United States Patent (19)
`Honda et al.
`
`(54)
`
`(75
`
`73
`
`22
`21
`
`(30)
`
`METHOD FOR IMPROVING THE
`ADHERING ABILITY OF WULCANIZED
`RUBBER SURFACES
`inventors: Toshio Honda; Shoji Tanaka, both
`of Akigawa, Yukio Fukuura,
`Kodaira; Yoshikatsu Suzuki; tsuo
`Tanuma, both of
`Higashi-Murayama; Koichi Iwami,
`Kunitachi; Shoson Shibata, Tokyo,
`all of Japan
`Assignee: Bridgestone Tire Company Limited,
`Tokyo, Japan
`Jan. 28, 1974
`Filed:
`Appl. No.: 437,081
`
`Foreign Application Priority Data
`Jan. 26, 1973 Japan................................ 48-10775
`Feb. 16, 1973 Japan................................ 48-18418
`May 12, 1973 Japan................................ 48-52885
`
`(52)
`
`(5)
`58)
`
`U.S. Cl................................. 264/343; 264/232;
`264/265; 423/365
`nt. C.’.................... B29C 25/00; COB 21/12
`Field of Search .............. 423/365; 156/308, 96,
`15671 10 A; 264/36, 232, 340, 343, 265
`
`11,
`(45)
`
`3,968,198
`July 6, 1976
`
`(56)
`
`2,976,910
`3,642,553
`3,754,973
`3,755,165
`3,846, 160
`
`References Cited
`UNITED STATES PATENTS
`3/961 Nowak.................................. 156796
`2f1972 Georges.............................. 56/308
`8/1973 Spurlin................................ 1561308
`8/1973
`Bhakuni et al.................. 56/ O A
`1 1/974 Hirakawa et al.................... 156/308
`
`Primary Examiner-Jeffery R. Thurlow
`Attorney, Agent, or Firm-Sughrue, Rothwell, Mion,
`Zinn & Macpeak
`
`ABSTRACT
`57
`A method for improving the adhering ability of a vul
`canized rubber surface by treating said surface with a
`solution of iodine isocyanate or a mixed solution of
`iodine isocyanate and iodine to provide a high adher
`ing ability to said surface.
`The thus treated vulcanized rubber surface can be
`adhered strongly to other vulcanized rubber or the
`other various materials by contacting these materials
`tightly using an adhesive or without using an adhesive.
`8 Claims, 7 Drawing Figures
`
`
`
`AO
`
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`
`--------------
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`O 5O
`70
`9O
`76/7perature (C)
`
`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 1
`
`

`

`U.S. Patent July 6, 1976
`
`Sheet 1 of 5
`
`3,968,198
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`
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`Yita v. MacNeil IP, IPR2020-01139
`Page 2
`
`

`

`U.S. Patent July 6, 1976
`
`Sheet 2 of 5
`
`3,968,198
`
`A/G 2
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`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 3
`
`

`

`U.S. Patent July 6, 1976
`
`Sheet 3 of 5
`
`3,968,198
`
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`Aressure (Ag/cm?)
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`
`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 4
`
`

`

`U.S. Patent July 6, 1976
`
`Sheet 4 of 5
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`3,968,198
`
`
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`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 5
`
`

`

`U.S. Patent July 6, 1976
`
`Sheet 5 of 5
`
`3,968,198
`
`A/G 6
`
`A.
`
`4.
`
`Eage N4
`A
`5
`
`
`
`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 6
`
`

