[go: up one dir, main page]

WO1994018015A1 - Pneumatique leger - Google Patents

Pneumatique leger Download PDF

Info

Publication number
WO1994018015A1
WO1994018015A1 PCT/US1994/001404 US9401404W WO9418015A1 WO 1994018015 A1 WO1994018015 A1 WO 1994018015A1 US 9401404 W US9401404 W US 9401404W WO 9418015 A1 WO9418015 A1 WO 9418015A1
Authority
WO
WIPO (PCT)
Prior art keywords
tire
tires
fibers
cords
pbz
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1994/001404
Other languages
English (en)
Inventor
Kazuyuki Yabuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Priority to US08/491,832 priority Critical patent/US5948186A/en
Priority to EP94908742A priority patent/EP0683734A1/fr
Publication of WO1994018015A1 publication Critical patent/WO1994018015A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles

Definitions

  • the present invention relates to light weight tires.
  • a tire is defined as a "continuous solid or pneumatic rubber cushion encircling a wheel," p. 1237, Webster's Ninth New Collegiate Dictionary, ⁇ 1989 by Merriam-Webster Inc.
  • a tire is made from rubber, fabric, chemicals, and metal (steel). See Tires, pp. 834-861 , of Vol. 16 of the Encyclopedia of Polymer Science and Engineering, ⁇ 1989 by John Wiley & Sons, Inc.
  • a pneumatic tire is a toroidal, high performance polymer composite which includes an external rubber-and-fabric covering. In these tires there are reinforcing cords which provide stability and resistance to bruises, fatigue and heat.
  • the reinforcing cords extend diagonally across the tire from bead- -to-bead. Layers of reinforcing cords are applied at an opposing angle of 30 to 70 degrees to balance the tire strength symmetrically across the tread-center line.
  • a radial tire is a pneumatic tire in which the plies of the reinforcing cords or filaments in the casing run in a radial direction (from bead-to-bead) at a 60 to 90 degree bias or crown angle in relation to the centerline of the tread (which is also the axis of rotation).
  • Steel belts are used in radial tires in order to constrain the 90 degree carcass plies. The belt rigidity is essential to the functioning of the tire. Without it, a radial ply casing would be unstable.
  • polyester cords and/or steel cords are used in the foundation structure or "carcass" (the carcass is that part of the tire between the liner and the tread) of the tire to reinforce the performance of the tire as a pressure container.
  • the first aspect of this invention is a tire characterized in that it contains polybenzazole fibers.
  • the third aspect of this invention is a tire containing polybenzazole fibers characterized in that the polybenzazole fibers are incorporated into the reinforcing belts.
  • the fourth aspect of this invention is a tire containing polybenzazole fibers characterized in that the polybenzazole fibers are incorporated into the carcass of the tire.
  • polybenzazole includes polybenzoxazole
  • PBO polybenzothiazole
  • PBT polybenzothiazole
  • Polybenzoxazole, polybenzothiazole and random, sequential and block copolymers of polybenzoxazole and polybenzothiazole are described in references such as Wolfe et al., Liquid Crystalline Polymer Compositions, Process and Products, U.S. Patent 4,703, 103 (October 27, 1987); Wolfe et al., Liquid Crystalline Polymer Compositions, Process and Products, U.S. Patent 4,533,692 (August 6, 1985); Wolfe et al., Liquid Crystalline Poly(2,6-Benzothiazole) Compositions, Process and Products, U.S. Patent 4,533,724
  • Units within the polybenzazole polymer are preferably chosen so that the polymer is lyotropic liquid-crystalline.
  • Preferred monomer units are illustrated in Formulae (a)- (h).
  • the polymer more preferably consists essentially of monomer units selected from those illustrated in (a)-(h), and most preferably consists essentially of a number of identical units selected from those illustrated in (a)-(c).
  • Solvents suitable for formation of dopes of polybenzazole polymers include cresol as well as non-oxidizing acids capable of dissolving the polymer.
  • suitable acid solvents include polyphosphoric acid, methanesulfonic acid and highly concentrated sulfuric acid and mixtures of those acids.
  • a highly preferred solvent is polyphosphoric acid or methanesulfonic acid.
  • a most highly preferred solvent is polyphosphoric acid.
  • concentration of the polymer in the solvent is preferably at least about 7 weight percent, more preferably at least about 10 weight percent and most preferably at least about 14 weight percent.
  • the maximum concentration is limited primarily by practical factors, such as polymer solubility and, as already described, dope viscosity. Because of these limiting factors, the concentration of polymer is seldom more than 30 weight percent, and usually no more than about 20 weight percent.
  • Suitable polymers or copolymers and dopes can be synthesized by known procedures, such as those described in Wolfe et al., U.S. Patent 4,533,693 (August 6, 1985); Sybert et al., U.S. Patent 4,772,678 (September 20, 1988); and Harris, U.S. Patent 4,847,350 (July 1 1 , 1989).
  • Polybenzazole polymers can be advanced rapidly to high molecular weight at relatively high temperatures and high shear in a dehydrating solvent acid, according to Gregory et al., U.S Patent No 5,089,591.
