Classifications

• • G—PHYSICS
  • G07—CHECKING-DEVICES
  • G07F—COIN-FREED OR LIKE APPARATUS
  • G07F17/00—Coin-freed apparatus for hiring articles; Coin-freed facilities or services
  • G07F17/32—Coin-freed apparatus for hiring articles; Coin-freed facilities or services for games, toys, sports, or amusements
  • G07F17/3202—Hardware aspects of a gaming system, e.g. components, construction, architecture thereof
  • G07F17/3204—Player-machine interfaces
  • G07F17/3209—Input means, e.g. buttons, touch screen
• • G—PHYSICS
  • G07—CHECKING-DEVICES
  • G07F—COIN-FREED OR LIKE APPARATUS
  • G07F17/00—Coin-freed apparatus for hiring articles; Coin-freed facilities or services
  • G07F17/32—Coin-freed apparatus for hiring articles; Coin-freed facilities or services for games, toys, sports, or amusements
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
  • C23C2222/20—Use of solutions containing silanes

Definitions

• Silanes are applied to metal surfaces for several purposes including corrosion resistance and adhesion promotion.
• steel tire cord must adhere to the rubber in order to function properly. Steel does not bond well to rubber.
• the steel tire cord has been coated with a layer of brass.
• the rubber forms a chemical bond with the brass.
• This rubber/metal bond is formed only with sulfur vulcanized rubber which requires a relatively high sulfur level, greater than 4 phr, as well as certain accelerators, i.e., a delayed action sulfonamide and cobalt in the form of cobalt naphthenate to achieve proper cure and good adhesion, as well as zinc oxide.
• the cobalt improves the stability of the rubber/brass bond. However, it also has a negative effect on the stability of the rubber network in that it accelerates reversion in the presence of oxygen at elevated temperatures. The increased sulfur and cobalt are believed to be necessary in order to achieve a satisfactory bond between the tire cord and the rubber.
• Silane coatings are also applied to other forms of metals. They may be applied in aqueous solution, or suspension, or dissolved in a volatile solvent.
• SUMMARY OF THE INVENTION The present invention is premised on the realization that metal such as tire cord can be coated with a silane coating by running the metal through an oil bath containing a small percentage of silane. Excess material is simply wiped off using an air wipe or other similar device. With respect to coating tire cord, this is advantageous because the tire cord normally must pass through an oil bath during processing.
• any organo-functional silane can be employed.
• Such silanes are known to improve adhesion and prevent corrosion.
• the silane can be any organosilane that improves rubber/metal adhesion. These can include, for example, vinylsilanes, aminosilanes, polysulfidesilanes, as well as blends of organosilanes.
• the silane will be a blend of an amino silane and a polysulfide silane.
• This method can be used to coat any type of metal, including brass, aluminum, steel and galvanized metal.
• metal is coated with an organofunctional silane utilizing an oil bath containing the silane.
• the organosilane can be any organosilane. These may be added to provide corrosion resistance or as an adhesion promoter, in particular a metal-rubber adhesion promoter.
• the metal is a wire, and in particular steel or brass coated steel tire cord.
• the rubber can be any rubber that incorporates metal such as tires and conveyor belts.
• Typical organofunctional silanes used in these applications include vinyl silanes, aminosilanes, and polysulfidesilanes, as well as mixtures thereof.
• Such silanes are disclosed in U.S. patent 6,416,869; U.S. patent 6,756,079; PCT application WO2004/009717; pending application U.S.2005/0058843; and U.S. patent 6,919,469, the disclosures of which are hereby incorporated by reference.
• One preferred silane coating composition for sulfur cured rubber systems is a blend of a bis-silyl amino silane and a bis-silyl polysulfur silane, with the ratio of bis-silyl amino silane to bis-silyl polysulfur silane from about 1 :10 to about 10:1 , preferably 1 :3, by weight.
• the preferred bis-silyl aminosilanes which may be employed in the present invention have two trisubstituted silyl groups, wherein the substituents are individually chosen from the group consisting of alkoxy, aryloxy and acyloxy.
• these bis-silyl aminosilanes have the general structure:
• each R 1 is chosen from the group consisting of: C 1 -C 24 alkyl (preferably C 1 -C 6 alkyl), and C 2 -C 24 acyl (preferably C 2 -C 4 acyl).
• Each R 1 may be the same or different, however, in the hydrolyzed silane solutions, at least a portion (and preferably all or substantially all) of the R 1 groups are replaced by a hydrogen atom.
• each R 1 is individually chosen from the group consisting of: ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec- butyl, ter-butyl and acetyl.
• Each R 2 in the aminosilane(s) may be a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group, and each R 2 may be the same of different.
• each R 2 is chosen from the group consisting of: C 1 -C 10 alkylene, C 1 -C 10 alkenylene, arylene, and alkylarylene. More preferably, each R 2 is a C 1 -C 10 alkylene (particularly propylene).
• X may be: R 3 R3 R3
