WO2009012079A2 - Pneu rétroréfléchissant - Google Patents

Pneu rétroréfléchissant Download PDF

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Publication number
WO2009012079A2
WO2009012079A2 PCT/US2008/069405 US2008069405W WO2009012079A2 WO 2009012079 A2 WO2009012079 A2 WO 2009012079A2 US 2008069405 W US2008069405 W US 2008069405W WO 2009012079 A2 WO2009012079 A2 WO 2009012079A2
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WO
WIPO (PCT)
Prior art keywords
retroreflective
polyol
article
binder layer
polyurethane
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Ceased
Application number
PCT/US2008/069405
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English (en)
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WO2009012079A3 (fr
Inventor
Ningyong Huang
Jinyu Chen
Huijin Li
Michael A. Johnson
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of WO2009012079A2 publication Critical patent/WO2009012079A2/fr
Publication of WO2009012079A3 publication Critical patent/WO2009012079A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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)
    • B29D30/72—Side-walls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/047—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
    • B32B3/16—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side secured to a flexible backing
    • 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
    • B60C1/0025—Compositions of the sidewalls
    • 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
    • B60C13/00—Tyre sidewalls; Protecting, decorating, marking, or the like, thereof
    • B60C13/001—Decorating, marking or the like
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6576—Compounds of group C08G18/69
    • C08G18/6582—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6588—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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)
    • B29D30/72—Side-walls
    • B29D2030/728—Decorating or marking the sidewalls after tyre vulcanization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • B29L2011/0083—Reflectors
    • B29L2011/0091—Reflex reflectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/764—Photographic equipment or accessories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/025—Particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles

Definitions

  • This disclosure relates to retroreflective vulcanized rubber articles such as retroreflective tires. Also disclosed are methods for making such articles using retroreflective sheeting.
  • Retroreflectivity is a phenomenon that has been successfully used to prepare safety related articles. Retroreflection may be defined as a phenomenon in which a large portion of luminous radiation is returned in the direction from which it originates. This may be achieved through the use of spherical retroreflectors, which may be glass beads or microspheres that are at least partially coated with a reflective material, directly or via an intermediate layer.
  • retroreflectivity is rubber articles such as tires.
  • Bicycle and motorcycle tires are a particular example since visibility at night is a particular safety issue for cyclists.
  • cycles come with attached reflectors on the frame and/or the tire rims, but often the tires themselves are not reflective. If the tires are reflective they are generally made retroreflective by the attachment of a reflector or the compounding of retroreflective elements with the tire when it is manufactured.
  • the attached reflectors may not provide good visibility due to the limited area which is covered and the ease with which the attached reflectors can be damaged or fall off.
  • An issue with compounding retroreflective beads with the tire is that such reflectors generally provide poor brightness.
  • Retroreflective vulcanized rubber articles with retroreflective sheeting bonded to it are provided.
  • the vulcanized rubber article comprises a vulcanized rubber portion; and a retroreflective sheeting element comprising a polyurethane binder layer with first and second surfaces; and, a plurality of retroreflective elements at least partially embedded in the first surface; wherein the second surface of the polyurethane binder layer is directly bonded to the vulcanized rubber portion.
  • the retroreflective elements may be, for example, metal- coated microspheres.
  • the polyurethane binder comprises the reaction product of at least one diisocyanate, at least one polyisocyanate, at least one polyol, at least one unsaturated polyol, and at least one chain extension agent.
  • the polyurethane binder may also comprise a polyol with a functionality greater than 2.
  • the polyurethane binder also contains a silane coupling agent.
  • the method of making a vulcanized rubber article comprises providing a retroreflective sheeting element comprising a polyurethane binder layer with first and second surfaces having unsaturated sites for co-vulcanization, and a plurality of retroreflective elements partially embedded in the first surface; contacting the second surface of the polyurethane binder layer with unvulcanized rubber material; and vulcanizing the unvulcanized rubber material under heat and pressure such that the second surface of the binder layer of the retroreflective sheeting element is bonded to the vulcanized rubber material.
  • contacting the second surface of the polyurethane binder layer with unvulcanized rubber material comprises placing the retroreflective sheeting and the unvulcanized rubber into a mold and applying heat and pressure.