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`5
`
`()
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`15
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`20
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`25
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`30
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`35
`
`METHOD FOR IMPROVING THE ADHERING
`ABITY OF WUCANIZED RUBBER SURFACES
`BACKGROUND OF THE INVENTION
`l. Field of the Invention
`The present invention relates to a method for im
`proving the adhering ability of the surface of vulca
`nized rubber.
`2. Description of the Prior Art
`It is generally difficult to adhere a vulcanized rubber
`to the other materials and such an adhering is more
`difficult than the case when an unvulcanized rubber is
`superposed on or contacted with the other materials
`and vulcanized and simultaneously adhered.
`As a method for adhering a vulcanized rubber, it has
`been proposed that the surface of the vulcanized rub
`ber is applied with a solution of a unvulcanized rubber
`in an organic solvent, such as toluene and the like, that
`is a rubber cement and dried, after which the thus
`treated vulcanized rubber and an unvulcanized rubber
`are superposed and pressed and vulcanized to ahdere
`the unvulcanized rubber to the vulcanized rubber.
`However, there is a defect that a mold corresponding to
`the requirement in an integrating molding must be
`manufactured in every molding and further a compli
`cated mechanical apparatus is necessary for the press
`ing and heating. Furthermore, the object to be adhered
`is limited to the same kind of unvulcanized rubber.
`As the other method, there has been proposed that a
`rubber cement obtained by dissolving unvulcanized
`polychloroprene (CR), acrylonitrile-butadiene co
`plymeric rubber (NBR), generally referred to as "ni
`trile rubber," a graft copolymeric rubber obtained by
`grafting a vinyl compound, such as methyl methacryl
`ate and the like to the above described rubbers or
`blends of these rubbers with phenolic resins, in an or
`ganic solvent, is used for adhering the vulcanized rub
`ber to the other materials, but this method cannot pro
`40
`vide a satisfactory adhesion.
`Moreover, there has been a process wherein a spon
`taneous vulcanizing rubber cement which vulcanizes at
`room temperature by using vulcanizing superaccelera
`tors or sulfur chloride, is used, but this process also
`cannot provide a satisfactory adhesion.
`As a surface treating process of a vulcanized rubber
`which has been heretofore carried out, there has been
`proposed that the surface of the vulcanized rubber is
`strongly oxidized with concentrated sulfuric acid, po
`tassium permanganate, potassium dichromate and the
`50
`like and washed with water to remove the above de
`scribed treating agent and then the vulcanized rubber is
`bent to form fine cracks on the whole surface, thereaf
`ter the thus treated vulcanized rubber is applied with an
`adhesive and then adhered to the other materials.
`However, the user of these strong acids or strong
`oxidizing agents must pay a full attention in the han
`dling. Nevertheless, the adhesion is not satisfactory and
`the vicinity of the surface of the vulcanized rubber is
`deteriorated by such strong oxidizing agents.
`In addition, it has been well known that the surface of
`a vulcanized rubber is treated with a solution of an
`organic polyisocyanate compound, for example, triphe
`nylmethane triisocyanate solution (made by Bayer,
`Germany, Desmodur R (Trade Mark)) but this process
`was not possible to provide a satisfactory adhesion.
`The present invention enables one to adhere strongly
