TW200902600A - Vulcanized rubber articles and its preparation - Google Patents

Abstract

The present invention provides a reverse reflective vulcanized rubber article, containing a reverse reflective sheet connected to the article. The reverse reflective sheet includes a plurality of reverse reflective elements that are at least partially embedded into a polyurethane adhesive layer. The polyurethane adhesive layer contains a product formed by reacting at least one diisocyanate ester, at least one polyisocyanate ester, at least one polyhydric alcohol, at least one unsaturated polyhydric alcohol, and at least one chain extender. The present invention also provides a method for preparing the reverse reflective vulcanized rubber article.

Description

200902600 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to retroreflective vulcanized rubber articles, such as retroreflective tires. The invention also relates to a method of making such an article from a retroreflective sheeting. 5 [Prior Art] Retroreflection is a phenomenon that has been successfully used to prepare safety-related articles. Retroreflection can be defined as a phenomenon in which most of the illuminating light returns to the direction in which it is produced. This can be achieved by using a spherical mirror 10, which can be a glass bead or a glass microsphere that is at least partially coated with a reflective material. Among these articles, articles which benefit from the use of retroreflection are rubber articles such as tires. Bicycle tires and motorcycle tires are examples of the extreme need for retroreflective performance because visibility at night is a particular safety issue for riders. Bicycles typically have a reflective effect on their brackets and/or tire edges, but the tire itself is not reflective. To make the tire reflective, it is often possible to achieve reflexivity by installing a reflector or compounding the tire with retroreflective elements during the manufacturing process. However, when the reflection number is mounted on the tire, the installed reflector 2 is damaged and falls due to the continuous movement during use, and the visibility is not limited by the coverage area and the reflection of the women's clothing does not provide good visibility. . The problem with mixing retroreflective beads with tires is that the brightness of such reflectors is generally poor. The introduction of retroreflective retroreflective tape into rubber articles such as tires enables the rubber article to maintain consistently stable retroreflective properties during use. 200902600 SUMMARY OF THE INVENTION The present invention provides a retroreflective vulcanized rubber article having a reflective tape attached thereto. In some embodiments, the vulcanized rubber article comprises a vulcanized rubber and a retroreflective tape of a polyurethane adhesive layer. The adhesive layer has a first surface having a plurality of retroreflective elements partially embedded in the first surface and a second surface; the second surface of the adhesive layer may be directly bonded to the vulcanized rubber portion. The retroreflective element can be a microsphere coated with a metal portion. The polyurethane binder contains the reaction product of at least one diisocyanate, up to 10 polyisocyanates, at least one polyol, at least one unsaturated polyol, and at least one chain extender. Polyurethane adhesives may also contain polyols having a functionality greater than two. In some embodiments, the polyurethane adhesive also contains a decane coupling agent. The present invention provides a method of making a retroreflective vulcanized rubber article. In some embodiments, a method of making a vulcanized rubber article includes providing a retroreflective sheeting member comprising a polyurethane adhesive layer having a second surface of an unsaturated site co-vulcanized with T and a plurality of retroreflective element portions Disperse into the first surface. The second surface of the polyurethane adhesive layer is contacted with the unvulcanized rubber material; the unvulcanized rubber material 20 is vulcanized under heat and pressure to adhere the second surface of the adhesive layer of the retroreflective sheeting to the vulcanized rubber knee material. Pick up. In some embodiments, the step of contacting the second surface of the polyurethane adhesive layer with the unvulcanized rubber material comprises: placing the retroreflective & optical tape and the uncoated rubber in a mold, and heating and pressing . The polyurethane self-adhesive agent package 3 is an anti-200902600 product of at least one type of diisocyanate, at least one polyisocyanate, at least one type of 25 polyol, at least one type of unsaturated polyol, and at least one type of chain extender. In some embodiments, the polyurethane binder is the reaction product of two parts of a reaction mixture, wherein the first portion comprises a polyurethane prepolymer comprising at least one diisocyanate, at least one polyisocyanate, at least one polyol, and at least one unsaturated polyol. The second portion comprises at least one chain extension agent. [Embodiment]