  • the polyurethane binder comprises the reaction product of at least one diisocyanate, at least one polyisocyanate, at least one polyol, at least one unsaturated polyol, and at least one chain extension agent.
  • the polyurethane binder is the reaction product of a two part reaction mixture wherein the first part comprises a polyurethane prepolymer comprising at least one diisocyanate, at least one polyisocyanate, at least one polyol, at least one unsaturated polyol and the second part comprises at least one chain extension agent.
  • Figure 1 shows a schematic cross sectional view of a segment of co-vulcanizable retroreflective sheeting as described in the present disclosure.
  • Figure 2 shows a schematic cross sectional view of a segment of co-vulcanizable retroreflective sheeting as described in the present disclosure.
  • Figure 3 shows a schematic cross sectional view of a segment of a vulcanized rubber article as described in the present disclosure.
  • Retroreflective vulcanized rubber articles with retroreflective sheeting bonded to it are provided.
  • the articles are prepared from retroreflective sheeting which contains retroreflective elements and a polyurethane binder.
  • the polyurethane binder is co- vulcanized with unvulcanized rubber to form the rubber article.
  • the rubber article is a tire, such as a bicycle tire.
  • the retroreflective sheeting comprises a plurality of retroreflective elements at least partially embedded in a polyurethane binder.
  • the polyurethane binder preferably is the reaction product of at least one diisocyanate, at least one polyisocyanate, at least one polyol, at least one unsaturated polyol, and at least one chain extension agent.
  • the diisocyanate component of the polyurethane binder may be any aliphatic, cycloaliphatic, aromatic or heterocyclic diisocyanate, or any combination of such diisocyanates.
  • Particularly suitable diisocyanates correspond to the formula:
  • Q(NCO) 2 in which Q represents: an aliphatic hydrocarbon radical containing from 2 to 100 carbon atoms and zero to 50 heteroatoms; a cycloaliphatic hydrocarbon radical containing from 4 to 100 carbon atoms and zero to 50 heteroatoms; an aromatic hydrocarbon radical or heterocyclic aromatic radical containing from 5 to 15 carbon atoms and zero to 10 heteroatoms; or an araliphatic hydrocarbon radical containing from 8 to 100 carbon atoms and zero to 50 heteroatoms.
  • heteroatoms that may be present in Q include non-peroxidic oxygen, sulfur, non-amino nitrogen, halogen, silicon, and non-phosphino phosphorous.
  • suitable diisocyanates include ethylene diisocyanate, 1,4- tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane- 1,3 -diisocyanate, cyclohexane-1,3- and - 1 ,4-diisocyanate, 1 -isocyanato-3 ,3 ,5 -trimethyl-5 -isocyanotomethy lcyclohexane (isophorone diisocyanate, IDPI), 2,4- and 2,6-hexahydrotolylene diisocyanate, perhydro- 2,4'- and -4,4'-diphenylmethane diisocyanate (H 12 MDI), hexahydro-1,3- and -1,4- phenylene diisocyanate, 1,3-
  • Diisocyanates that are commercially available and which impart good processability to the urethane prepolymer are preferred.
  • Illustrative examples of such diisocyanates include hexamethylene diisocyanate, methylene -bis-(4- cyclohexylisocyanate), isophorone diisocyanate, naphthalene 1,5-diisocyanate, toluene diisocyanate, isomers of diphenylmethane diisocyanate, or a mixture thereof.
  • Isophorone diisocyanate such as DESMODUR I commercially available from Bayer MaterialScience,
  • Leverkusen, Germany is particularly useful.
  • the polyisocyanate component of the polyurethane binder is similar to the diisocyanate component described above but is generally a higher molecular weight analog prepared by chain extension of diisocyanates. These higher molecular weight analogs may be aliphatic, cycloaliphatic, aromatic or heterocyclic diisocyanate, or any combination thereof. In addition the functionality of the polyisocyanates may be greater than 2.
  • An example of a useful polyisocyanate is the commercially available DESMODUR VL from Bayer MaterialScience, Leverkusen, Germany which is an aromatic polyisocyanate based on diphenylmethane diisocyanate. Generally the amount of polyisocyanate is 5-30 weight percent of the amount of diisocyanate. In some embodiments, the amount of polisocyanate is 10-20 percent by weight of the amount of diisocyanate.