`vulcanized rubbers mutually or a vulcanized rubber to
`
`3,968, 198
`2
`the other various materials by using an ahdesive or
`without using an adhesive by treating the vulcanized
`rubber surface with a solution of iodine isocyanate or a
`mixed solution of iodine isocyanate and iodine to pro
`vide a high adhering ability on said surface and then
`contacting the thus treated vulcanized rubber with a
`vulcanized rubber or the other materials to be adhered
`tightly and pressing and heating them.
`The method for improving the adhering ability of a
`vulcanized rubber surface according to the present
`invention can be effectively utilized particularly in the
`following fields;
`a. composite materials, in which vulcanized rubber
`particles are dispersed and embedded in a matrix,
`b. a method for retreading pneumatic tires,
`c. pneumatic safety tires in which the bead portion
`and the bead seat of the rim are integrated,
`d. a method for partially repairing pneumatic tires,
`and
`e. a dock fender wherein a synthetic resin layer is
`integrally formed to an impact receiving portion.
`A. It has been already known that vulcanized rubber
`particles can be dispersed in a castable polymer, for
`example, polyurethane elastomer. However, the inven
`tors have found that the composite material produced
`by the conventional process has great defects. Namely,
`when a stress is periodically applied to such composite
`materials, a satisfactory bending fatigue resistance can
`not be obtained. The composite material produced by
`the conventional process in which black vulcanized
`rubber particles compounded with carbon are dis
`persed in a colorless and transparent polyurethane
`elastomer matrix, is generally seen black but when this
`composite material is bent and the bent surface is ob
`served, it is found that the maximum bent portion, that
`is, only a zone where the stress has most concentrated,
`is seen to be white so that said portion floats. This is
`because numerous fine breakages are formed inside the
`portion where the stress concentrates.
`B. As the method for retreading pneumatic tires, it
`has been known that a vulcanized tread rubber is
`wholly or partially fixed to a base tire to be retreaded.
`The prior such type method is as follows as shown in
`U.S. Pat. No. 2,976.9 O.
`A tread rubber layer of tire run for a given distance is
`carefully removed and said tire is subjected to a buffing
`and then on the resulting base tire, a vulcanized or
`semi-vulcanized tread rubber layer having a tread pat
`tern is forcedly contacted through an unvulcanized
`rubber sheet and then the assembly is pressed and
`heated, whereby the vulcanization and adhering are
`effected. Even if this method has made various im
`provements as compared with the conventional meth
`ods for retreading tires, there are the following defects.
`That is, since the vulcanization step is necessary, the
`installation therefor is necessary.
`By selecting the quality of the rubber to be inserted
`between the base tire and said vulcanized tread rubber
`layer, a certain variation may be made but the heating
`O
`is essential for the vulcanization and this heating brings
`about the heat deterioration of the base tire. For solv
`ing this defect, the vulcanization at a low temperature
`for a long time has been proposed but this means low
`ers the production efficiency and particularly in the
`spontaneous vulcanizing rubber the adhesion is defi
`cient. In addition, in the use of an adhesive, the defi
`ciency of the adhesive has never been solved.
`
`45
`
`55
`
`65
`
`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 7
`
`

