CN101342789A - Vulcanized rubber product and method of producing the same - Google Patents

Vulcanized rubber product and method of producing the same Download PDF

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Publication number
CN101342789A
CN101342789A CN 200710129186 CN200710129186A CN101342789A CN 101342789 A CN101342789 A CN 101342789A CN 200710129186 CN200710129186 CN 200710129186 CN 200710129186 A CN200710129186 A CN 200710129186A CN 101342789 A CN101342789 A CN 101342789A
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CN
China
Prior art keywords
polyurethane
polyalcohol
retrodirective reflection
goods
vulcanized rubber
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Pending
Application number
CN 200710129186
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Chinese (zh)
Inventor
黄宁勇
陈进宇
李慧金
迈克尔·A·约翰逊
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to CN 200710129186 priority Critical patent/CN101342789A/en
Priority to PCT/US2008/069405 priority patent/WO2009012079A2/en
Publication of CN101342789A publication Critical patent/CN101342789A/en
Pending legal-status Critical Current

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    • 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 form; Layered products 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 form; Layered products 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 form; Layered products 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 form; Layered products 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

Abstract

The invention provides a retrodirective reflection vulcanite product, which is provided with a retrodirective reflector plate connected with the product. The retrodirective reflector plate comprises a plurality of retrodirective reflection components embedded in a polyurethane bonding layer at least partially. The polyurethane bonding layer comprises the reaction products of at least one diisocyanate, at least one polyisocyanate, at least one polyhydric alcohol, at least one unsaturated polyhydric alcohol and at least one chain extension agent. The invention further provides a method for preparing the retrodirective reflection vulcanite product.

Description

Vulcanized rubber article and preparation method thereof
Technical field
The present invention relates to the retrodirective reflection vulcanized rubber article, for example the retrodirective reflection tire.The present invention also relates to prepare the method for this goods with Rectroreflective sheet.
Background technology
Retrodirective reflection is a kind of phenomenon that successfully has been used to prepare with security-related goods.Retrodirective reflection can be defined as a kind of phenomenon, and wherein most of luminous radiation is back on the direction of its generation.This can realize that spherical reflector can be bead or glass microsphere by using spherical reflector, and it is coated with reflecting material to small part.
In these goods, having benefited from using the goods of retrodirective reflection is rubber, for example tire.Bicycle tyre and motorcycle tyre are extremely to need reflex reflection performance example, because be a special safety problem for the cyclist in night visibility.Usually bicycle is equipped with reflector at its support and/or tyre rim, but tire itself does not have reflectivity.Make tire have reflectivity, so usually can be by the installation reflector or with tire and the compound reflectivity that obtains of reflective elements in manufacture process.But when reflector is installed on the tire,, and owing to be subjected to the restriction of its overlay area and the reflector of installation can not provide good visibility owing to the continuous motion in the use makes the reflector of installing be damaged and falls down.The retrodirective reflection pearl is mixed the problem that produces with tire be that the brightness of this reflector is relatively poor usually.The reflective tape that will have a retroreflectiveness is incorporated into rubber for example in the tire, can make rubber in use keep continual and steady retrodirective reflection performance.
Summary of the invention
The retrodirective reflection vulcanized rubber article is provided, and described goods have coupled reflective tape.In some embodiments, vulcanized rubber article contains the retrodirective reflection reflective tape of vulcanized rubber and the bonding layer of polyurethane.Described adhesive layer has first surface and second surface, and a plurality of reflective elements that are partly embedded in the first surface are arranged on the first surface; The second surface of adhesive layer can be directly and the vulcanized rubber part bonding.Reflective elements can be the microballoon that partly applies with metal.Polyurethane binder contains the product of at least a vulcabond, at least a polyisocyanates, at least a polyalcohol, at least a unsaturated polyol and at least a chain elongation agent.Polyurethane binder also can contain degree of functionality greater than 2 polyalcohol.In some embodiments, polyurethane binder also contains silane coupler.
The method for preparing the retrodirective reflection vulcanized rubber article is provided.In some embodiments, the method for preparing vulcanized rubber article comprises provides the retrodirective reflection piece element that contains the bonding layer of polyurethane, second surface and a plurality of reflective elements that the bonding layer of described polyurethane has the unsaturated position that is used for co-vulcanization are partly embedded in first surface.The second surface of the bonding layer of polyurethane is contacted with unvulcanized rubber material; Under heating and pressure, vulcanize unvulcanized elastomeric material and make that the second surface of adhesive layer of retrodirective reflection piece element is mutually bonding with vulcanized rubber material.In some embodiments, the second surface and the contacted step of unvulcanized rubber material of the bonding layer of polyurethane comprise: retrodirective reflection reflective tape and half finished rubber are placed in the mould, and heating and pressurization.Polyurethane binder comprises the product of at least a vulcabond, at least a polyisocyanates, at least a polyalcohol, at least a unsaturated polyol and at least a chain elongation agent.In some embodiments, polyurethane binder is the product of two parts of reactant mixtures, and wherein first part comprises the polyurethane prepolymer that contains at least a vulcabond, at least a polyisocyanates, at least a polyalcohol and at least a unsaturated polyol; Second part comprises at least a chain elongation agent.