10 15 20 The present invention provides a retroreflective vulcanized rubber article having a retroreflective reflective tape attached thereto. The retroreflective tape is prepared by a retroreflective element and a urethane binder which is used to co-vulcanize with an unvulcanized rubber to form a rubber article. In some embodiments, the rubber article is a tire, such as a bicycle tire. The retroreflective tape comprises a plurality of retroreflective elements at least partially embedded in the polyurethane bond aJ. Preferably, the polyurethane adhesive is a 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 extender. The diisocyanate component of the a polyurethane binder may be any aliphatic, cycloaliphatic, aromatic or heterocyclic diisocyanate, or any combination of such diisocyanates. A particularly suitable diisocyanate is a compound of the formula q (nc〇M, wherein Q represents: a fat=smoke group containing 2 to 100 carbon atoms and 〇_5〇 a hetero atom, containing 4·_ carbon atoms and (d) a heteroatom of a cycloaliphatic group: a divalent aromatic hydrocarbon group or a hetero atom having 5 to 15 carbon atoms and (d) a hetero atom: or a hetero atom which may be present in 2 of a hetero atom Including non-peroxy oxygen, sulfur, non-amino nitrogen, _, 矽 and non-phosphino phosphorus. 25 200902600 Representative examples of suitable diisocyanates include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, hydrazine ^hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,12-dodecyl diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane_1, 3_ and _ 1,4_diisocyanate, 5 1 -isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IDPI), 2, 4 - and 2,6-hexahydrobenzylidene diisocyanate, perhydro-2,4,- and-4,4'-diphenylmethane diisocyanate_(Hi2MDI), hexahydro-1,3- and 1,4-phenylene diisocyanate, 匕弘 and 丨'Phenylene diisocyanate, 2,4- and 2,6-benzylidene diisocyanate, diphenylmethane 2,4,_ and 10 _4,4'·diisocyanate, 2,2,4- and 2 , a mixture of 4,4,-trimethylhexamethylene diisocyanate (TMDI), naphthylene diisocyanate 'comprising a mixture of these isomers and oligomers thereof, and a combination of the above-mentioned diisocyanates. 15 Diisocyanates are commercially available, such as DESMODURI produced by Bayer, Germany, which is isophorone diisocyanate. It is preferred that those di-isocyanates have good adhesion to the compound. Representative examples of these diiso-^=esters include hexamethylene diisocyanate, methylene-bis-hexyl hexyl isocyanate, isophorone diisocyanate, naphthylene 15 bis- phthalate, phthalic acid diisocyanate, Isomers of diphenylnonane diisocyanate or mixtures thereof. The polyisocyanate component of the v-polyurethane binder is similar to the above-mentioned diisocyanate group = but is often a high-lower homologue prepared by a diisocyanate (tetra) polymerization process. These higher molecular weight analogs may be aliphatic, cyclamate, aromatic or heterocyclic diisocyanate, or any electrical combination thereof. In addition to 200902600, the functionality of the polyisocyanate can be greater than two. For example, an aromatic polyisocyanate based on diphenylnonane diisocyanate available from Bayer, Germany, DESMODUR VL. Usually, the weight of the polyisocyanate S is from 5 to 30% by weight of the diisocyanate. In some embodiments, the weight of the polyisocyanate is from 10 to 20% by weight based on the weight of the diisocyanate. The polyol component of the urethane binder may be in liquid form or may be an oligomeric difunctional alcohol. The polyol preferably has a number average molecular weight (??) in the range of from about 90 to about 5,000, or even from about 90 to about 1000 g/mole. Representative examples of suitable polyols 10 include polyepoxylate compounds such as the CARBOWAX 400, 600, 800 and looo series available from Dow Chemical; caprolactone polyols such as TONE 200, 201 available from Dow Chemical, Polyols of the 210, 230, 240 and 260 series; poly(tetramethylene oxide) polyols such as Poly 15 THF 25 0, 650, 1000 and 2000 series of polyols available from BASF Corp., Parsippany, NJ; Polyglycidyl alcohol, polycarbonate from SV·', for example, from KH-10-1667 and KM-10-1733 from Stahl USA, Peabody, Mass., polycarbonate diol, for example from DESMOPHEN C1200 and DESMOPHEN X2501; polyurethane polyols such as K-flex UD-320-100 polyurethane diol from King Industries, Norwalk, CN; 20 aromatic polyether polyols, for example from Milliken Chemical SYNFAC 8024 polyol available from Spartanburg, SC; random copolymer of poly(tetramethylene oxide) polycarbonate, such as Poly THF CD series polyol available from BASF Corporation, Mount Olive, NJ; Ester polyol, package FOMREZ series (from 200 902 600