`

`3,968,
`198
`3
`4
`C. The pneumatic tire has the following skeleton
`process cannot be simply effected. A simple and effec
`struture. A pair of bead wires having ring forms com
`tive method for adhering the tire to the rim, by which
`posed of non-elongating metal wires are provided at a
`the defects of these prior technics, can be obviated and
`space in the axial direction of tire and carcass plies in
`the pneumatic tires and rims are strongly and 'simply
`which the cords composed of fibers, such as textile, 5
`integrated, so that when the tires run on road in normal
`metal or glass are covered with a rubber, are held and
`state, even if a greatly large side force occurs, the tires
`secured in a toroidal form aside from one bead wire to
`neither separate nor get out from the rims, and further
`another bead wire.
`even if the inner pressure of the tires decreases or in an
`Such a pneumatic tire is set to a rim in the following
`extreme case, is exhausted, the tires do not get out from
`manner. A bead seat of the rim mounts the bead por- 10
`the rims and can run safely and in which, if necessary,
`tion housing the above described head wire and sup
`the tires can be removed from the rims relatively easily,
`ports the whole tire and air is filled in the inside of the
`has been demanded.
`tire and the inner pressure of the filled air compresses
`D. Some methods for partially repairing tires have
`the bead portion to the bead seat of the rim which
`been known. In these methods, when a damaged hole
`inclines at a given angle against the axial direction of 5
`which perforates from the tread rubber layer to the
`tire and the rim flange which limits the outer periphery
`carcass layer (rubber applied cord cloth layer), is
`of the bead seat.
`caused by a sharp rock or metal piece and the like,
`This compressing force is strong and therefore, of
`muddy soils and the like around the damaged portion
`course, when the tires run straightly and even when the
`are removed by washing and then a rubber is embedded
`running direction of tires is curved and the tires are 20
`into the damaged hole and said portion is partially
`subjected to the force of the axial direction of tires
`pressed and heated to effect a partial vulcanization or
`(referred to as "side force' hereinafter), if said force is
`said portion is embedded with a spontaneous vulcaniz
`mild, the bead portion neither separates nor gets out
`ing rubber in order to omit the vulcanization step.
`from the bead seat of the rim.
`However, the tire to be repaired is composed of a
`However, when the car speed is high over a certain 25
`vulcanized rubber and as well known, the vulcanized
`degree, if a particularly large side force is applied as
`rubber has many difficulties in the adhering and there
`when the tires are rapidly curved, the side force be
`fore the circumference of the damaged hole must be
`comes larger than the compressing force owing to the
`previously subjected to buffing, applied with a rubber
`inner pressure and the bead portion separates or may
`cement (a solution of unvulcanized rubber dissolved in
`get out from the bead seat. When a tube is used in the 30
`an organic solvent, such as gasoline) and then fully
`inner portion of the tire, the unstability of the handle
`dried, after which the thus treated damaged hole is
`and the cutting of the tube only occur. However, in the
`embedded with a rubber. Accordingly, this method is
`tubeless tire recently broadly used in view of safety
`very troublesome and nevertheless the adhesion is low
`against puncture, which is caused, for example, by
`and the complete repairing cannot be made.
`stepping on a nail, in which a rubber sheet having a 35
`E. It has been already known that synthetic resins,
`given thickness is adhered to the inner surface of the
`such as polyurethane resins, epoxy resins, polyethylene
`tire and a tube is omitted, said tire and the rim are
`resins and the like are adhered to the surface of an
`directly sealed at the bead portion, so that as soon as
`impact receiving portion of a dock fender composed of
`the bead portion is separated from the rim flange in the
`a vulcanized rubber to protect the rubber body from
`manner as described above, the inner pressure is rap- 40
`abrasion and impact due to the impact of ships. How
`idly exhausted and such a case is very dangerous.
`ever, the adhesion of the synthetic resins to the rubber
`Therefore, the tire designers have attempted to make
`is poor, so that the synthetic resins are readily sepa
`the compression of the bead wire to the rim fully strong
`rated and dropped off due to the difference of elastic
`but if such a means is adopted, it is very difficult to set
`strain and satisfactory dock fender has never been
`the tire into the rim.
`45
`obtained.
`On the other hand, in such a type tire that the tire and
`The object of the present invention is to solve the
`the rim are integrated by the inner pressure in this
`above described various problems which are caused
`manner, if the inner pressure is exhausted or decreased
`because of the low adhesion of the vulcanized rubber,
`owing to any cause, the tire separates from the rim and
`by providing a high adhering ability to the surface of
`gets out from the rim and the running becomes impossi- 50
`the vulcanized rubber in order to obtain a strong adhe
`ble or if this phenomenon occurs suddenly, there is a
`sion between mutual vulcanized rubbers or between a
`possibility of occurrence of a great accident.
`vulcanized rubber and the other various materials and
`to provide,
`Heretofore, various attempts have been made for
`solving this problem.
`a. composite materials having a satisfactory bending
`For example, Japanese laid open Pat, application No. 55
`fatigue resistance in which vulcanized rubber parti
`4,552/7 and U.S. Pat. No. 3,669, 74 disclose that the
`cles are dispersed and embedded in a matrix,
`bead portion is mechanically fixed from the inside and
`b. a method for retreading pneumatic tires by which
`outside of the tire.
`any vulcanization step for adhering is omitted and
`Alternatively, West Germany laid open Pat. applica
`the retreated pneumatic tires having a high durabil
`tion No. 2,055, 172 discloses that the rim and the tire 60
`ity can be obtained,
`are pressed and heated to effect vulcanization and
`c. a safety tire in which the bead portion of pneu
`adhering.
`matic tire and the bead seat in the rim are strongly
`In the former process, the cost of the rim raises and
`and simply integrated,
`further when the inner spacer and the outer spacer are
`d. a method for partially repairing tires in which the
`bound by bolts and the like, the airtight sealing process 65
`repairing operation is easy and can be effected in a
`is complicated and this process is not reliable.
`short time and further a high durability is obtained
`In the latter process, the surface treatment of the rim
`and the performance of the retreated tire is not
`and the large size apparatus are necessary and this
`lowered by the repairing, and
`
`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 8
`
`