Description of drawings
Fig. 1 has shown the cross sectional representation of the Rectroreflective sheet of one section described co-vulcanization of the present invention.
Fig. 2 has shown the cross sectional representation of the Rectroreflective sheet of one section described co-vulcanization of the present invention.
Fig. 3 has shown the cross sectional representation of one section described vulcanized rubber article of the present invention.
The specific embodiment
The retrodirective reflection vulcanized rubber article is provided, and described goods have coupled retrodirective reflection reflective tape.The retrodirective reflection reflective tape prepares by reflective elements and polyurethane binder, and the retrodirective reflection reflective tape is used for forming rubber with the half finished rubber co-vulcanization.In some embodiments, rubber is a tire, for example bicycle tyre.
The retrodirective reflection reflective tape contains a plurality of reflective elements that are partly embedded at least in polyurethane binder.The product of preferably at least a vulcabond of polyurethane binder, at least a polyisocyanates, at least a polyalcohol, at least a unsaturated polyol and at least a chain elongation agent.
The vulcabond component of polyurethane binder can be any aliphatic, cycloaliphatic, aromatic series or heterocycle vulcabond, or the combination of any this class vulcabond.Specially suitable vulcabond is following formula Q (NCO) 2Compound, wherein Q representative: contain 2-100 carbon atom and 0-50 heteroatomic aliphatic alkyl, contain 4-100 carbon atom and 0-50 heteroatomic cycloaliphatic alkyl, contain 5-15 carbon atom and 0-10 heteroatomic aromatic hydrocarbyl or heterocycle alkyl, or contain 8-100 carbon atom and 0-50 heteroatomic araliphatic alkyl.The hetero atom that may exist among the Q comprises non-peroxy oxygen, sulphur, non-amino nitrogen, halogen, silicon and non-phosphino-phosphorus.
The illustrative example of suitable vulcabond comprises ethylene diisocyanate, 1, the 4-tetramethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 1,12-dodecyl vulcabond, cyclobutane-1, the 3-vulcabond, cyclohexane-1,3-and-1, the 4-vulcabond, 1-isocyanato--3,3, and 5-trimethyl-5-isocyanato-hexahydrotoluene (IPDI, IDPI), 2,4-and 2,6-six hydrogen benzal vulcabond, perhydro-2,4 '-and-4,4 '-methyl diphenylene diisocyanate (H 12MDI), six hydrogen-1,3-and 1,4-phenylene vulcabond, 1,3-and 1,4-phenylene vulcabond, 2,4-and 2,6-benzal vulcabond, diphenyl methane-2,4 '-and-4,4 '-vulcabond, 2,2,4-and 2,4,4, the mixture of-trimethyl hexamethylene diisocyanate (TMDI), naphthylene-1, the 5-vulcabond, comprise these mixture of isomers with and any combination of oligomer and above-mentioned vulcabond.
Vulcabond is can buy on the market, is IPDI as the DESMODUR I of German Baeyer production.Those vulcabond that preferably the polyurethane prepolymer had good workability.The illustrative example of these vulcabond comprises hexamethylene diisocyanate, methylene-two (4-cyclohexyl isocyanate), IPDI, naphthylene 1, the isomers of 5-vulcabond, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate or its mixture.
Polyisocyanate component of polyurethane binder and above-mentioned vulcabond component are similar, but usually are the more HMW homologues by the preparation of vulcabond polycondensation method.These more the HMW analog can be aliphatic, cyclic aliphatic, aromatics or heterocycle vulcabond, or their any combination.In addition, the degree of functionality of polyisocyanates can be greater than 2.For example, from the aromatic polyisocyanate that German Baeyer is buied based on methyl diphenylene diisocyanate, DESMODUR VL.
Usually the weight of polyisocyanates be vulcabond weight 5～30%.In some embodiments, the weight of polyisocyanates be vulcabond weight 10～20%.
The polyol component of polyurethane binder can be a liquid form, maybe can be oligomeric two functional alcohol.Polyalcohol preferred number average molecular weight (Mn) scope be about 90～about 5000, or even about 90～about 1000g/mole.The illustrative example of suitable polyalcohol comprises the PEO compound, for example the CARBOWAX400 that buys from Dow Chemical, 600,800 and 1000 series; Caprolactone polyol, for example polyalcohol of the TONE200 that buys from Dow Chemical, 201,210,230,240 and 260 series; Poly-(tetramethylene oxide) polyalcohol, for example from BASFCorp., the Poly THF250,650 that Parsippany, NJ buy, the polyalcohol of 1000 and 2000 series; The PPOX polyalcohol; Polycarbonate polyol, for example from Stahl USA, KM-10-1667 that Peabody, Mass. buy and KM-10-1733; PCDL, for example DESMOPHEN C1200 and the DESMOPHEN X2501 that buys from Baeyer; Polyurethane polyol, for example from King Industries, the K-flex UD-320-100 polyurethane dihydroxylic alcohols that Norwalk, CN buy; The aromatic-polyether polyalcohol, for example from Milliken Chemical, SYNFAC 8024 polyalcohols that Spartanburg, SC buy; The random copolymer of poly-(tetramethylene oxide) Merlon, BASF Corporation for example, the polyalcohol of the Poly THF CD series that Mount Olive, NJ buy; PEPA, comprise that FOMREZ series is (from Chemtura CorporationMiddlebury, CT 06749, USA buys), for example FOMREZ11-112,22-55,33-56,44-58,55-112 polyalcohol, perhaps RUCOFLEX series is (from RUCO PolymerCorporation, Hicksville, N.Y. buy), for example RUCOFLEX S-101, S-102, S-105, S-107, S-1014, S-1021, S-1028 and S-1034 dihydroxylic alcohols.Owing to considering weather-proof reason, usually preferred polycaprolactone polyol, polycarbonate polyol, polyurethane dihydroxylic alcohols and PEPA.