Chemtura Corporation Middlebury, CT 06749, USA available, for example, FOMREZ 11-112, 22-55, 33-56, 44-58, 55-112 polyol, or RUCOFLEX series (available from RUCO Polymer Corporation, Hicksville 'NY) For example, RUCOFLEX S-101, S-102, 5 S-105, S-107, S-1014, S-1021, S-1028 and S-1034 diols. Polycaprolactone polyols, polycarbonate polyols, urethane diols, and polyester polyols are generally preferred because of the weathering resistance. Other polyols suitable for use in the present invention include those obtained by addition of an optionally substituted alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide, 10 to the above polyol. Alkyl ether. Preferable examples of the benzyl alcohol-containing polyol include diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, and 1,4-bis-(2-hydroxyethoxy) ring. Hexane and 1,4-bis-(2-hydroxyethoxy-methyl)cyclohexane, 1,4-bis-(2-hydroxyethoxy)benzene. These materials have a relatively low molecular weight and help to introduce stiffness into the urinary prepolymer backbone. In addition to the above, in some embodiments, one or more polyols having a functionality greater than 2, such as a trifunctional or greater functional polyol, may be added to the polyurethane binder in an amount that does not compromise the thermoformability of the binder. Examples of trifunctional or larger functional polyols include glycerin, trihydroxydecyl propane, tris-20 hydroxydecylethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, pentaerythritol, mannose Sugar alcohol, sorbitol, formitol and mixtures thereof. Further, a high molecular polyfunctional polyol can be used. Examples of such polyols include, for example, some DESMOPHEN polyols such as DESMOPHEN 670 and DESMOPHEN 800, available from Bayer Meterial Science, Leverkusen, ίο 200902600 Germany. The unsaturated polyol component of the polyurethane adhesive can be any aliphatic, cycloaliphatic, aromatic or heterocyclic polyol, or any combination of these polyols, which contain an unsaturated group. A particularly suitable polyol corresponds to the following formula 5

10 15

Z(OH)n, wherein !! is 2 or more, z represents an n-valent hydrocarbon group, and contains an unsaturated group along a hydrocarbon chain or suspended on the side of the hydrocarbon chain. The hydrocarbyl group may or may not contain a hetero atom. Various unsaturated polyol materials are commercially available, including, for example, hydroxy-terminated polybutadiene materials, such as p〇LY BD series polyols (from

ATOFINA Chemica Bu Philadelphia's PA, including p〇LY

BD R-45HTLO ' POLY BD R-20LM, POLY BD 600 and p〇LY BD 605. Another class of commercially available unsaturated polyols are HTBN (hydroxyl terminated poly(butadiene-co-acrylonitrile liquid rubber. Generally, the weight of the unsaturated polyol is 1 of the weight of the polyurethane binder composition male polyol) ~"%, more particularly the total length of the polyol, the chain extender component of the 40~8 〇 urethane adhesive is usually a diol. The diol is usually a well-known low-density early in the field of polyurethane __ knife 1. Short-chain diterpene alcohol. In some embodiments, the number of the 'chain transfer agent is evenly distributed - 120 or less. The bond extender is usually introduced into the polyurethane skeleton to increase the ductility or Strength. These diols may be aliphatic, aromatic, cyclolipid, */human glutinous or a combination thereof. The chain extender used in the present invention is, for example, ethylene glycol, 1 4-butyl ρ 丄, 4 butanol, diethylene glycol, ^-propanediol '1,3-propanediol, 1,6-hexanediol, slanting ^^ fly bis(2-hydroxyethyl)ether (HQEE), bisphenol A, Bisphenol F, 2,2,4-trimethyl 〇, ^ τ丞_1,3-pentanediol, dipropylene glycol, 20 200902600 1,5-pentanediol