• each R 3 may be a hydrogen, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group, and each R 3 may be the same or different.
• each R 3 is chosen from the group consisting of hydrogen, C 1 -C 6 alkyl and C 1 -C 6 alkenyl. More preferably, each R 3 is a hydrogen atom.
• R 4 in the aminosilane(s) may be a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group.
• R 4 is chosen from the group consisting of: C 1 -C 10 alkylene, C 1 -C 10 alkenylene, arylene, and alkylarylene. More preferably, R 4 is a C 1 -C 10 alkylene (particularly ethylene).
• Exemplary preferred bis-silyl aminosilanes which may be used in the present invention include bis-(trimethoxysilylpropyl) amine (which is sold under the tradename Silquest® A-1170 by GE Silicones); and bis-(trimethoxysilylpropyl)ethylene diamine.
• the preferred bis-silyl polysulfur silanes which may be employed in the present invention include:
• each R 1 is as described before.
• at least a portion (and preferably all or substantially all) of the R 1 groups are replaced by a hydrogen atom.
• Z is -Q -S x -Q -, wherein each Q is an aliphatic (saturated or unsaturated) or aromatic group, and x is an integer of from 2 to 10.
• Q within the bis-functional polysulfur silane can be the same or different.
• each Q is individually chosen from the group consisting of: C 1 -C 6 alkyl (linear or branched), C 1 -C 6 alkenyl (linear or branched), C 1 -C 6 alkyl substituted with one or more amino groups, C 1 -C 6 alkenyl substituted with one or more amino groups, benzyl, and benzyl substituted with C 1 -C 6 alkyl.
• bis-silyl polysulfur silanes include bis- (triethoxysilylpropyl) sulfides having 2 to 10 sulfur atoms. Such compounds have the following formula:
• x is an integer of from 2 to 10.
• One particularly preferred compound is bis-(triethoxysilylpropyl) tetrasulfide (also referred to as bis- (triethoxysilylpropyl) sulfane, or "TESPT").
• TESPT bis-(triethoxysilylpropyl) tetrasulfide
• Commercially-available forms of TESPT such as Silquest® A-1289, available from GE Silicones
• Silquest® A-1289 available from GE Silicones
• these commercially-available forms of TESPT have a distribution of sulfide chain lengths, with the S 3 and S 4 sulfides predominating.
• Silanes can be either hydrolyzed or unhydrolyzed, and can be utilized in combination with an aqueous resin dispersion. Typically, the silanes are not hydrolyzed when combined with the resin dispersion, as well as when added directly to the oil bath as described below. However, the silanes tend to hydrolyze through exposure to air.
• a variety of water dispersible resins can be employed including epoxy resins, novolac resins, acrylate resins, and polyurethane resins. In addition to the water dispersible resins, neat resins can also be used that are compatible with the oil and the selected
• the water borne dispersion of polymeric resin may also include a
• an organic solvent such as an alcohol (e.g. ethanol), as well as surfactants used to keep the resin in solution or
• the dispersion includes about
• the resin dispersion may be purchased commercially and can include, for example, Epi-rez 5522-WY-55, a 55% solids dispersion of a
• reducible epoxy resin or ECO CRYL 9790, an aqueous acrylic with 42%
• the silane is applied to the metal in an oil bath. If silane is used without resin the silane is added directly to the oil bath.
• the concentration of the silane should be from about .5% to about 10% by weight, preferably about 2%, with 6% most preferred.
• the oil should comprise 80% or more of the bath (by weight) with at least 95% preferred.
• the silane is combined with an aqueous dispersion of a resin, the ratio of resin dispersion (50-55 active) to silane by weight should be from about 1 :5 to about 5:1 , with 1:1 preferred. It is generally desirable to minimize the amount of resin, using only enough to insure the silane is dispersed in the mixture. If added, the silane is mixed with the resin dispersion, sufficient dispersion is added to the oil bath to provide .5-10% by weight silane in the bath, with 6% by weight preferred.
• the oil should be a non VOC lubricating oil and can be any mineral, animal orvegetable based oil.
• Oil includes synthetic lubricants such as polyglycols, dibasic acid esters, chlorofluoro carbons, silicone oils, neopentyl polyol esters, and polyphenyl ethers.
• the oil will be a mineral oil, such as a paraffinic or naphthenic lubricating oil, having a viscosity such that it flows at application temperature. Any oil which can be used in a tire cord manufacturing process can be used in the present invention.
• One such oil is a heavily hydrotreated naphthenic having a viscosity of 60 SUS @ 100 0 F CAS 647-52-5.
• the metal Prior to coating the metal in the oil bath, the metal should be cleaned with an acid or alkaline cleaner and rinsed with deionized water, preferably, an alkaline cleaner.
• the silane oil mixture can be applied to the metal surface by any common method such as spraying, brushing, emersion coating, curtain coating, and the like.
• the Figure shows an exemplary coating apparatus 10 adapted to coat tire cord 12 with oil 17 containing the silane.
• the apparatus 10 is a trough which is divided by barrier 11 into first and second sections 13 and 15.
• First section 13 includes first and second grooved rollers 14 and 16.