`

`3,968, 98
`6
`5
`Solution mainly consisting of the above described io
`le. a lock fender in which a synthetic resin layer is
`dine isocyanate is left to stand and the solvent is volatil
`strongly integrated with the dock fender body com
`ized, the remaining solidified substance causes a small
`posed of the Vulcanized rubber. Furthermore, the
`explosion of a slight degree owing to a slight shock. The
`present invention can be applied broadly to indus
`trial articles, for example, endless workings of con
`inventors have found that in the treatment of the vulca
`nized rubber with the solution mainly consisting of
`veyor belts and rubber crawlers and the method of
`iodine isocyanate, if said solution is used by mixing
`the present invention can be effectively used for
`molding of articles, in which the vulcanized rubber
`treating assistants mentioned in detail hereinafter, the
`is a constituting element.
`above described small explosion does not occur and the
`surface treatment can be safely effected.
`SUMMARY OF THE INVENTON
`When the vulcanized rubber, the surface of which
`has been improved by the method of the present inven
`The present invention relates to a method for im
`proving the adhering ability of the surface of the vulca
`tion, is to be adhered to the other vulcanized rubber or
`nized rubber in which the surface of the vulcanized
`the other various materials using an adhesive, various
`rubber is previously treated with a solution of iodine
`adhesives can be used. Among them the adhesives
`isocyanate or : mixed solution of iodine isocyanate and
`capable of curing through the progress of hydrogen
`iodine. The vulcanized rubber, the surface of which has
`transfer reaction of electrophilic group with nucleo
`been improved by the present invention, can be
`philic group or the adhesives of chain extended ther
`strongly adhered to the other vulcanized rubber or the
`moplastic resins formed by the reaction of electrophilic
`other various materials by contacting the improved
`group with nucleophilic group of the thermosetting
`vulcanized rubber with the other vulcanized rubber or
`resins which are thermally cured by cross-linkage
`the other various materials tightly and pressing and
`through the reaction of electrophilic group with nu
`heating them using an adhesive or without using an
`cleophilic group, are preferable.
`According to the present invention, it is possible to
`adhesive.
`As mentioned above, it has been well known that the
`strongly adhere mutual vulcanized rubbers or the vul
`surface of the vulcanized rubber is treated with a solu
`canized rubber with the other various materials, and
`tion of an organic polyisocyanate compound, for exam
`therefore when the articles where the vulcanized rub
`ple, a solution of triphenylmethane triisocyanate (made
`bers are used for adhering are produced, the method of
`by Bayer, German, Desmodur R (Trade Mark)), but
`the present invention can be utilized in various modes.
`this process can not provide a desirable adhesion. How
`Particularly, in the fields of
`ever, if the surface of the vulcanized rubber is treated
`a. composite materials in which the vulcanized rub
`with a solution of iodine isocyanate, in spite of the fact
`ber particles are dispersed and embedded in a ma
`that iodine isocyanate is monoisocyanate, a very strong
`trix composed of castable polymers,
`adhesion can be obtained. This difference is based on
`b. a method for retreading the pneumatic tires,
`the fact that the organic polyisocyanate compound is
`c. a pneumatic safety tire in which the bead portion
`difficulty chemically reacted with the surface of the
`and the bead seat are integrated,
`vulcanized rubber, while iodine isocyanate is easily and
`d. a method for partially repairing the pneumatic
`rapidly added to unsaturated bonds of polymer exposed
`tires, and
`on the surface of the vulcanized rubber. It has never
`e. dock fenders in which a synthetic resin layer and
`been known that iodine isocyanate is effective in such
`the impact receiving portion are integrated and the
`a manner for the adhering of the vulcanized rubber.
`like, the present invention have solved various
`lodine isocyanate (INCO) is different from the other
`problems which have been encountered because of
`organic isocyanate and shows a specific reactivity and
`the low adhering ability of the vulcanized rubber,
`reacts with the unsaturated double bond as follows,
`and can accomplish the above described objects
`(a)-(e). Therefore, the present invention has very
`high commercial merits.
`BRIEF DESCRIPTION OF THE DRAWINGS
`FIG. 1 is a diagram showing the storage stability of
`various treating solutions containing iodine isocyanate
`to be used in the method for improving the vulcanized
`rubber surface according to the present invention;
`FIGS. 2 and 3 are diagrams showing the results of
`peeling test when the vulcanized rubbers, the surfaces
`of which have been improved by the method of the
`present invention, are mutually contacted tightly and
`then pressed and heated;
`FIG. 4 is a cross-sectional view of the pneumatic
`safety tire obtained by utilizing the present invention;
`FIG. 5 is a detailed view showing the structure for
`binding the vicinity of the bead portion to the rim of the
`embodiment as shown in FIG. 4;
`FIG. 6 is a view for explaining the method for par
`tially repairing tire utilizing the present invention; and
`FlG. 7 is a perspective view of the dock fender, which
`has been produced using the method of the present
`invention.
`
`50
`Such a reaction cannot be expected in the treatment
`with an organic polyisocyanate, for example, De
`smodur R. Accordingly, in the case of Desmodur R the
`adhesion is low.
`The inventors have found that the properties of the
`surface of the vulcanized rubber are rapidly changed
`only by applying a solution of iodine isocyanate to the
`surface of the vulcanized rubber at room temperature,
`to form the surface which can be very easily adhered.
`Furthermore, the inventors have found that when
`there is any possibility of deterioration of the rubber
`surface, if the surface of the vulcanized rubber is
`treated with a mixed solution of iodine isocyanate and
`iodine, it is possible to prevent the deterioration of the
`rubber surface and to improve the adhering ability of
`the surface of the vulcanized rubber satisfactorily and
`effectively.
`It has been (bserved that when a brush and the like
`usel in the treatment of the vulcanized rubber with a
`
`55
`
`6)
`
`f's
`
`35
`
`4)
`
`45
`
`a Y - - 1 Nr. r1
`INCO +cc = C <>, <
`N = C = O
`
`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 9
`
`