3-Methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, cyclohexide gas ester binder may also contain other commonly used in the preparation of polyurethane polymer gamma materials including catalysts, fillers, leveling Agent, antifoaming agent, coloring agent 5, antioxidant, UV light stabilizer, and the like. ... a catalyst for the reaction of a polyisocyanate with an active hydrogen-containing compound is: '", see, for example, US Pat. No. 4,491,061 ( Mayer et al.). Preferred catalysis (the organic compound and the amine are included. The organometallic compound may be Organotin compounds such as dimethyltin dilaurate, dibutyltin dilaurate monohydrazine, dibutyltin dithiolate, dimethyltin dithioacetate and dioctyltin dithioacetate The amine catalyst is preferably a tertiary amine such as triethylenediamine, dimorphine di-ethyl and tris(dimethylaminoethyl)benzene. Usually the amount of the catalyst in the reaction mixture is 5 Qppm~5_〇ppm. (per million parts by weight of total composition), or ι〇〇ρ_~2〇〇〇, 15 or even 200~1 〇〇〇ppm. 有用 Useful filler for polyurethane S-bond composition Including, for example, carbon black, metal oxides such as cerium oxide, aluminum oxide, titanium oxide, etc. can be used as long as it does not interfere with the preparation or use of the polyurethane adhesive composition. In the example, Shi Xi burning coupling agent can be used for polyurethane In the mixture group 5, the chelating agent is a conventional reagent in the field of polyamines. Usually, the zebra coupling agent is bifunctional, and at its end, it has a (four) fluorene-substituted Shixiyuan group. The anti-seam group. The money group _ sub-comprising Shi Xi-sing, burning base stone Xi Xuan and silk base material. (d) in the polyamine (four) system of reactive groups 12 200902600 includes any group that can react with isocyanate or polyol. Such groups include, for example, isocyanate groups, primary or secondary amino groups, hydroxyl groups, ethoxy groups, thiol' acetate groups, etc. Examples of particularly suitable decane coupling agents include compounds such as KH-560 'a commercially available couple Co-agent (3 glycidyloxypropyl) 5 trimethoxy sulphur, KH550, or DC Z 6020 and DC Z 6040 available from D〇w Corning, Midland, MI. The amount of decane coupling agent is usually polyurethane. The total weight of the binder composition is from 1 to 7% by weight of the total weight of the binder composition. In some embodiments, the star-shaped h coupling agent is used in an amount of from 1 to 3% by weight based on the total weight of the polyurethane-filled binder composition. Retroreflective elements at least partially embedded in the agent (7). In some embodiments Inverse 2 retroreflective beads. The retroreflective beads useful in the present application are microsphere-shaped and generally have a substantially spherical shape to provide the most uniform and effective retroreflection. The microspheres are preferably substantially transparent. To minimize the absorption of light and to reflect the incident light to a greater extent. The term "transparent" as used herein refers to the ability to transmit light. Microspheres are generally essentially colorless, but in some other cases, It may be colored or colored. The microspheres may be made of glass, non-glass ceramic composition, or synthetic resin. Usually, glass microspheres are preferred, so they are cheaper and harder than microspheres made of synthetic resin. It is more durable. The average particle size of the 20 microspheres is usually about 1 〇 to 200 μm, or about 25 to 80 μm. The microspheres have a refractive index in the range of from 25 to 25, and the U spheres used in some embodiments have a refractive index of about 1 91. The choice of the refractive index of the microspheres depends on the desired application of the reflective tape. The microspheres are typically coated with a specularly reflective metal reflective layer disposed beneath the urethane adhesive portion of the microspheres 13 200902600 or on the back of the microspheres. As used herein, the term "specular reflection layer" refers to a layer containing elemental metal capable of reflecting light, preferably specularly reflected light. The metal may be continuously coated by vacuum deposition, vapor coating, chemical deposition or electroless ore. Various metals can be used to provide a specularly reflective layer. 5. It includes aluminum, silver, chromium, nickel, magnesium, etc. in elemental form. Aluminum and silver are most commonly used for the metal of the specularly reflective layer. Some metals can be metal oxides and/or hydroxides. In the form of objects, aluminum and silver metals are the most preferred because they provide good retroreflective brightness. The specularly reflective layer should be thick enough to reflect incident light. Typically the specularly reflective layer has a thickness of 10 to about 50 to 150 nm. As an alternative to the metal layer, a dielectric mirror can be used as the specularly reflective layer. The dielectric mirror can be similar to the known dielectric mirrors disclosed in U.S. Patents 3,700, 305 and 4, 763, 985 to Bingham. In general, retroreflective tapes are prepared by retroreflective elements such as 15 glass microspheres. A single layer is embedded in a carrier tape (Fig. 1, 20) with a binder (Fig. 1, 20) with an embedded depth not exceeding the diameter of each microsphere 5〇%; depositing a specularly reflective material on the retroreflective element; coating the urethane adhesive composition disclosed herein on the specularly reflective deposit; heat curing the adhesive composition to form a thermoplastic or thermosetting adhesive layer; peeling with adhesive The carrier 20 band 'has a reflective tape as shown in Fig. 2, that is, the retroreflective element is partially lost in the polyurethane bond layer. Referring to Fig. 1, the carrier tape 10 may be paper, enamel or other material. The adhesive having the adhesive coating 20' may be polyethylene. The partially dispersed beads may be any transparent beads such as glass beads. The beads have a reflective layer 14 200902600 40, such as a metal coating, functionally Provided on the side opposite to the coating (four) and the cutting (four), the metal coating may be disposed on the bead and may at least partially cover the portion of the bead surface. The bead 3〇 is at least partially embedded in the binder, the binder The polyurethane composition may be 疋. The reflective layer is disposed between the binder column 5 and the beads 30. Other suitable intermediate layers may also be disposed therein. The point is called 5_0 usually ^ 〇〇 ~ _ micron thick 'or even thin ~ willow The thickness of the meter is not the same as that of the non-targeted retroreflective sheeting, which is the same as that of the figure, in which the carrier tape 1 with the adhesive coating 20 is removed. ^ The polyurethane adhesive composition may be a diisocyanate , polyisocyanate 10 S, polyol, unsaturated polyol, chain extender and any desired additives such as a mixture of catalysts, pigments, etc., or also a mixture of poly-prepolymers. If pre-polymerization is used The mixture usually contains f 2# part A and part B. Typically, part A contains the reaction product of a diisocyanate, a polyisocyanate, a polyol and an unsaturated polyol, and part B contains one or more bonds 15 = a long agent. Parts A and B are usually mixed prior to use. The thermal cure of the polyurethane is typically about 70. (: ~ about 18 (per temperature at rc, using an oven or other heating technique. In some cases, heating at a temperature of about 7 Torr to about 15 Torr: the curing rate can also be increased by using the above catalyst. The properties of the polyurethane S-polymer can be varied by changing the composition and content of the isocyanate and hydroxyl reaction samples used to make the polyurethane. The Tongwei binder composition contains isocyanate groups: hydroxyl groups. The molar ratio is JA丨.5.1, and more specifically, the binder composition contains isocyanate: the molar ratio of the base is 1:1 to 1.3: 1. Usually, the polyurethane adhesive contains 30 to 60% by weight. Hard segment. "Hard segment 15 200902600 (hard segment)" and "softsegment" are well-known concepts in the polyurethane field. In this paper, hard segment elements are diisocyanates, polyisocyanates, chain extenders and functionalities greater than 2 Any of the polyols, and the soft segment element is a polyol, which is a glycol. 5 A retroreflective vulcanized rubber article is prepared by co-vulcanizing a retroreflective tape and an unvulcanized rubber, said retroreflection The tape contains a plurality of retroreflective elements at least partially embedded in the urethane adhesive. The urethane adhesive contains an unsaturated group which can be co-vulcanized with the unf-vulcanized rubber during the vulcanization process. Examples of curable substrates Articles comprising rubber and/or coated with 10 rubber, and other substrates having curable groups. The unvulcanized rubber used to prepare the co-vulcanized retroreflective rubber article is typically an uncured elastomer composed of various elastomer-forming sheets. A class of such monomers is a variety of co-dienes having 4 to 12 carbon atoms. Specific examples of the monomers include butadiene, isoprene, pentadiene, hexadiene, Geng 15 Diene, octadiene, 2,3-dimethyl-i,3-butadiene, 2-methyl-l53-pentadiene, etc. An example of such an elastomer is natural rubber. The term "natural rubber, , refers to an elastomeric material obtained from various trees and plants, which are usually grown in tropical or desert regions of the world. This material contains very high levels (more than 90%, often more than 95%) of cis 1 4-isoprene Conjugated 20 dienes also include various copolymers or their interpolymers. Other types of uncured elastomers can also be used. Some of these elastomers are called "synthetic rubbers" because they are not from trees or plants. A useful class of elastomers are prepared from the above monomers having a conjugated diene having 4 to 12 carbon atoms and a vinyl-substituted aromatized 16 200902600 compound having 8 to 15 carbon atoms. Examples of the aromatic compound include styrene, α-mercaptostyrene, 4-tert-butylstyrene, vinyl fluorene, divinylbenzene, isopropenylbenzene, diisopropenylbenzene, etc. Some of these copolymerizations Examples of the material include SBR (poly(styrene-butadiene)), poly(α-mercaptostyrene. 5 butadiene), and poly(4-tert-butylstyrene-butadiene). Another type of synthetic rubber is butyl rubber. Butyl rubber is a copolymer of isobutylene and a small amount of isoprene. Gas butadiene rubber is another type of synthetic rubber that can be used. The gas butadiene rubber is a polybutadiene (2-chloro-1,3-butadiene). Another type of synthetic rubber is nitrile rubber. The nitrile rubber is a co-polymer of the above diene having 4 to 12 carbon atoms and an acrylonitrile monomer. The particular rubber or rubbers used will vary with the type and type of use of the rubber article. For example, when the rubber article is a bicycle tire, a mixture of natural rubber and synthetic rubber is usually used. In some embodiments, the rubber is a mixture of 75% natural rubber and 25% synthetic rubber, but the percentage of natural rubber 15 and synthetic rubber varies with the particular application. Typically, the unvulcanized rubber contains one or more vulcanizing agents which are capable of crosslinking the elastomeric rubber and are capable of co-vulcanizing with the unsaturated groups on the polyurethane adhesive of the retroreflective sheeting. Typically, the amount of vulcanizing agent is less than about 5% by weight. Typically, the vulcanizing agent includes sulfur or a sulfur-containing compound such as 骸20 benzo. Seychelles and Ν-cyclohexyl 2 benzoin sulphur amide, or may contain a peroxide vulcanizing agent. Peroxide vulcanizing agents include, for example, peroxy vinegars, basal peroxides, ternary peroxides, and peroxy condensates. Furthermore, the vulcanization can be carried out with xenon radiation. The reflective rubber is completed by co-vulcanization of the retroreflective sheeting and the unvulcanized rubber. 17 200902600 远; The far product can be prepared by a retroreflective chelating agent containing retroreflective elements. The polyurethane adhesive contains an unsaturated group which is co-vulcanized with an unvulcanized rubber to form a rubber article. In one example, the rubber article is a tire, such as a bicycle tire. — 15 Reverse: The way of reflecting the month and the unvulcanized rubber knee is to contact the side of the non-vulcanized rubber that does not contain the retroreflective sheeting. This kind of connection is carried out. A technique that is useful in the manufacture of tires is that the molding apparatus and method used to manufacture and cure tires are known in the art of tires. The retroreflective sheeting and the unvulcanized rubber are typically placed in 'expanding the inflatable in-mold airbag with steam or other such pressure' to expand the retroreflective sheeting and the unvulcanized rubber into the mold, reverse reverse:: reverse The reflective element faces the inner surface of the mold. The further expansion of the mold airbag allows the retroreflective sheeting and the unvulcanized rubber knee to conform to the shape of the mold, thereby achieving the desired tire shape, texture and tread pattern. The co-vulcanized retroreflective sheeting and the unvulcanized rubber are overcome by pressurizing for a predetermined period of time to properly hold the bladder during which the heat and pressure are transferred to the bladder by a base steam or other known method. The outer surface of the mold can also be heated to aid in co-vulcanization. After removing the tire product from the mold, the reverse polarity of the formed tire was measured. In some embodiments, the retroreflective brightness is at least 50% of the brightness of the vulcanization process = front retroreflective sheeting. In other embodiments, the retroreflective redundancy is 8% of the brightness of the retroreflective tape prior to the vulcanization process. In some embodiments, the retroreflective elements of the formed tire have a retroreflective illumination of 25 〇 cpl (cpl stands for candela/lux/square meter). In other embodiments, the retroreflective elements of the formed tire have a retroreflective brightness of 400 cpl. Referring to Figure 3', an exemplary vulcanized rubber article 300 disclosed herein is shown. The bead 30 is at least partially embedded in the urethane adhesive 50, the reflective coating 40 is disposed between the bead 30 and the urethane adhesive 50, and the urethane adhesive 50 is bonded to the vulcanized rubber layer 60. While layer 60 is shown as a planar article, those skilled in the art will readily appreciate that layer 60 may be cured, or generally it may be of any desired shape and size. The drawings also do not have a marking scale. The examples are for illustrative purposes only and are not intended to limit the scope of the appended claims. All parts, percentages, ratios and the like in the examples and the rest of the specification represent weight unless otherwise indicated. The solvents and other reagents used were obtained from Sigma-Aldrich Chemical Company; 15 Milwaukee, Wisconsin, unless otherwise stated. Reference table abbreviations or trademarks, naming description DESMOPHEN C1200 polycarbonate diol having a molecular weight of approximately 2000, from Bayer MeterialScience, Leverkusen, Germany, DESMOPHEN X2501 polycarbonate diol having a molecular weight of approximately 1000, from Bayer MeterialScience, Leverkusen, Germany, purchased HTPB 2800 hydroxy-terminated polybutylene 19 having a molecular weight of approximately 2,800 200902600 dilute 1,4-BDO 1,4-butanediol DESMODUR I isophorone diisocyanate, purchased from Bayer MeterialScience, Leverkusen, Germany DESMODUR VL based on diphenylmethane diisocyanate-based aromatic polyisocyanate, purchased from Bayer MeterialScience, Leverkusen, Germany, DESMODUR NZ1 aliphatic polyisocyanate g, from Bayer MeterialScience, Leverkusen, Germany, purchased FOMREZ UL29 tin Catalyst, REGAL 99R carbon black was purchased from GE Silicones, BICAT Z secret-zinc catalyst was purchased from Cabot, and KH-560 stearic coupling agent (3 glycidyloxypropyl) trimethoxy was obtained from Shepherd Chemical Company. Base decane unvulcanized rubber used to prepare bicycle tires containing natural rubber Chemical rubber and sulfur vulcanizing agent temporary carrier film for polyethylene carrier paper with a temporary carrier layer for microspheres. Test method: 20 200902600 Retroreflective brightness: According to test method ASTM E808-81, the following is obtained with a reverse luminometer Retroreflective test results for each piece of material. Information is expressed in candelas / lux / square meters (cpl). 5 Adhesion to rubber The adhesion of the retroreflective sheeting to rubber was measured by the following method: The reflective sheet was covered with a polyethylene terephthalate (PET) film half of the surface of the rubber co-vulcanized. The PET film is used to prevent a part of the retroreflective sheet from sticking to the rubber surface. The resulting laminate was placed in a template where it was cured at 180 10 ° C for 15 minutes under a pressure of 15 Newtons. After vulcanization, the PET film was removed and the sample was cut into strips. According to ASTM D 1876-95 T-Peel Test, the unbonded portion of the reflective tape began to peel off front side to determine the peel strength. Example 1