  • the polyol component of the polyurethane binder may be in a liquid form, or may be an oligomeric difunctional alcohol.
  • the polyol preferably has a number average molecular weight (M n ) ranging from about 90 to about 5,000 or even about 90 to about
  • suitable polyols include the CARBOWAX 400, 600, 800 and 1000 series of poly(ethylene oxide) compounds (commercially available from Dow Chemical, Midland, MI), caprolactone polyols such as the TONE 200, 201, 210, 230, 240 and 260 series of polyols (commercially available from Dow Chemical), poly(tetramethylene oxide) polyols such as the Poly THF 250, 650, 1000 and 2000 series of polyols (commercially available from BASF Corp., Parsippany, NJ), polypropylene oxide polyols, polycarbonate polyols, such as KM-10-1667 and KM-10-1733 polycarbonate diols (commercially available from Stahl USA, Peabody, Mass.) and the DESMOPHEN series of polycarbonate diols such as DESMOPHEN C 1200 and DESMOPHEN X 2501 polycarbonate diols (commercially available from Bayer MaterialScience, Leverkusen,
  • Polyester polyols include the FOMREZ family (commercially available from Chemtura Corporation, Middlebury, CT), such as FOMREZ 11-112, 22-55, 33-56, 44-58, 55-112 polyols or the RUCOFLEX family (commercially available from RUCO Polymer Corporation, Hicksville, N.Y.) such as RUCOFLEX S-IOl, S-102, S-105, S-107, S-1014, S-1021, S-1028 and S-1034 diols.
  • Polycaprolactone polyols, polycarbonate polyols, polyurethane diols and polyester polyols are generally preferred for weatherability reasons.
  • polyols suitable for use in the invention include the hydroxyalkyl ethers obtained by the addition of optionally substituted alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide, onto the abovementioned polyols.
  • hydroxyalkyl ether polyols include diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, l,4-bis-(2- hydroxyethoxy)cyclohexane and 1 ,4-bis-(2-hydroxyethoxy-methyl)-cyclohexane, 1 ,4-bis- (2-hydroxyethoxy)-benzene.
  • one or more polyols with a functionality greater than 2 such as trifunctional or greater- functional polyols may be added to the polyurethane binder at a level which will not hamper the thermoformability of the binder.
  • trifunctional or greater- functional polyols include glycerol, trimethylol propane, trimethylol ethane, 1,2,6-hexane triol, 1,2,4-butanetriol, pentaerythritol, mannitol, sorbitol, formitol and mixtures thereof.
  • polymeric multifunctional polyols may be used. Examples of such polyols include, for example, some of the DESMOPHEN polyols such as DESMOPHEN 670 and DESMOPHEN 800 commercially available from Bayer MaterialScience, Leverkusen, Germany.
  • the unsaturated polyol component of the polyurethane binder may be any aliphatic, cycloaliphatic, aromatic or heterocyclic polyol, or any combination of such polyols that contain unsaturated groups.
  • Particularly suitable polyols correspond to the formula:
  • n 2 or greater and Z represents an n valent, hydrocarbon-based, radical which contains unsaturated groups along or pendant from the hydrocarbon chain.
  • the hydrocarbon-based group may or may not contain heteroatoms.
  • unsaturated polyol materials are commercially available including, for example, hydroxy-terminated polybutadiene materials, such as the POLY BD series of polyols (commercially available from ATOFINA Chemical, Philadelphia, PA), including POLY BD R-45HTLO, POLY BD R-20LM, POLY BD 600 and POLY BD 605.
  • hydroxy-terminated polybutadiene materials such as the POLY BD series of polyols (commercially available from ATOFINA Chemical, Philadelphia, PA), including POLY BD R-45HTLO, POLY BD R-20LM, POLY BD 600 and POLY BD 605.
  • Another class of commercially available unsaturated polyols are the HTBNs (hydroxy-terminated poly(butadiene-co-acrylonitrile)) liquid rubbers.
  • the amount of unsaturated polyol is 1-99 weight percent of the total polyol content of the polyurethane binder composition, more typically 40-80 weight percent of the total polyol content.
  • the chain extension agent component of the polyurethane binder is typically a diol.
  • the diols are typically low molecular weight, short chain diols well known in the polyurethane art.
