a thirty eighth aspect of the invention is the production method according to any one of the thirty fifth to the thirty seventh aspect, wherein the solvent has a temperature of at least room temperature (for example, 23 °C), preferably between 50 and 90 °C.
  • a thirty ninth aspect of the invention is the production method according to any one of the thirty fourth to the thirty eighth aspects, wherein the ultrasonic wave(s) has a frequency of more than 20 kHz, preferably between 25 and 100 kHz.
  • the invention relates to the rubber compositions and the above articles, both in the mixed state (after mixing and before curing) and in the cured state (i.e., after crosslinking or vulcanization) unless expressly stated otherwise.
  • T-1 and T-2 Three specimens (identified as T-1 and T-2 (examples according to invention), and T-3 (a comparative example)) comprising a rubber composition were tested.
  • T-1 and T-2 can be a portion (10) of an article according to the invention.
  • the formulation of the rubber composition with the content of the various products expressed in phr is given at Table 1.
  • Each rubber composition was produced as follows: The reinforcing filler, the, the elastomer matrix and the various other ingredients, with the exception of sulfur and a sulfenamide type vulcanization accelerator (as a vulcanization accelerator) in the crosslinking system, were successively introduced into an internal mixer having an initial vessel temperature of approximately 60°C; the mixer was thus approximately 70% full (% by volume). Thermomechanical working (non-productive phase) was then carried out in one stage, which lasts in total approximately 3 to 4 minutes, until a maximum “dropping” temperature of 165°C was reached.
  • the rubber compositions thus obtained were subsequently calendered, either in the form of sheets (thickness of 1 to 3 mm) or of fine sheets of rubber, for the measurement of their physical or mechanical properties, or in the form of profiled elements which could be used directly, after cutting, assembling or both to the desired dimensions, for example as tire semi-finished products, in particular as tire treads (2).
  • thermoplastic fibers means the fibers predominately comprising the thermoplastic resin, that is, the fibers comprising more than 50% by weight of thermoplastic resin per 100% by weight of the fibers) in parallel to each other at each equal interval over each of the sheets to form a laminated cuboid:
  • T-1 Polyvinyl alcohol fiber (cross section area on the external face (12): 2.4 mm 2 , diameter: 1.75 mm, length: 30 mm, amount by weight of poly butenediol vinyl alcohol per 100% by weight of the fiber: more than 99 %, melting point of polyvinyl alcohol: 200 °C, monofilament, produced by Nippon Synthetic Chemical Industry Cooperation);
  • - T-2 Polyvinyl alcohol fiber (cross section area on the external face (12): 4.9 mm 2 , diameter: 2.5 mm, length: 30 mm, amount
  • Each of the laminated cubic was placed in a press with heated platens at a temperature (typically 160 °C), for the time that was necessary for the crosslinking of each of these rubber compositions (typically 25 minutes), at a pressure (typically 16 bar).
  • thermoplastic fibers extended to the direction of the width of the cuboid, and had both tips being in contact with air.
  • thermoplastic fibers were melted, and the space was filled in the rubber composition during the above curing.
  • an ultrasonic wave (the frequency: 42 kHz) generated from an ultrasonic generator (SUS-100, produced by Shimadzu Cooperation) was applied to each of the specimens (T-1, T-2 and T-3) for 16 hours in a water bath, that is, a container of water heated (as a solvent) to a given temperature (from 60 to 80 °C), in order to remove the thermoplastic fibers from each of the specimens.
  • a water bath that is, a container of water heated (as a solvent) to a given temperature (from 60 to 80 °C), in order to remove the thermoplastic fibers from each of the specimens.

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Abstract

La présente invention concerne un article qui comprend une partie (10) comprenant une composition de caoutchouc durcie ou destinée à être durcie à une température de durcissement, la partie (10) étant pourvue d'au moins une face externe (12) et d'au moins une fibre (11) traversant la partie, la fibre (11) comprenant une résine thermoplastique présentant un point de fusion supérieur à la température de durcissement, la fibre (11) possédant une aire de section transversale (s) sur la face externe (12). Dans un mode de réalisation, l'aire de section transversale (s) de la fibre est supérieure à 1,0 mm2. L'invention concerne également un procédé de production d'un article durci comprenant au moins une étape consistant à retirer une fibre dudit article.
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