15 DESMOPHEN C 1200, DESMOPHEN X 2501, HTPB 2800 and 1,4-BDO were mixed in a container at 500 rpm for 30 minutes in the amounts shown in Table 1. To the mixture, DESMODUR I, DESMODUR VL, FOMREZ UL29 in the amounts shown in Table 1 were added, and the resulting mixture was stirred at 500 rpm for 30 minutes. The mixture was coated onto a carrier tape with glass beads, 20 glass beads were aluminized and coated to a thickness of 300 microns. The coated sheets were placed in an oven at 125 ° C for 30 minutes and then annealed in an oven at 65 ° C for 2 days. The carrier tape was peeled off, and the retroreflective brightness (initial retroreflective brightness) was measured, and the adhesion to the rubber and the retroreflective brightness after vulcanization were tested. The results are shown in Table 2. 25 Example 2 21 200902600 The same procedure as described in Example 1 was carried out in the amounts shown in Table 1, and the results are shown in Table 2. Table 1 Reagent Example 1 Example 2 DESMOPHEN C 1200 (weight 25.04 9.00 parts) DESMOPHEN X 2501 (weight 9.74 16.00 parts) HTPB 2800 (parts by weight) 14.90 30.56 l, 4-BDO (parts by weight) 11.72 9.34 DESMODUR I (weight Part 27.31 24.18 DESMODUR VL (parts by weight) 9.71 9.34 FOMREZ UL29 (per million) 50 50 Comparative Example C1:

5 The same procedure as described in Example 1 was carried out except that the commercially available product 3M SCOTCHLITE 8150 was used instead of the experimental retroreflective sheet prepared in Example 1, and the results are shown in Table 2. Table 2 Test Example 1 Example 2 Comparative Example C1 Initial retroreflective brightness (cpl) 444 459 480 Retroreflective brightness after vulcanization (cpl) 268 263 400 22 200902600 Adhesion to rubber (N/mm) 3.20 3.84 1.80 ~ Example 3 - ~~~ Part A Preparation: DESMOPHEN C 1200, HTPB 2800, DESMODUR I, 5 DESMODUR VL and REGAL 99R were mixed in a container at 1000 rpm for 3 hours in the amount shown in Table 3. Part B Preparation: l,4-BDO, BYK359 and BICATZ were mixed in a container at 500 rpm for 30 minutes in the amounts shown in Table 3. Mixing, Coating and Curing 10 Part A and Part B prepared above were mixed in a mixer and coated on a glass bead carrier tape which had been coated with a thickness of 4 μm. The coated sheets were placed in an oven at 165 ° C for 30 minutes and then annealed in 15 (TC oven for 2 hours. Stripped glass beads were carried out and the retroreflective brightness (initial retroreflective brightness) was measured 'testing the adhesion to rubber' And retroreflective brightness after vulcanization, 15 results are shown in Table 4. Table 3 Reagent A (parts by weight) Part B (parts by weight) DESMOPHEN C 43.40 — 1200 HTPB 2800 8.00 ---- DESMODUR I 29.00 ---- DESMODUR VL 4.69 ---- REGAL 99R 4.95 ---- 1,4-BDO — 8.68 23 200902600 BYK359 —— 1.00 BICAT Z -— 0.29 Table 4 Test Example 3 Comparative Example C1 Initial Retroreflective Brightness (cpl) 450 480 Vulcanization Post-retroreflective brightness (cpl) 270 400 Adhesion to rubber (N/mm) > 1.20 1.80 Example 4 - 9 parts A Preparation:

5 Mix DESMOPHEN C 1200, DESMOPHEN X 25 (U, HTPB 2800, DESMODUR I, DESMODUR VL, DESMODUR NZ1 and FOMREZ UL 29 in a container at 500 rpm ' for 5 hours according to the amount shown in Table 5. Part B Preparation: 10 1,4-BDO, glycerin, FOMREZ UL 29 and KH-560 were mixed in a container for 15 minutes at 100 rpm in the amounts shown in Table 5. Mixing, coating and curing the parts A and B prepared above were mixed at 500 rpm. Stir for 15 minutes, then apply to the glass bead carrier tape as shown in Table 6. The glass beads have been plated with aluminum. 15 The coated sheets are placed in an oven at 125 ° C for 30 minutes and then at 65. (: in an oven Annealing for 2 days, stripping the glass bead carrier, measuring the retroreflective brightness (initial retroreflective brightness), testing the adhesion to rubber, and the retroreflective brightness after vulcanization, 24 200902600

The results are shown in Table 7. Table 5: Part A Reagent Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 DESMOPHEN C1200 (parts by weight) 9.00 7.25 0 0 0 0 DESMOPHEN X 2501 (parts by weight) 16.00 16.91 26.75 24.53 24.64 24.64 HTPB 2800 (parts by weight) 30.56 29.53 26.75 24.53 24.64 24.64 DESMODUR I (parts by weight) 24.18 23.69 26.66 25.81 25.93 25.93 DESMODUR VL (parts by weight) 9.34 0 10.30 0 0 0 DESMODUR NZ1 (parts by weight) 0 13.65 0 15.71 15.78 15.78 FOMREZ UL 29 (per million) 0 150 0 150 150 150