  • the chain transfer agent has a number average molecular weight of 120 or less.
  • Chain extension agents are generally incorporated into polyurethane backbones, to improve ductility or strength characteristics. These diols may be aliphatic, aromatic, cycloaliphatic or combinations thereof.
  • chain extension agents useful in the present disclosure are, for example, ethylene glycol, 1 ,4-butanediol, diethylene glycol, 1 ,2-propanediol, 1,3-propanediol, 1,6-hexanediol, hydroquinone bis(2- hydroxyethyl) ether (HQEE), bisphenol A, bisphenol F, 2,2,4-trimethyl-l,3-pentanediol, dipropylene glycol, 1,5-pentanediol, 3-methyl-l,5-pentanediol, 1,4- cyclohexanedimethanol, cyclohexanediol, and the like.
  • the polyurethane binder may additionally comprise other materials typically used in the generation of preparation of polyurethane polymers. Among these are catalysts, fillers, leveling agents, defoamers, colorants, antioxidants, UV light stabilizers and the like.
  • Catalysts for the reaction of polyisocyanates and active hydrogen-containing compounds are well-known in the art; see, for example, U.S. Pat. No. 4,495,061 (Mayer et al.).
  • Preferred catalysts include organometallic compounds and amines.
  • the organometallic compounds may be organotin compounds such as dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dimethyltin dithioglycolate, and dioctyltin dithioglycolate.
  • the amine catalysts preferably are tertiary amines such as triethylene diamine, dimorpholinodiethyl ether, and tris(dimethylamino ethyl)phenol.
  • the catalyst is present in the reaction mixture at 50 ppm (parts per million by weight of the total composition) to 50,000 ppm, or 100 ppm to 2,000 ppm, or even 200 to 1,000 ppm.
  • Useful fillers that may be used in the polyurethane binder composition include, for example, carbon black, metal oxides such as silica, alumina, titanium oxide and the like. Any suitable filler may be used as long as it doesn't interfere with the preparation or use of the polyurethane binder composition.
  • a silane coupling agent may be used in the polyurethane binder composition.
  • Silane coupling agents are reagents well known in the polyurethane art. Typically the silane coupling agents are bifunctional having a silane or substituted silane group on one end and a reactive group on the other end. Examples of silane groups include silane, alkyl silanes and alkoxy silanes.
  • Reactive groups suitable for use with polyurethane systems include any group which may react with an isocyanate or a polyol. Such groups include, for example, isocyanate groups, primary or secondary amine groups, hydroxyl groups, epoxy groups, thiol groups, acetic acid groups and the like.
  • silane coupling agents include, for example, such compounds as KH- 560 a commercially available coupling agent of (3 glycidyloxypropyl) trimethoxy silane or Z 6020, Z 6040, KH-550, commercially available from Dow Corning, Midland, MI. If used, the silane coupling agent is generally present in the amount of 0.1 to 7 weight percent based on the total weight of the polyurethane binder composition. In some embodiments, the amount of silane coupling agent is 1-3 weight percent.
  • the retroreflective sheeting comprises a plurality of retroreflective elements at least partially embedded in the polyurethane binder.
  • the retroreflective elements are retroreflective beads.
  • the retroreflective beads useful for this application are microspheres that, generally, are substantially spherical in shape in order to provide the most uniform and efficient retroreflection.
  • the microspheres preferably also are substantially transparent so as to minimize absorption of light so that a large percentage of incident light is retroreflected.
  • the term "transparent" is used herein to mean capable of transmitting light.
  • the microspheres often are substantially colorless but may be tinted or colored in some other fashion.
  • the microspheres may be made from glass, a non-vitreous ceramic composition, or a synthetic resin. In general, glass microspheres are preferred because they tend to be less expensive, harder, and more durable than microspheres made from synthetic resins.
  • the microspheres may have any suitable size. Typically, the microspheres have an average diameter in the range of about 10 to 200 micrometers, or about 25 to 80 micrometers. Microspheres used in some embodiments typically have a refractive index of about 1.91, although values in the range of about 1.5 to 2.5, or any other suitable values, may be useful as well, depending on the type of sheeting desired.
  • the microspheres may have a reflective metal layer disposed beneath the embedded portions of the microspheres.