  • the dope is spun into fibers by known dry-jet, wet-spin techniques in which the dope is spun through a spinneret to form dope filaments that are collected together to form one or more dope fibers.
  • Fiber spinning techniques for PBZ polymers are described in jointly owned, allowed, U.S. Patent Application Numbers 07/985,079 (Method for Spinning a
  • the dope fiber(s) After passing through an air-gap the dope fiber(s) is/are contacted with a fluid that dilutes the solvent and is a non-solvent for the polymer. This contact causes the separation of the polymer from its solvent. This separation process is known as coagulation. After coagulation, most of the remaining residual solvent is washed/leached from each fiber, leaving the fiber wet. See jointly owned, co-pending, U S. Patent Application number 08/1 10, 149 (Improved Process for Coagulation and Washing of Polybenzazole Fibers) for a description of the coagulation process.
  • the fiber After the fiber is dried, it may optionally be heat-treated to improve its physical properties. Heat-treatment of PBZ fiber is described in jointly owned, allowed, U.S. Patent Application Serial Numbers 07/985,068 (Rapid Heat Treatment Method for Polybenzazole Polymer) and 07/985,067 (Steam Heat-Treatment Method for Polybenzazole Fiber).
  • PBZ reinforcing fibers can be used as part of the carcass component of a tire.
  • the carcass of a tire is that part of the tire between the liner and the tread, which is also referred to as the foundation structure, and it includes the reinforcing cord plies.
  • PBZ fibers can also be used in the circumferentially restrictive belt material of a tire.
  • PBZ fibers In order to be useful in tires, PBZ fibers must be formed into cords through a twisting process. See the article by Addis Finney, entitled, “That Left-hand Turn and its Effect on Tires” in the May 1979 issue of Rubber World, for a description and drawing of ply cords and cables PBZ fibers are formed into ply cords by twisting "T/10 cm” is the number of twists per 10 cm of cord. Once PBZ ply cords have been formed, two or more of these ply cords can then be twisted together to make cable cords. The twist number for these cable cords is expressed by the number of cable twists (turns/10 cm) x the number of ply twists (turns/10 cm).
  • twist number can vary from 20 x 20 to 100 x 100.
  • the twist factor for PBZ cords is calculated as follows: twist factor equals (number of twists/ 10 cm) x square root of (total denier of fiber/density of fiber) .
  • the twist factor for PBZ cords used in this application ranges from 800 to 3000.
  • the PBZ ply cords, at this stage, are referred to as a greige cord, which is descriptive of the cords before dipping condition. These PBZ greige cords have a gauge, or thickness of from 30 mm to 60 mm.
  • the greige cords In order to transform the greige cords into a condition such that they can be used to make layers of reinforcing material, or layers of belt material, the greige cords must be dipped in adhesives to form "dipped" cords and/or cables which will then adhere to the other components of a tire.
  • These adhesives can be standard epoxy adhesi ves such as a glycerol polyglycidyl ether or compounds such as PexulTM which is a 2,6-bis(2',4'-dihydroxyphenyl- methyl)-4-chlorophenol compound (this compound is also marketed under the name of Vulcanbond-ETM by Rhone-Poulenc) or RFL (resorcinol formaldehyde latexes) .
  • PexulTM which is a 2,6-bis(2',4'-dihydroxyphenyl- methyl)-4-chlorophenol compound (this compound is also marketed under the name of Vulcanbond-ETM by Rhone-Poulenc) or RFL (resorcinol formaldehyde latexes) .
  • RFL resorcinol formaldehyde latexes
  • the actual dipping is a two-step process wherein the cords/cables are dipped in the first dipping solution, which can contain epoxy or PexulTM as a major adhesive component, and then the cords/cables are exposed to a temperature of from 235°C to 250°C for about 60 seconds.
  • the cords/cables are then contacted with the second dipping solution which can be RFL (resorcinol-formaldehyde latexes) and then exposed to a temperature of 230°C to 240°C for about 60 seconds.
  • RFL resorcinol-formaldehyde latexes
  • PBZ cords/cables Once the PBZ cords/cables have been formed they are incorporated into tires using standard tire making techniques with the tires then being tested for various properties.
  • carcass material for tires used in passenger cars of this invention can be a 2 ply cord of 500 (or less) denier PBZ fiber as compared to a 2 ply cord of 1000 denier p-aramid fiber.
  • Denier is the weight in grams of 9000 meters of the fiber.
  • the performance properties of the cords in the tire are enhanced if the PBZ fiber used to make the cords has a tensile strength of preferably at least about 2.8 GPa, more preferably at least about 4.0 GPa, more highly preferably at least about 5.7 GPa and most preferably about 6.9 GPa, and a tensile modulus of preferably at least about 140 GPa, more preferably at least about 276 GPa and most preferably at least about 380 GPa.
  • the average mean diameter of the voids in the PBZ fiber can be determined by using "Small angle X-ray scattering" techniques which can measure voids in the fiber of smaller than 100 ⁇ .