Other is applicable to that polyalcohol of the present invention comprises by choosing the alkylene oxide of replacement wantonly, as oxirane, expoxy propane, epoxy butane and styrene oxide, and the hydroxy alkyl ether that obtains with above-mentioned polyalcohol addition.The preferred example of these hydroxy alkyl ethoxylated polyhydric alcohols comprises diethylene glycol (DEG), triethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, 1,4-pair-(2-hydroxyl-oxethyl) cyclohexane and 1,4-pair-(2-hydroxyl-oxethyl-methyl) cyclohexane, 1,4-pair-(2-hydroxyl-oxethyl) benzene.These materials have low relatively molecular weight, and help rigidity is incorporated in the urethane prepolymer skeleton.
Except above-mentioned, in some embodiments, degree of functionality greater than one or more polyalcohols of 2 for example trifunctional or bigger sense polyalcohol can join in polyurethane binder, its consumption should not damage the hot formability of adhesive.The example of trifunctional or bigger sense polyalcohol comprises glycerine, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butantriol, pentaerythrite, mannitol, D-sorbite, formitol and composition thereof.In addition, can use the macromolecule multi-functional polyol.The example of this polyalcohol comprises, some DESMOPHEN polyalcohols for example, and for example DESMOPHEN 670 and DESMOPHEN 800, from Bayer MeterialScience, Leverkusen, Germany buys.
The unsaturated polyol component of polyurethane binder can be any aliphatic series, cyclic aliphatic, aromatics or heterocycle polyalcohol, or any combination of these polyalcohols, and it contains unsaturated group.Specially suitable polyalcohol is corresponding to following formula Z (OH) n, and wherein n is 2 or bigger, and Z represents n valency alkyl, contains along hydrocarbon chain or is suspended from the unsaturated group of hydrocarbon chain side.Alkyl can contain or not contain hetero atom.
Various unsaturated polyol materials are commercially available, comprise for example hydroxyl terminated poly-butadiene material, for example POLY BD series polyalcohol is (from ATOFINA Chemical, Philadelphia, PA buys), comprise POLY BD R-45HTLO, POLY BD R-20LM, POLY BD 600 and POLY BD 605.Another kind of commercially available unsaturated polyol is HTBN (hydroxy-end capped poly-(butadiene-be total to-acrylonitrile)) liquid rubber.
Usually, the weight of unsaturated polyol is 1～99% of the total polyalcohol weight of polyurethane adhesive compositions, 40～80% of more especially total polyalcohol weight.
The chain elongation agent component of polyurethane binder is dihydroxylic alcohols normally.Dihydroxylic alcohols is the known low-molecular-weight of polyurethane field normally, the short chain dihydroxylic alcohols.In some embodiments, the number-average molecular weight of chain-transferring agent is 120 or lower.The chain elongation agent is introduced in the polyurethane skeleton usually to increase ductility or intensity.These dihydroxylic alcohols can be aliphatic series, aromatics, cyclic aliphatic or its combination.Be used for chain elongation agent of the present invention and be for example ethylene glycol, 1,4-butanediol, diethylene glycol (DEG), 1,2-propane diols, 1, ammediol, 1,6-hexylene glycol, two (2-ethoxy) ethers (HQEE) of quinhydrones, bisphenol-A, Bisphenol F, 2,2,4-trimethyl-1,3-pentanediol, dipropylene glycol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,4-cyclohexanedimethanol, cyclohexanediol etc.
Polyurethane binder also can contain the material that other is usually used in preparing polyether polyols with reduced unsaturation, comprising catalyst, filler, levelling agent, defoamer, colouring agent, antioxidant, UV light stabilizer etc.
Polyisocyanates is well known in the art with containing the compound bearing active hydrogen catalyst for reaction, for example referring to US4495061 (Mayer etc.).Preferred catalyst comprises organo-metallic compound and amine.Organo-metallic compound can be for example stannous methide two laurate salt, dibutyl tin two laurate salt, dibutyl tin two mercaptides, stannous methide two sulfo-oxyacetates and dioctyl tin two sulfo-oxyacetates of organo-tin compound.Amines catalyst is preferably tertiary amine for example triethylenediamine, dimorpholino diethyl ether and three (dimethyl aminoethyl) phenol.Usually the consumption of catalyst in reactant mixture is 50ppm～50000ppm (composition that each 1,000,000 weight portion is total), or 100ppm～2000ppm, even 200～1000ppm.