  • the reflective layer is disposed on the embedded or rear portions of the microspheres.
  • the reflective layer may be disposed directly on the microspheres or it can be disposed on the microspheres via an intermediate layer.
  • the term "reflective layer" is used herein to mean any suitable layer capable of reflecting light, and preferably it is capable of specularly reflecting light.
  • the reflective layer may be a layer comprising elemental metal.
  • the metal may be a continuous coating produced by vacuum-deposition, vapor coating, chemical-deposition, or electroless plating. A variety of metals may be used to provide a reflective layer.
  • Aluminum and silver are the typically used metals in the reflective layer. It is to be understood that in the case of aluminum, some of the metal may be in the form of the metal oxide and/or hydroxide. Aluminum and silver metals are desirable because they tend to provide good retroreflective brightness.
  • the reflective layer should be thick enough to reflect incoming light. Typically, the reflective layer is about 50 to 150 nanometers thick. Although the reflective color of a silver coating can be brighter than an aluminum coating, an aluminum reflective layer is typically used.
  • a dielectric mirror may be used as a specularly reflective layer.
  • the dielectric mirror may be similar to known dielectric mirrors disclosed in U.S. Pat. Nos. 3,700,305 and 4,763,985 to Bingham.
  • the sheeting material is prepared by embedding substantially a monolayer of retroreflective elements such as glass microspheres into a carrier web to a depth not exceeding 50% of the diameter of each microsphere; depositing specularly reflecting material over the retroreflective element-bearing surface of the carrier web; coating the binder composition of this disclosure over the specularly reflecting deposit; applying thermal energy to the binder composition to form a thermoplastic or thermosetting binder layer; and stripping away the carrier web while leaving the retroreflective elements partially embedded in the binder layer.
  • the exemplary retroreflective sheet article, 100 has a carrier web, 10, which may be paper, fabric, film or other material.
  • Carrier web 10 has a coating, 20, which may be polyethylene for example in which are at least partially embedded beads, 30, which may be any transparent beads such as glass beads.
  • Beads 30 have a reflective layer, 40, such as a metal coating or a polymeric reflector, functionally disposed on the side of the beads opposite to the coating 20 and the carrier web 10.
  • the reflective coating may be disposed on the beads and it may at least partially cover a portion of the bead surface.
  • the beads 30 are at least partially embedded in the binder, 50,which may have polyurethane composition.
  • the reflective layer 40 may be disposed between the binder 50 and the beads 30.
  • the binder 50 typically is 100-600 micrometers thick, or even 200-400 micrometers thick.
  • Figure 2 shows the exemplary retroreflective sheet article, 200, which is the same construction as in Figure 1 in which the carrier web, 10, with coating, 20, has been removed.
  • the binder composition may be either a mixture of the diisocyanate, polyisocyanate, polyol, unsaturated polyol, chain extension agent and any desired additives such as catalysts, pigments and the like; or it may be a polyurethane prepolymer mixture. If a prepolymer mixture is used, generally the mixture contains 2 parts, Part A and Part B.
  • Part A contains the reaction product of a diisocyanate, polyisocyanate, polyol and unsaturated polyol
  • Part B contains one or more chain extension agents.
  • Part A and Part B are combined and mixed prior to application.
  • the binder composition can be discharged or coated onto the beaded support web.
  • the thermal curing process for the polyurethane is generally carried out at temperatures of about 70 to about 180° C, using an oven or other heating techniques. In some instances heating may be carried out at temperatures of about 70 to about 150° C.
  • the cure rate may also be accelerated by using a catalyst as above described, if desired.
  • the properties of a polyurethane polymer can be varied by varying the composition and content of the isocyanate and hydroxyl reactive species used to make the polyurethane polymer.
  • the binder composition contains a mole ratio of isocyanate groups: hydroxyl groups of from 0.7 : 1 to 1.5 : 1. More typically the binder composition contains an isocyanate: hydroxyl ratio of from l : 1 to 1.3 : 1.
  • the polyurethane binder comprises 30-60 percent by weight hard segment.
  • hard segment and soft segment concept is one that is well understood in the polyurethane art.
  • hard segment elements are the diisocyanate, polyisocyanate, chain extension agents and any polyols with functionality greater than 2 while the soft segment elements are the polyols which are diols.