  • a tire made with PBZ cord in the carcass which has voids with an average diameter of 25 ⁇ or less, has been found to have two times higher durability as compared with the same tire when it is made with PBZ cords that have an average void size of 30 ⁇ or more.
  • passenger car tires could be made that had only PBZ cords in the belts and in the carcass (these would be the lightest tires) and that passenger car tires could be made with steel belts and with PBZ cords in the carcass (these tires would be heavier than tires made with only PBZ cords) and that passenger car tires could be made with PBZ cords in the belts and polyester cords in the carcass (these tires would be less expensive than the other tires).
  • truck/bus tires could be made that had only PBZ cords in the belts and in the carcass (these would be the lightest tires) and that truck/bus tires could be made with steel belts and with PBZ cords in the carcass (these tires would be heavier than tires made with only PBZ cords) and that truck/bus tires could be made with PBZ cords in the belts and steel in the carcass (these tires would be heavier than tires made with only PBZ cords).
  • Measurement of small angle X-rays scattering intensity is performed using suitable X-ray equipment such as a Kratkey camera. About 6 m of sample fiber is wound around a measurement holder, and X-rays are generated underthe condition of 45 kv and 150 mA. A CuKa line filtered with a nickel filter is used for measurement.
  • the collimating slit of a Kratkey camera is 42 mm (length) x 0 14 mm (width) and the receiving slit is 10 mm (length) x 0 14 mm (width).
  • An equatorial scattering of fiber sample is measured from 0 1 degrees to 3 degree with 0.25 degrees of step width for 30 seconds or more of integration. Compensation of background scattering is performed using the following formula from the result of
  • I is an actual intensity
  • l sample is the intensity measured with a measuring sample
  • I air is the intensity measured without sample.
  • the intensity at scattering angle of 0 is measured in order to determine the absorption coefficient of a sample.
  • the measurement of void size is determined by the use of a Guinier plot.
  • the disk fatigue test results are expressed in a percentage of strength retention and the tube fatigue test results are expressed in the number of minutes.
  • the test protocol is based on JIS-L1017-1983.
  • In-door drum test is used for high speed durability and load durability.
  • the test protocol is based on JIS-D4230-1986.
  • the Iife-to-failure of tire is expressed as an index which is compared with 100 for passenger car tires (Table III) and with 100 for truck and bus tires (Table V).
  • Rolling resistance is measured on an in-door drum tester and expressed as an index which is compared to 100 for passenger car tires (Table III), and with 100 for truck and bus tires (Table V).
  • the index is an average value of the tests performed at a speed of from 20 to 150 km/h.
  • the riding feeling is based on a subjective evaluation of a panel ist through actual driving of a vehicle on a test course. The riding feeling is expressed as an index which is compared with 100 for passenger car tires (Table III), and with 100 for truck and bus tires (Table V).
  • Fuel consumption is expressed as an index which is compared with 100 for passenger car tires (Table III) and 100 for truck and bus tires (Table V). The results show that fuel consumption for vehicles with tires with PBO fibers in them is better than it is for vehicles with tires that do not have PBO fibers.
  • High speed durability testing is done by applying a designed load to a tire using an in-door drum tester .
  • the running speed is increased in a stepwise manner as follows:
  • a constant running speed is applied to a tire using an in-door drum test.
  • the load for the tire is increased with stepwise manner as follows:
  • Cornering Power is the cornering force divided by the slip angle. It is expressed as an index which is compared with 100 for passenger car tires (Table III) and 100 for truck and bus tires (Table V).
  • Polyester, para-oriented aramid, and polybenzoxazole fiber were twisted, and 2 ply greige cords were made.
  • the strength coefficient is the value of a tensile strength divided by the square of the cord gauge. The higher this value means the more strength in the cord per unit of thickness. Therefore, this strength coefficient is an important measure of fiber properties for reduction of tire weight.
  • Tires for passenger cars are made using these dipped cords in the carcass and in the reinforcing belts, and the tire performance is tested.
  • the composition of each tire and test results for each tire are shown in Table III.
  • Epoxy is a glycerol polyglycidyl ether (trade name DenakolTM marketed by Nagase)
  • RTL is a resorcinol-formaldehyde-latex
  • Para-oriented aramid fiber and PBO fiber were twisted, and 2-ply greige cords made.
  • Each greige cord was dipped in the same manner as described and shown in Example 1, Table I to make dipped cords.
  • the properties of the dipped cords obtained are shown in Table IV.
  • a radiai-ply tire for use on trucks or busses was made using these dipped PBO cords and/or steel cords, and the performance of these tires was tested.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Tires In General (AREA)