The useful filler that can be used for polyurethane adhesive compositions for example comprises carbon black, metal oxide for example silica, aluminium oxide, titanium oxide etc.Can use any appropriate filler, as long as it does not disturb preparation or uses polyurethane adhesive compositions.
In some embodiments, silane coupler can be used in the polyurethane adhesive compositions.Silane coupler is the known reagent of polyurethane field.Usually silane coupler is to have dual functionally, has silane or substituted silane group at the one end, and the other end has reactive group.The example of silane group comprises silane, alkyl silane and alkoxy silane.The reactive group that is applicable to polyurethane system comprise any can with the group of isocyanates or polyol reaction.This group comprises for example isocyanate groups, uncle or secondary amino group, hydroxyl, ethyoxyl, mercapto, aceticoceptor etc.The example of specially suitable silane coupler comprises for example KH-560 of compound, a kind of commercially available coupling agent (3 glycidyl oxygen base propyl group) trimethoxy silane, and KH550, or from Dow Corning, DC Z 6020 that Midland, MI buy and DC Z 6040.The silane coupler consumption is generally 0.1～7% of polyurethane adhesive compositions gross weight.In some embodiments, the silane coupler consumption is 1～3% of a polyurethane adhesive compositions gross weight.
The retrodirective reflection reflective tape contains a plurality of reflective elements that are partly embedded at least in polyurethane binder.In some embodiments, reflective elements is the retrodirective reflection pearl.The retrodirective reflection pearl that wherein can be used for the application is microspheric, and its shape is essentially spherical usually, so that the most even effective retrodirective reflection to be provided.Microballoon is transparent preferably basically also, thus so that the minimum retrodirective reflection incident light to a greater degree of the absorption of light.The term of Shi Yonging " transparent " refers to transmit light herein.Microballoon is colourless usually basically, but under some other pattern situations, also can be coloured or painted.Microballoon can be by the ceramic composition of glass, non-glass shape, or synthetic resin makes.Usually, the preferred glass microballoon, so they are more cheap, harder and more durable than microballoon that synthetic resin makes.
The average grain diameter of microballoon is generally about 10～200 microns, or about 25～80 microns.The ranges of indices of refraction of microballoon is 1.5～2.5, and the refractive index of the microballoon of Shi Yonging is about 1.91 in some embodiments.The application of desirable reflective tape is depended in the selection of the refractive index of microballoon.
Microballoon scribbles the metallic reflector of minute surface reflection usually, and it is arranged on being embedded under polyurethane binder part of microballoon, or on the back of microballoon.Term used herein " specular layer " refers to catoptrically to contain the layer of metal element, preferred specular light.Metal can be coated with continuously by vacuum moulding machine, steam coating, chemical deposition or electroless plating.Various metals can be used for providing specular layer.It comprises aluminium, silver, chromium, nickel, magnesium of element form etc.Aluminium and silver are most commonly used to the metal of specular layer.Some metals can be the forms of metal oxide and/or hydroxide.Aluminium and silver metal are inclined to use most, because they can provide good retrodirective reflection brightness.Specular layer should be enough thick and can reflects incident light.Usually specular layer thickness is about 50～150nm.
As the substitute of metal level, but the working medium mirror is as specular layer.Dielectric mirror can be similar with 4763985 disclosed known media mirrors to the US3700305 of Bingham.
Usually, reflective tape prepares by following method: reflective elements for example glass microsphere individual layer is embedded on the carrier band (Fig. 1,10) that has adhesive (Fig. 1,20), and its insert depth is no more than 50% of each microsphere diameter; On reflective elements, deposit specular reflective material; Coating polyurethane adhesive compositions disclosed herein on minute surface reflection deposit; Adhesive composition is heating and curing to form thermoplasticity or thermosetting adhesive layer; Peel off the carrier band that has adhesive, obtain reflective tape such as Fig. 2, promptly reflective elements is partly embedded in the bonding layer of polyurethane.
Referring to Fig. 1, carrier band 10 can be paper, film or other material.Carrier band 10 has adhesive coating 20, and adhesive can be a polyethylene.The pearl 30 that is partially submerged into, it can be a for example bead of arbitrarily transparent pearl.Pearl 30 has reflecting layer 40, metal coating for example, and that side opposite that is arranged on pearl functionally with coating 20 and carrier band 10, metal coating can be arranged on the pearl and can cover on the part of bead surface to small part.Pearl 30 is partly embedded in the adhesive 50 at least, and adhesive 50 can be a urethane composition.Reflecting layer 40 is arranged between adhesive 50 and the pearl 30.Other suitable intermediate layer also can be provided with therein.Adhesive 50 is generally 100～600 micron thickness, or even 200～400 micron thickness.Fig. 2 has shown exemplary retroreflective sheeting articles 200, and its structure with Fig. 1 is identical, and the carrier band 10 that wherein has adhesive coating 20 is removed.