  • Retroreflective vulcanized rubber articles are prepared by co-vulcanizing a retroreflective sheet which comprises a plurality of retroreflective elements at least partially embedded in a polyurethane binder with an unvulcanized rubber.
  • the polyurethane binder comprises unsaturated groups which may co-vulcanize with the unvulcanized rubber during the vulcanization process to form, for example, a tire.
  • the unvulcanized rubber used to make the co-vulcanized retroreflective rubber article generally is an uncured elastomer which is made from various elastomer- forming monomers.
  • One class of such monomers are the various conjugated dienes having from 4 to 12 carbon atoms. Specific examples of monomers include butadiene, isoprene, pentadiene, hexadiene, heptadiene, octadiene, 2,3-dimethyl-l,3-butadiene, 2 -methyl- 1,3- pentadiene, and the like.
  • An example of such an elastomer is natural rubber.
  • natural rubber By the term “natural rubber”, it is meant, the elastomeric substance obtained from various trees and plants which generally grow in the tropics or desert portions of the world. Such material contains a very high content (in excess of 90% and often in excess of 95%) of cis-1,4- isoprene. Also included within the class of conjugated dienes are various copolymers and interpolymers thereof.
  • uncured elastomers may also be used. Some of these elastomers are classified as "synthetic rubbers" since they are not obtained from trees or plants.
  • One class of useful elastomers are those prepared from monomers of conjugated dienes having 4 to 12 carbon atoms as described above and vinyl-substituted aromatic compounds containing from 8 to 15 carbon atoms. Examples of vinyl-substituted aromatic compounds include styrene, alphamethyl styrene, 4-t-butyl styrene, vinyl toluene, divinyl benzene, isopropenyl benzene, di-isopropenyl benzene and the like.
  • copolymers in this class include SBR (poly(styrene-butadiene)), poly(alphamethyl styrene-butadiene) and poly (4-t-butyl-styrene-butadiene).
  • SBR poly(styrene-butadiene)
  • Another class of synthetic rubbers are the butyl rubbers.
  • Butyl rubbers are copolymers of isobutylene with small amounts of isoprene.
  • Neoprene is another synthetic rubber which may be used.
  • Neoprene rubber is polychloroprene (2-chloro-l,3-butadiene).
  • Another class of synthetic rubbers are the nitrile rubbers.
  • the nitrile rubbers are copolymers of dienes with 4 to 12 carbon atoms as described above
  • the specific rubber or rubbers used will vary depending upon the style and type of use for the rubber article.
  • the rubber article is a bicycle tire
  • typically a mixture of natural rubber and synthetic rubber is used.
  • the rubber is a mixture of 75% natural rubber and 25% synthetic rubber, however, the percentages of natural and synthetic rubber may vary in particular applications.
  • the unvulcanized rubber contains one or more vulcanizing agents capable of crosslinking the elastomeric rubber and co-vulcanizing with the unsaturated groups on the polyurethane binder of the retroreflective sheet.
  • the vulcanizing agent is present in an amount of less than about 0.25 weight percent.
  • Typical vulcanization agents include sulphur or sulphur containing compounds such as, for example, mercaptobenzothiazole and N-cyclohexyl-2 benzothiazolesulfenamide, or may contain a peroxide vulcanization agent.
  • Peroxide vulcanization agents include, for example, classes such as peroxyesters, diacyl peroxides, dialkyl peroxides, and peroxyketals. Additionally, in some instances, vulcanization can be carried out with gamma radiation.
  • the preparation of reflective rubber articles is achieved through the co- vulcanization of a retroreflective sheet with unvulcanized rubber.
  • the articles are prepared from retroreflective sheeting which contains retroreflective elements and a polyurethane binder.
  • the polyurethane binder contains unsaturated groups which can co- vulcanize with the unvulcanized rubber to form the rubber article.
  • the rubber article is a tire, such as a bicycle tire.
  • the retroreflective sheeting is contacted with unvulcanized rubber such that the side of the retroreflective sheeting which does not contain the retroreflective elements contacts the unvulcanized rubber.
  • This contact can be effected in a variety of ways.
  • One technique, which is useful in the manufacture of tires is the use of a mold.