Abstract

Un pneumatique comprenant des fibres de polybenzazole (PBZ) est décrit. Les fibres de PBZ peuvent être utilisées soit comme une partie de la carcasse du pneu, soit comme nappes d'armature de ce dernier, ou les deux. Les pneus fabriqués avec ces fibres de PBZ sont moins lourds que ceux fabriqués avec de l'acier ou d'autres fibres organiques, de sorte que le rendement du carburant de véhicules pourvus de pneus contenant les fibres de PBZ est supérieur à celui de véhicules ne comprenant pas de telles fibres.
PCT/US1994/001404 1993-02-09 1994-02-08 Pneumatique leger Ceased WO1994018015A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US08/491,832 US5948186A (en) 1993-02-09 1994-02-08 Light weight tire including polybenzazole fibers
EP94908742A EP0683734A1 (fr) 1993-02-09 1994-02-08 Pneumatique leger

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5/21210 1993-02-09
JP2121093 1993-02-09

Publications (1)

Publication Number Publication Date
WO1994018015A1 true WO1994018015A1 (fr) 1994-08-18

Family

ID=12048636

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/001404 Ceased WO1994018015A1 (fr) 1993-02-09 1994-02-08 Pneumatique leger

Country Status (6)

Country Link
EP (1) EP0683734A1 (fr)
KR (1) KR100308429B1 (fr)
CN (1) CN1061390C (fr)
CA (1) CA2153809A1 (fr)
IL (1) IL108535A0 (fr)
WO (1) WO1994018015A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525638A (en) * 1994-09-30 1996-06-11 The Dow Chemical Company Process for the preparation of polybenzazole filaments and fibers
WO2000020236A1 (fr) * 1998-10-01 2000-04-13 The Goodyear Tire & Rubber Company Structure amelioree pour pneu pouvant rouler a plat
WO2000026045A1 (fr) * 1998-11-02 2000-05-11 The Goodyear Tire & Rubber Company Renforcement de bande de roulement pour pneu a affaissement limite, a deux nappes
US6536495B1 (en) 1998-11-02 2003-03-25 The Goodyear Tire & Rubber Company Tread stiffening for two ply runflat tire
WO2005024120A3 (fr) * 2003-08-29 2006-08-17 Kordsa Inc Appareil et procede de fabrication d'un ruban de tissu ecru pouvant servir de pli de couche superieure de pneumatiques