Polyurethane adhesive compositions can be for example mixture of catalyst, pigment etc. of vulcabond, polyisocyanates, polyalcohol, unsaturated polyol, chain elongation agent and any desirable additive, perhaps also can be poly-propylhomoserin pre-polymer mixture.If the use pre-polymer mixture, then usual hybridization contains 2 parts, part A and part B.Usually part A contains the product of vulcabond, polyisocyanates, polyalcohol and unsaturated polyol, and a part B contains one or more chain elongation agent.Part A and part B mix usually before use.The curing process of polyurethane carries out under about 70 ℃～about 180 ℃ of temperature usually, uses baking oven or other heating technique.In some cases, heat under about 70～about 150 ℃ of temperature, curing rate also can improve by using above-mentioned catalyst.
The character of polyether polyols with reduced unsaturation can be used to prepare the isocyanates of polyether polyols with reduced unsaturation and the component and the content of hydroxyl reaction sample changes by change.The isocyanate groups that common adhesive composition contains: the mol ratio of hydroxyl is 0.7: 1～1.5: 1, and more specifically, the isocyanates that adhesive composition contains: the mol ratio of hydroxyl is 1: 1～1.3: 1.
Usually polyurethane binder contains hard section of 30～60% weight portions." hard section (hard segment) " and " soft section (soft segment) " are the notions that polyurethane field is known.In this article, hard section element is vulcabond, polyisocyanates, chain elongation agent and degree of functionality greater than any polyalcohol of 2, and soft section element is polyalcohol, and described polyalcohol is a dihydroxylic alcohols.
Prepare the retrodirective reflection vulcanized rubber article by retrodirective reflection reflective tape and half finished rubber co-vulcanization, described retrodirective reflection reflective tape contains a plurality of reflective elements that are partly embedded at least in polyurethane binder.Polyurethane binder contains unsaturated group, and described unsaturated group can be in sulfidation and the half finished rubber co-vulcanization.The example of curable matrix comprises rubber and/or is coated with the goods of rubber, and other has the matrix of curable groups.
The half finished rubber that is used to prepare co-vulcanization retrodirective reflection rubber is uncured elastomer normally, and it is formed elastomeric monomer and made by various.One class of this monomer is the various conjugated dienes with 4-12 carbon atom.The object lesson of monomer comprises butadiene, isoprene, pentadiene, hexadiene, heptadiene, octadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl isophthalic acid, 3-pentadiene etc.This elastomeric example has natural rubber.Term " natural rubber " refers to the elastomer substances that obtains from various trees and plant, described trees and plant are grown in the torrid zone or the desert region in the world usually.This material contain very high-load (surpass 90%, usually surpass 95%) along 1, the 4-isoprene.Conjugated diene also comprises various copolymers or its interpretation.
Also can use other class uncured elastomer.In these elastomers some are called as " synthetic rubber ", because they are not to obtain from trees or plant.The useful elastomer of one class is to prepare from the monomer of the conjugated diene of the above-mentioned 4-12 of a having carbon atom and the vinyl substituted aromatic that contains 8-15 carbon atom.The example of vinyl substituted aromatic comprises styrene, αJia Jibenyixi, 4-t-butyl styrene, vinyltoluene, divinylbenzene, isopropenylbenzene, di isopropenylbenzene etc.The example of some copolymers comprises SBR (poly-(styrene-butadiene)), poly-(αJia Jibenyixi-butadiene) and poly-(4-t-butyl styrene-butadiene) in this class.Another kind of synthetic rubber is a butyl rubber.Butyl rubber is the copolymer of isobutene and a small amount of isoprene.Neoprene is another kind of spendable synthetic rubber.Neoprene is polychlorobutadiene (a 2-chloro-1,3-butadiene).Another kind of synthetic rubber is an acrylonitrile-butadiene rubber.Acrylonitrile-butadiene rubber is above-mentioned the have diene of 4～12 carbon atoms and the copolymer of acrylonitrile monemer.
Used one or more concrete rubber are along with the pattern of rubber purposes and type and change.For example when rubber is bicycle tyre, use natural rubber and elastomeric mixture usually.In some embodiments, rubber is 75% natural rubber and 25% elastomeric mixture, but natural rubber and elastomeric percentage change along with concrete purposes.
Usually half finished rubber contains one or more vulcanizing agents, and described vulcanizing agent can cross-linking elasticity rubber, and can carry out co-vulcanization with the unsaturated group on polyurethane binder of Rectroreflective sheet.Usually the consumption of vulcanizing agent is less than about 0.25 weight %.Usually vulcanizing agent comprises sulphur or sulfur-containing compound, and for example mercaptobenzothiazoler and N-cyclohexyl-2 benzothiazole sulfenamide maybe can contain peroxide vulcanizing agent.Peroxide vulcanizing agent comprises for example peroxyesters, diacyl peroxide, dialkyl peroxide and peroxy ketal.In addition, in some cases, sulfuration can be carried out with the γ radiation.
Finish the preparation of reflection rubber by Rectroreflective sheet and half finished rubber co-vulcanization.These goods can prepare by Rectroreflective sheet and the polyurethane binder that contains reflective elements.Polyurethane binder contains unsaturated group, its can with the half finished rubber co-vulcanization to form rubber.In some embodiments, rubber is a tire, for example bicycle tyre.