  • the molding equipment and methods useful for making and curing tires is well known to those in the tire making art.
  • the retroreflective sheeting and the unvulcanized rubber are placed in the mold and an expandable interior mold bladder is expanded using steam or other such pressure to cause the retroreflective sheeting and the unvulcanized rubber to expand into the mold with the retroreflective elements of the retroreflective sheeting facing the inner surface of the mold.
  • the mold bladder is retained in place by the pressure for a predetermined period of time during which the retroreflective sheeting and unvulcanized rubber are co-vulcanized by heat and pressure transmitted to the bladder by steam or other well known methods.
  • the outer surface of the mold may also be heated to aid the co-vulcanization.
  • the retroreflective brightness of the formed tire is measured.
  • the retroreflective brightness is at least 50% of the brightness of the retroreflective sheet prior to the vulcanization process. In other embodiments the retroreflective brightness is 80% of the brightness of the retroreflective sheet prior to the vulcanization process.
  • the retroreflective brightness of the retroreflective elements in the formed tire are in some embodiments 250 cpl (cpl stands for candelas per lux per square meter). In other embodiments the retroreflective brightness of the retroreflective elements in the formed tire are 400 cpl.
  • FIG. 3 shows an exemplary embodiment of the vulcanized rubber article, 300, of this disclosure.
  • Beads, 30, are at least partially embedded in polyurethane binder, 50.
  • a reflective coating, 40 is disposed between the beads 30 and the polyurethane binder 50.
  • Polyurethane binder 50 is bonded to vulcanized rubber portion or layer 60.
  • the layer 60 is shown as a planar article, those of ordinary skill in the art will readily appreciate that the layer 60 may be curved, or, generally, it may be any desired shape and size. The figure is also not drawn to scale.
  • Retroreflectivity measurements for each of the following sheet materials were obtained using a retroluminometer according to the test method ASTM E808-81. The data are reported in candelas per lux per square meter (cpl).
  • the adhesion of the retroreflective sheeting to rubber was tested by covering half of the surface area of the urethane side of the sheeting with a polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • the PET film is to prevent that portion of the sheeting from bonding with the rubber surface.
  • the resulting sheet was contacted with unvulcanized rubber and the resulting laminate was placed in a plate mold where it was cured at 18O 0 C with a pressure of 15 Newtons for 5 minutes. After vulcanization the PET film was removed and the sample was cut into strips.
  • the peel strength was measured according to ASTM D 1876- 95 T-Peel Test using the unbonded portion of the strip to start the peel front.
  • Example 1 In a vessel DESMOPHEN C 1200, DESMOPHEN X 2501, HTPB 2800, and 1,4-
  • BDO in the amounts shown in Table 1 were mixed for 30 minutes at 500 rpm.
  • DESMODUR I, DESMODUR VL, FOMREZ UL 29 in the amounts shown in table 1 and the resulting mixture was stirred for 30 minutes at 500 rpm.
  • the mixture was coated onto a web containing aluminum-vapor-coated glass beads embedded in a temporary support film, at a coating thickness of 300 micrometers. The coated sheet was placed in a 125 0 C oven for 30 minutes and then allowed to anneal for 2 days in a 65 0 C oven.
  • the sheeting was stripped from the temporary support film and the Retroreflective Brightness was measured (Initial Retroreflective Brightness), the Adhesion to Rubber test was carried out, and the Retroreflective Brightness test was again carried out (Post Vulcanization Retroreflective Brightness) using the test methods described above. The results are shown in Table 2.
  • Example 2 The same procedure used for Example 1 above was followed with the amounts of reagents shown in Table 1. The results are shown in Table 2.
  • Example 2 The same procedure described for Example 1 was followed except instead of the experimental retroreflective sheeting prepared in Example 1, the commercially available product 3M SCOTCHLITE 8150 was used. The results are shown in Table 2.
  • Part A and Part B prepared above were mixed in an online mixer and coated to a thickness of 400 micrometers on a web containing aluminum-vapor-coated glass beads embedded in a temporary support film.
  • the coated sheet was placed in a 165 0 C oven for 30 minutes and then allowed to anneal for 2 hours in a 15O 0 C oven.