• the cord 12 runs back and forth in grooves in rollers 14 and 16 and is thus repeatedly submersed in the oil 17 in first section 13.
• the cord 12 moving in the direction o f arrows 26 then passes through an air wipe 18 which forces off excess oil and coating material. This excess is then taken from second section 15 of apparatus 10 and redirected through line 20 and redeposited back on roller 14 into the first section 13 of the coating trough 10.
• the temperature of the oil bath will generally be about room temperature (50-120 0 F), but can be raised up to the boiling point of the oil.
• the cord should be in oil for .1 to 10 seconds, preferably 1-2 seconds. This is controlled by controlling the path through the oil as well as the speed of cord 12.
• the cord After being coated, the cord is simply rolled onto a spool and then can subsequently be used to form belting for tires, conveyer belts, and the like.
• Typical rubber formulations are disclosed in U.S. patent 6,919,469, the disclosure of which is incorporated herein by reference.
• Tire cords amino silane A1170, Sulfane A1289, Epi-rez 3510 W-60, Epi-rez WD 510, Lubesnap 60 lubricant.
• Test compounds include a typical tire rubber formulation that has excellent adhesion to brass incorporating cobalt naphthenate and a compound used for test purposes that has no adhesion to brass, i.e., without cobalt naphthenate.
• Vulcanization parameters 172 0 C for 16 minutes at 43 kg/m 2 .
• Epi-rez WD 510 contains 100% solid with greater than 90% bisphenol A epoxy resin and less than 10% polymeric dispersant.
• Epi-rez 3510 W-60 is an aqueous dispersion of bisphenol A epoxy resin, which contains 61 % solid in water. The below matrix describes the physical constituents of the hydrolyzed silane mixtures.
• the below listed values are measured on a 100g total weight basis.
• the wires were cleaned as previously described. A 1:3 ratio was maintained between A1170 and A1289.
• the wires after being cleaned were coated with the above silane mixtures and cured in rubber and tested under tension for adhesion.
• the matrix listed below assesses the effect of cleaning and drying on the oil based WD 510 resin silane system.
• the neat silane concentration was 20% by weight and the ratio of A1170 to A1289 is 1 :3. Equal parts of A1170 and WD 510 were added.
• the tire cords were cured in the experimental rubber and tested under tension for adhesion. Table 3
• the oil based silane resin mixture B works better than the water based resin silane mixture A. Both these mixtures offered the same rubber coverage.
• Silane mixture D is the best performing mixture of the oil based resin silane system in terms of pull out force and rubber coverage. It contains hydrolyzed A1289 and A1170. Stoichiometric quantity of water was added to just hydrolyze the A1289. Acetone was added in equal parts to water.
• silane mixture #1 gave the maximum coverage.
• the rubber coverage dropped off at higher silane concentrations.
• the cleaned wires were coated with the above silane mixtures and cured in the rubber compound and later tested in tension for adhesion. Hydrolyzed mixtures 6 and 8 gelled when the respective components were mixed. As such, they were not tested.
• Silane mixture #1 was the best performer among the 16 different solutions. Among the hydrolyzed solutions, mixture
• Control, hydrolyzed mixture #6 and hydrolyzed mixture #8 have zero rubber coverage. Highest rubber coverage is offered by both neat and hydrolyzed silane mixture #1. In other cases, neat silane mixtures offer more rubber coverage except in mixture #7 where the hydrolyzed mixture offers 125% more coverage than the neat solution.
• An analysis of line speed to drying temperature indicated that maximum pull out force was achieved at about 4m/min with a drying temperature of 140 0 C.
• the present invention permits the application of a wide variety of different silane formulations onto metal surfaces using an oil.
• the applied silanes then function to improve adhesion and provide other attributes typically associated with a silane coating, such as corrosion inhibition.
• Applying the silane coating with an oil bath provides greater flexibility in applying the silane, allowing it to be incorporated in line with many different processes. Many different processes require an oil coating, therefore the application of silane can be accomplished without additional equipment. This is particularly the case when the metal being coated is tire cord.
• the applied silane coating significantly improves the adhesion of the sulfur cured rubber to the tire cord while at the same time permitting the use of a rubber formulation that does not include a cobalt compound and has lower levels of sulfur, thereby improving the overall physical characteristics of the rubber itself.

Applications Claiming Priority (3)

Publications (2)

Family

ID=39521663

Family Applications (1)

Country Status (3)

Cited By (1)

Families Citing this family (3)

Family Cites Families (5)

• 2006
  • 2006-09-06 CN CN2006800329455A patent/CN101273102B/zh not_active Expired - Fee Related
  • 2006-09-06 JP JP2008530166A patent/JP5468259B2/ja not_active Expired - Fee Related
  • 2006-09-06 EP EP06803035.2A patent/EP1943314B1/de not_active Not-in-force

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events