The mode that Rectroreflective sheet contacts with half finished rubber is that the side of the Rectroreflective sheet that does not contain reflective elements is contacted with half finished rubber.This contact can be carried out in many ways.A kind of technology useful in the tire manufacturing is to use mould.The device for producing molds and the method that are used to make with cure tyre are that tire manufacturing field is known.Usually Rectroreflective sheet and half finished rubber are placed in the mould, make air bag expansion in the expandable mould with steam or other this pressure, so that Rectroreflective sheet and half finished rubber expand in the mould, the reflective elements of Rectroreflective sheet is towards the inner surface of mould.The further expansion of mould air bag makes Rectroreflective sheet and half finished rubber meet the shape of mould, thereby has obtained desirable tire shape, texture and tread contour.Time by the pressurization intended duration during this period, by steam or other known method, sends heat and pressure to air bag and comes co-vulcanization Rectroreflective sheet and half finished rubber suitably to keep air bag.The outer surface of mould also can be heated to help co-vulcanization.
After from mould, removing tire product, measure the retrodirective reflection brightness of the tire that forms.In some embodiments, retrodirective reflection brightness is at least 50% of sulfidation Rectroreflective sheet brightness before.In other embodiments, retrodirective reflection brightness is 80% of sulfidation retrodirective reflection reflective tape brightness before.In some embodiments, the retrodirective reflection brightness of the reflective elements of formed tire is 250cpl (cpl representative may moral draws/Lux/square metre).In other embodiments, the retrodirective reflection brightness of the reflective elements in the formed tire is 400cpl.
With reference to Fig. 3, it has shown exemplary vulcanized rubber article 300 disclosed by the invention.Pearl 30 is to be partly embedded at least in polyurethane binder 50, and reflection paint 40 is placed between pearl 30 and polyurethane binder 50, and polyurethane binder 50 is bonding with vulcanized rubber layer 60.Although layer 60 is shown as flat article, one skilled in the art will readily appreciate that layer 60 can be cured, or it can be any desirable shape and size usually.Accompanying drawing does not have reference mark yet.Embodiment
These embodiment only are used to the purpose set forth, and do not mean that the scope that limits the claim of enclosing.All part, percentage, ratio etc. are represented weight in the remainder of embodiment and specification, except as otherwise noted.Used solvent and other reagent are from Sigma-Aldrich ChemicalCompany; Milwaukee, Wisconsin obtains, except as otherwise noted.
Contraction table
Abbreviation or trade mark, name Explanation
DESMOPHEN C 1200 Molecular weight is about 2000 PCDL, from Bayer MeterialScience, and Leverkusen, Germany buys
DESMOPHEN X2501 Molecular weight is about 1000 PCDL, from Bayer MeterialScience, and Leverkusen, Germany buys
HTPB 2800 Molecular weight is about 2800 hydroxyl terminated poly-butadiene
1，4-BDO 1, the 4-butanediol
DESMODUR I IPDI, from Bayer MeterialScience, Leverkusen, Germany buys
DESMODUR VL Based on the aromatic polyisocyanate of methyl diphenylene diisocyanate, from Bayer MeterialScience, Leverkusen,
Germany buys
DESMODUR NZ1 Aliphatic polyisocyanate, from Bayer MeterialScience, Leverkusen, Germany buys
FOMREZ UL29 Tin catalyst is buied from GE Silicones
REGAL 99R Carbon black is buied from Cabot
BICAT Z Bismuth-zinc catalyst is buied from Shepherd Chemical Company
KH-560 Silane coupler (3 glycidyl oxygen base propyl group) trimethoxy silane
Half finished rubber Be used to prepare the half finished rubber that contains natural rubber and the sulfur vulcanization agent of bicycle tyre
Interim carrier film The scraps of paper that are used for the interim carrier layer of microspheroidal pearl with polyethylene coating
Method of testing
Retrodirective reflection brightness
According to method of testing ASTM E808-81, obtain the retrodirective reflection test result of following each sheet material with reverse luminometer.Data are may moral drawing/Lux/square metre (cpl) expression.
Viscosity to rubber
Measure the viscosity of Rectroreflective sheet by following method: described reflecting piece can be covered with half usefulness PETG (PET) film on rubber co-vulcanization surface to rubber.The PET film is used to prevent that the part of reflecting piece and rubber surface are bonding.The layered product that obtains is placed in the template, and therein in 180 ℃, 15 newton's pressure solidified 5 minutes down.After the sulfuration, remove the PET film and sample is cut to bar.According to ASTM D 1876-95T-Peel Test, the not stick portion of reflective tape begins the front and peels off to measure peel strength.
Embodiment 1:
Press the amount shown in the table 1, with 500rpm, with DESMOPHEN C 1200, DESMOPHEN X 2501, HTPB 2800 and 1,4-BDO mixed 30 minutes in container.Add DESMODUR I, DESMODUR VL, the FOMREZ UL29 of the amount of Table 1 in mixture, the mixture that obtains stirred 30 minutes under 500rpm.Mixture is applied on the carrier band that has glass microballoon, and bead is aluminized, and coating thickness is 300 microns.The sheet of coating was placed in 125 ℃ the baking oven 30 minutes, annealing 2 days in 65 ℃ of baking ovens then.Peel off carrier band, measure retrodirective reflection brightness (initial retrodirective reflection brightness), test is to the viscosity and the retrodirective reflection brightness of sulfuration back of rubber, and the result is as shown in table 2.