  • the sheeting was stripped from the temporary support film and the Retroreflective Brightness was measured (Initial Retroreflective Brightness), the Adhesion to Rubber test was carried out, and the Retroreflective Brightness test was again carried out (Post Vulcanization Retroreflective Brightness) using the test methods described above. The results are shown in Table 4.
  • Part A and Part B prepared above were mixed and stirred for 15 minutes at 500 rpm and then was coated to a thickness shown in Table 6 on a web containing aluminum- vapor-coated glass beads embedded in a temporary support film.
  • the coated sheet was placed in a 125 0 C oven for 30 minutes and then allowed to anneal for 2 days in a 65 0 C oven.
  • the sheeting was stripped from the temporary support film and the Retroreflective Brightness was measured (Initial Retroreflective Brightness), the Adhesion to Rubber test was carried out, and the Retroreflective Brightness test was again carried out (Post Vulcanization Retroreflective Brightness) using the test methods described above. The results are shown in Table 7.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des articles en caoutchouc vulcanisé rétroréfléchissants comprenant une enveloppe rétroréféchissante fixée sur lesdits articles. Ladite enveloppe contient une pluralité d'éléments rétroréfléchissants intégrés au moins partiellement dans une couche de liant polyuréthanne, cette couche contenant le produit de réaction d'au moins un diisocyanate, au moins un polyisocyanate, au moins un polyol, au moins un polyol non saturé et au moins un agent allongeur de chaîne. L'invention concerne également des procédés de préparation desdits articles en caoutchouc vulcanisé rétroréfléchissants.
PCT/US2008/069405 2007-07-13 2008-07-08 Pneu rétroréfléchissant Ceased WO2009012079A2 (fr)

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CN 200710129186 CN101342789A (zh) 2007-07-13 2007-07-13 硫化橡胶制品及其制备方法
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Cited By (4)

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DE102009044718A1 (de) 2009-12-01 2011-06-09 Contitech Ag Lasermarkierbarer Gummiartikel
US8551279B2 (en) 2008-03-25 2013-10-08 3M Innovative Properties Company Multilayer articles and methods of making and using the same
US8932424B2 (en) 2008-03-25 2015-01-13 3M Innovative Properties Company Paint film composites and methods of making and using the same
DE102015217699A1 (de) 2015-09-16 2017-03-16 Phoenix Conveyor Belt Systems Gmbh Mehrschichtiger Artikel auf Basis wenigstens einer Kautschukmischung und wenigstens eines Festigkeitsträgers

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CN110609342A (zh) * 2018-06-16 2019-12-24 上海清研新材料科技有限公司 一种汽车反光轮胎及其制备方法
CN109897590B (zh) * 2019-02-15 2021-09-07 美瑞新材料股份有限公司 一种双重固化反应型聚氨酯热熔胶及其制备方法和应用

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US3382928A (en) * 1966-08-04 1968-05-14 Halliburton Co Apparatus for use in measuring the pressure of fluids in wells
US5055347A (en) * 1988-12-09 1991-10-08 Minnesota Mining And Manufacturing Company Retroreflective sheeting adapted to be bonded to vulcanizable or curable substrate
US5474827A (en) * 1994-03-23 1995-12-12 Minnesota Mining And Manufacturing Company Retroreflective article and method of making the same
US7128799B2 (en) * 2002-12-06 2006-10-31 The Goodyear Tire & Rubber Company Method of manufacturing precured tread with reflective grooves

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8551279B2 (en) 2008-03-25 2013-10-08 3M Innovative Properties Company Multilayer articles and methods of making and using the same
US8932424B2 (en) 2008-03-25 2015-01-13 3M Innovative Properties Company Paint film composites and methods of making and using the same
US8992718B2 (en) 2008-03-25 2015-03-31 3M Innovative Properties Company Multilayer articles and methods of making and using the same
US9656442B2 (en) 2008-03-25 2017-05-23 3M Innovative Properties Company Paint film composites and methods of making and using the same
DE102009044718A1 (de) 2009-12-01 2011-06-09 Contitech Ag Lasermarkierbarer Gummiartikel
DE102015217699A1 (de) 2015-09-16 2017-03-16 Phoenix Conveyor Belt Systems Gmbh Mehrschichtiger Artikel auf Basis wenigstens einer Kautschukmischung und wenigstens eines Festigkeitsträgers

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