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103012764B (zh) * 2012-12-13 2013-11-13 江苏腾盛纺织科技集团有限公司 含噁唑结构的无规共聚酯树脂及其制备方法及高强度共聚酯纤维

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63145414A (ja) * 1986-12-09 1988-06-17 Toray Ind Inc 変成ポリ−パラ−フエニレンベンゾビスチアゾ−ル繊維及びその製造法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2589106B1 (fr) * 1985-10-24 1988-02-19 Michelin Rech Tech Enveloppe de pneumatique dont la carcasse est constituee par une fibre en cellulose regeneree
GB2183205B (en) * 1985-11-26 1989-11-08 Riyoukou Miura Non-slip tyre

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63145414A (ja) * 1986-12-09 1988-06-17 Toray Ind Inc 変成ポリ−パラ−フエニレンベンゾビスチアゾ−ル繊維及びその製造法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, 2nd Edition", 1988, JOHN WILEY & SONS, NEW YORK, US *
DATABASE WPI Section Ch Week 8830, Derwent World Patents Index; Class A, AN 88-209197 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525638A (en) * 1994-09-30 1996-06-11 The Dow Chemical Company Process for the preparation of polybenzazole filaments and fibers
WO2000020236A1 (fr) * 1998-10-01 2000-04-13 The Goodyear Tire & Rubber Company Structure amelioree pour pneu pouvant rouler a plat
WO2000026045A1 (fr) * 1998-11-02 2000-05-11 The Goodyear Tire & Rubber Company Renforcement de bande de roulement pour pneu a affaissement limite, a deux nappes
US6536495B1 (en) 1998-11-02 2003-03-25 The Goodyear Tire & Rubber Company Tread stiffening for two ply runflat tire
WO2005024120A3 (fr) * 2003-08-29 2006-08-17 Kordsa Inc Appareil et procede de fabrication d'un ruban de tissu ecru pouvant servir de pli de couche superieure de pneumatiques

Also Published As

Publication number Publication date
CN1061390C (zh) 2001-01-31
EP0683734A1 (fr) 1995-11-29
KR100308429B1 (ko) 2002-03-21
CA2153809A1 (fr) 1994-08-18
IL108535A0 (en) 1994-05-30
CN1117721A (zh) 1996-02-28

Similar Documents

Publication Publication Date Title
EP2408956B1 (fr) Câbles pour pneus
JP6040496B2 (ja) アラミド／ポリケトン複合繊維コード
Takeyama et al. Recent developments with tire cords and cord-to-rubber bonding
Wilfong et al. Future organic tire fibers
US5427165A (en) Reinforcement assemblages with monofilaments of liquid crystal organic polymers
EP0461900B1 (fr) Procédé de préparation de monofilaments polyesters
EP1225260B1 (fr) Corde enroulée
WO2005019509A1 (fr) Fibres en polyethylene-2, 6-naphtalate a grande tenacite
US7886791B2 (en) Pneumatic radial tire for passenger car
US5948186A (en) Light weight tire including polybenzazole fibers
EP2022651B1 (fr) Bandage pneumatique radial
WO1994018015A1 (fr) Pneumatique leger
WO1996030222A1 (fr) Fil et corde en cellulose pour des applications industrielles
US5223187A (en) Process of making polyester monofilaments for reinforcing tires
KR101273837B1 (ko) 아라미드 섬유 코드 및 그 제조방법
McDonel Tire cord and cord-to-rubber bonding
JPH02249705A (ja) 空気入りタイヤ
EP2022649B1 (fr) Pneumatique
JPS59124405A (ja) 均一性及び耐久性の優れた空気タイヤ
KR101277155B1 (ko) 아라미드 타이어 코오드 및 그의 제조방법
EP1967388B1 (fr) Pneumatique
JPH06294036A (ja) ゴム補強体
KR20090114507A (ko) 아라미드 타이어 코오드
KR20090114588A (ko) 아라미드 타이어 코오드 및 그의 제조방법
KR20040043448A (ko) 타이어 보강벨트 코드용 나일론 코드 및 이를 이용한승용차용 공기입 타이어

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 94191133.0

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CN US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 08491832

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2153809

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1994908742

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1994908742

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1994908742

Country of ref document: EP