Embodiment 2
Carry out embodiment 1 described same steps as with the amount shown in the table 1, the result is as shown in table 2.
Table 1
Reagent Embodiment 1 Embodiment 2
DESMOPHEN C 1200 (weight portion) 25.04 9.00
DESMOPHEN X 2501 (weight portion) 9.74 16.00
HTPB 2800 (weight portion) 14.90 30.56
1,4-BDO (weight portion) 11.72 9.34
DESMODUR I (weight portion) 27.31 24.18
DESMODUR VL (weight portion) 9.71 9.34
FOMREZ UL29 (per 1,000,000 parts) 50 50
Comparative example C1:
Carry out embodiment 1 described same steps as, except replace the experimental Rectroreflective sheet of embodiment 1 preparation with commercially available prod 3M SCOTCHLITE8150, the result is as shown in table 2.
Table 2
Test Embodiment 1 Embodiment 2 Comparative example C1
Initial retrodirective reflection brightness (cpl) 444 459 480
Sulfuration back retrodirective reflection brightness (cpl) 268 263 400
Viscosity (N/mm) to rubber 3.20 3.84 1.80
Embodiment 3
Part A preparation:
Press the amount shown in the table 3, under 1000rpm, in container, DESMOPHEN C 1200, HTPB 2800, DESMODUR I, DESMODUR VL and REGAL 99R were mixed 3 hours.
Part B preparation:
Press the amount shown in the table 3, with 500rpm, with 1,4-BDO, BYK359 and BICATZ mixed 30 minutes in container.
Mix coating and curing
Part A and part B of above-mentioned preparation mix in blender, and are coated on the bead carrier band, and bead is aluminized, and coating thickness is 400 microns.The sheet of coating was placed in 165 ℃ the baking oven 30 minutes, annealing 2 hours in 150 ℃ of baking ovens then.Divest the bead carrier band, measure retrodirective reflection brightness (initial retrodirective reflection brightness), test is to the viscosity and the retrodirective reflection brightness of sulfuration back of rubber, and the result is as shown in table 4.
Table 3
Reagent Part A (weight portion) Part B (weight portion)
DESMOPHEN C 1200 43.40 ----
HTPB 2800 8.00 ----
DESMODUR I 29.00 ----
DESMODUR VL 4.69 ----
REGAL 99R 4.95 ----
1，4-BDO ---- 8.68
BYK359 ---- 1.00
BICAT Z ---- 0.29
Table 4
Test Embodiment 3 Comparative example C1
Initial retrodirective reflection brightness (cpl) 450 480
Sulfuration back retrodirective reflection brightness (cpl) 270 400
Viscosity (N/mm) to rubber ＞1.20 1.80
Embodiment 4-9
Part A preparation:
Press the amount shown in the table 5,, in container, DESMOPHEN C 1200, DESMOPHEN X 2501, HTPB 2800, DESMODUR I, DESMODUR VL, DESMODURNZ1 and FOMREZ UL 29 were mixed 5 hours with 500rpm.
Part B preparation:
Press the amount shown in the table 5, with 100rpm, with 1,4-BDO, glycerine, FOMREZUL 29 and KH-560 mixed 15 minutes in container.
Mix coating and curing
Part A and part B of above-mentioned preparation mix stirring 15 minutes with 500rpm, are coated on the bead carrier band by the thickness shown in the table 6 then, and bead is aluminized.The sheet of coating was placed in 125 ℃ the baking oven 30 minutes, and annealing 2 days in 65 ℃ of baking ovens then divests the bead carrier band, measure retrodirective reflection brightness (initial retrodirective reflection brightness), test is to the viscosity and the retrodirective reflection brightness of sulfuration back of rubber, and the result is as shown in table 7.
Table 5: part A
Reagent Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9
DESMOPHEN C1200 (weight portion) 9.00 7.25 0 0 0 0
DESMOPHEN X 2501 (weight portion) 16.00 16.91 26.75 24.53 24.64 24.64
HTPB 2800 (weight portion) 30.56 29.53 26.75 24.53 24.64 24.64
DESMODUR I (weight portion) 24.18 23.69 26.66 25.81 25.93 25.93
DESMODUR VL (weight portion) 9.34 0 10.30 0 0 0
DESMODUR NZ1 (weight portion) 0 13.65 0 15.71 15.78 15.78
FOMREZ UL 29 (per 1,000,000 parts) 0 150 0 150 150 150
Table 6: part B
Reagent Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9
1,4-BDO (weight portion) 9.34 8.97 9.55 9.42 7.89 7.89
Glycerine (weight portion) 0 0 0 0 1.13 1.13
FOMREZ UL 29 (per 1,000,000 parts) 50 100 50 150 150 150
KH-560 (weight portion) 0 0 0 0 0 0.5
Table 7
Test Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9
Thickness (micron) 300 280 320 260 350 350
Initial retrodirective reflection brightness (cpl) 459 450 461 445 506 518
Sulfuration back retrodirective reflection brightness (cpl) 263 301 265 322 412 394
Viscosity (N/mm) to rubber ---- ---- ---- ---- 5.8 5.4

Claims (17)

1. vulcanized rubber article, contain:
The vulcanized rubber part; With
The retrodirective reflection piece element, this retrodirective reflection piece element contains:
The bonding layer of polyurethane with first and second surfaces; With
At least be partly embedded in a plurality of reflective elements on the first surface,
Wherein the second surface of the bonding layer of polyurethane directly and the vulcanized rubber part bonding.