Table 6: Part B Reagent Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 1,4-BDO (parts by weight) 9.34 8.97 9.55 9.42 7.89 7.89 25 200902600 Glycerin (parts by weight) 0 0 0 0 1.13 1.13 FOMREZ UL 29 (per million) 50 100 50 150 150 150 KH-560 (parts by weight) 0 0 0 0 0 0.5

Table 7 Test Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Thickness (micron) 300 280 320 260 350 350 Initial retroreflective brightness (cpl) 459 450 461 445 506 518 Retroreflective brightness after vulcanization ( Cpl) 263 301 265 322 412 394 Adhesion to rubber (N/mm) 5.8 5.4 C. [Simple description of the drawings] Figure 1 shows a schematic cross-sectional view of a co-vulcanized retroreflective sheeting of the invention. 26 200902600 Figure 2 shows a schematic of the present invention. A cross-sectional schematic view of the co-vulcanized retroreflective sheeting described in the section is shown in Figure 3. The cross-face of the vulcanized rubber article of the invention is shown in the following. Symbol of the main component 10 40 100 Carrier tape 20 Adhesive 30 Bead Reflective layer 50 Adhesive 60 Vulcanized rubber layer Reflective sheet product 200 Reflective sheet product 300 Rubber product 27

Claims (1)

200902600 X. Patent application scope: Γ ιο 15 20—Vulcanized rubber products, including: vulcanized rubber parts; and retroreflective sheeting elements, the reverse whistle-the two-gate reflective sheet element has: first and second surface a polyurethane adhesive layer; and a plurality of retroreflective elements on the first surface, the knife is inserted into the first surface of the polyurethane adhesive layer, and the vulcanized rubber is partially adhered. 2. As claimed in the patent garden The |y σ rubber product is a tire. The product described in the article "Vulcanized rubber II", such as the patent scope of the patent, includes at least one - 昱 昱 ;; ^ 丹 杈 杈 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰a reaction product of at least one unsaturated polyol and at least one of the reaction mixtures. A chain extender 4' is as described in claim 1, which is a polycaprolactam, a polycarbonate diol, a polyoxyalkylene glycol, a polyester diol or a mixture thereof. 5. The product as described in claim 4, wherein the polyol further comprises a polyol having a functionality greater than 2, and the polyol of the product of claim 3 is a hydroxyl terminated polybutadiene. . 7. The preparation according to item 3 of the patent application is a diol having a number average molecular weight of less than 丨2〇. δ. The product of claim 3, wherein the polyol, the alcohol, the polyurethane, wherein it is unsaturated, wherein the chain is extended, wherein the anti-28 200902600 mixture also includes a decane coupling agent. _ The article of claim 1, wherein the retroreflective 70 pieces have a retroreflective brightness of at least 250 cPl. Οο. A method of preparing a vulcanized rubber article, comprising: providing a retroreflective sheeting element comprising: a further polyurethane having an adhesive layer having first and second surfaces for co-vulcanized unsaturated sites, And a plurality of retroreflective π members partially embedded on the first surface to contact the second surface of the water urethane adhesive layer with the unvulcanized rubber material; and 10 - vulcanizing the unvulcanized rubber material under heat and pressure to reverse The second surface of the adhesive layer of the reflective sheet member is bonded to the vulcanized rubber material. 11. The method of claim 10, wherein the step of contacting the second surface of the adhesive layer with the unvulcanized rubber comprises: placing the retroreflective sheeting member in a mold; and 15 introducing the unvulcanized rubber material into the mold The mold is brought into contact with the second surface of the adhesive layer. 12. The method of claim 10, wherein the retroreflective sheeting after vulcanization has a brightness of at least 5% by weight of the sheet before vulcanization. 13. The method of claim 10, wherein the polyurethane 2 is a reaction mixture comprising at least one monoisocyanate, at least one polyisocyanate, at least one polyol, at least one unsaturated polyol, and at least one chain extender. reaction product. 14. The method of claim 13 wherein the at least one polyol further comprises a polyol having a functionality greater than two. 29 200902600 I5. As stated in claim 13, the alcohol is a hydroxyl terminated polybutadiene. The method, wherein the method of not reducing, wherein the method of reacting, wherein the polyurethane 16 is as described in claim 13 of the patent application, further comprises a catalyst. Q π. The reaction product of the two reaction mixtures as described in claim 11 of the patent scope, ίο The first of these includes: a polyurethane prepolymer comprising at least one less than one diisocyanate, to a small amount of polyhydric alcohol, a polyisocyanate, to an unsaturated polyol; and the first wound comprising at least one chain extender. 30