2. the goods of claim 1, wherein vulcanized rubber article is a tire.
3. the goods of claim 1, wherein polyurethane is the product that comprises the reactant mixture of at least a vulcabond, at least a polyisocyanates, at least a polyalcohol, at least a unsaturated polyol and at least a chain elongation agent.
4. the goods of claim 1, wherein polyalcohol is polycaprolactone glycol, PCDL, polyoxyalkylene diols, polyurethane diol, polyester-diol or its mixture.
5. the goods of claim 4, wherein said at least a polyalcohol comprise that also degree of functionality is greater than 2 polyalcohol.
6. the goods of claim 3, wherein unsaturated polyol is a hydroxyl terminated poly-butadiene.
7. the goods of claim 3, wherein the chain elongation agent is a number-average molecular weight less than 120 glycol.
8. the goods of claim 3, wherein said reactant mixture also comprises silane coupler.
9. the goods of claim 1, wherein the retrodirective reflection brightness of reflective elements is at least 250cpl.
10. method for preparing vulcanized rubber article comprises:
A kind of retrodirective reflection piece element is provided, and it comprises:
Have the bonding layer of polyurethane on first and second surfaces that possess the unsaturated position that is used for co-vulcanization and be partly embedded in a plurality of reflective elements on the first surface; The second surface of the bonding layer of polyurethane is contacted with unvulcanized elastomeric material; And
Vulcanizing unvulcanized elastomeric material under heating and pressure makes the second surface of adhesive layer of retrodirective reflection piece element combine with vulcanized rubber material.
11. the method for claim 10, the step that the second surface of adhesive layer is contacted with half finished rubber comprises:
The retrodirective reflection piece element is placed in the mould; And
Unvulcanized elastomeric material is incorporated into makes it contact in this mould with the second surface of adhesive layer.
12. the method for claim 10, wherein the brightness of sulfuration back Rectroreflective sheet is at least 50% of preceding this sheet brightness of sulfuration.
13. the method for claim 10, wherein polyurethane is the product that comprises the reactant mixture of at least a vulcabond, at least a polyisocyanates, at least a polyalcohol, at least a unsaturated polyol and at least a chain elongation agent.
14. the method for claim 13, wherein said at least a polyalcohol comprise that also degree of functionality is greater than 2 polyalcohol.
15. the method for claim 13, wherein unsaturated polyol is a hydroxyl terminated poly-butadiene.
16. the method for claim 13, wherein said reactant mixture also comprises catalyst.
17. the method for claim 11, wherein polyurethane is the product of two parts of reactant mixtures,
Wherein first part comprises:
The polyurethane prepolymer that contains at least a vulcabond, at least a polyisocyanates, at least a polyalcohol and at least a unsaturated polyol;
And second part comprises at least a chain elongation agent.
CN 200710129186 2007-07-13 2007-07-13 Vulcanized rubber product and method of producing the same Pending CN101342789A (en)

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CN109897590A (en) * 2019-02-15 2019-06-18 美瑞新材料股份有限公司 A kind of dual cure reaction type polyurethane hot-melt adhesive and its preparation method and application
CN110609342A (en) * 2018-06-16 2019-12-24 上海清研新材料科技有限公司 Automobile reflective tire and preparation method thereof

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BRPI0909077A2 (en) 2008-03-25 2015-08-25 3M Innovative Properties Co Multilayer articles and methods of preparation and use
KR101627875B1 (en) 2008-03-25 2016-06-07 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Paint film composites and methods of making and using the same
DE102009044718A1 (en) 2009-12-01 2011-06-09 Contitech Ag Laser-markable rubber products, useful as tire, hose, strap air spring or belt, comprises a rubber mixture that is formed from diene rubber e.g. natural or synthetic polyisoprene, and a laser-sensitive pigment e.g. metal oxide coated mica
DE102015217699A1 (en) 2015-09-16 2017-03-16 Phoenix Conveyor Belt Systems Gmbh Multilayer article based on at least one rubber mixture and at least one reinforcing agent

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US7128799B2 (en) * 2002-12-06 2006-10-31 The Goodyear Tire & Rubber Company Method of manufacturing precured tread with reflective grooves

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CN110609342A (en) * 2018-06-16 2019-12-24 上海清研新材料科技有限公司 Automobile reflective tire and preparation method thereof
CN109897590A (en) * 2019-02-15 2019-06-18 美瑞新材料股份有限公司 A kind of dual cure reaction type polyurethane hot-melt adhesive and its preparation method and application

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