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`O
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`15
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`20
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`25
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`
`7
`DESCRIPTION OF THE PREFERRED
`EMBODIMENTS
`The present invention relates to a method for adher
`ing the vulcanized rubber and more particularly to a
`method for adhering a vulcanized rubber to a vulca
`nized rubber or a vulcanized rubber to the other vari
`ous materials.
`The term 'vulcanization' used herein means the
`introduction of three dimensional cross-linked struc
`tures between rubber molecules. Thus, thiuram vulca
`nization, peroxide vulcanization, quinoid vulcaniza
`tion, resin vulcanization, metal salt vulcanization,
`metal oxide vulcanization, polyamine vulcanization,
`radiation vulcanization, hexamethylenetetramine vul
`canization, urethane cross-linker vulcanization and the
`like are included in addition to sulfur vulcanization
`which is usual and most important.
`Rubbers involve natural rubbers (NR) and synthetic
`rubbers.
`Synthetic rubbers include homopolymers of conju
`gated diene compounds, such as isoprene, butadiene,
`chloroprene and the like, for example, polyisoprene
`rubber (R), polybutadiene rubber (BR), polychloro
`prene rubber and the like; copolymers of the above
`described conjugated diene compounds with vinyl
`compounds, such as styrene, acrylonitrile, vinyl pyri
`dine, acrylic acid, methacrylic acid, alkyl acrylates,
`alkyl methacrylates and the like, for example, styrene
`butadiene copolymeric rubber (SBR), vinylpyridine
`butadiene-styrene copolymeric rubber, acrylonitrile
`butadiene copolymeric rubber, acrylic acid-butadiene
`copolymeric rubber, methacrylic acid-butadiene copol
`ymeric rubber, methyl acrylate-butadiene copolymeric
`rubber, methyl methacrylate-butadiene copolymeric
`rubber, acrylonitrile-butadiene-styrene terpolymer and
`the like; copolymers of olefins, such as ethylene, pro
`pylene, isobutylene and the like with dienes, for exam
`ple isobutylene-isoprene copolymeric rubber (IlR);
`copolymers of olefins with non-conjugated dienes
`40
`(EPDM), for example, ethylene-propylene-cyclopen
`tadiene terpolymer, ethylene-propylene-5-ethylidene
`2-norbornene terpolymer and ethylene-propylene-1,4-
`hexadiene terpolymer; polyalkenamer obtained by ring
`opening polymerization of cycloolefins, for example,
`polypentenamer; rubbers obtained by ring opening
`polymerization of oxirane ring, for example, polyepi
`chlorohydrin rubber and polypropylene oxide rubber
`which can be vulcanized with sulfur, and the like. Fur
`thermore, halides of the above described various rub
`5)
`ber, for example, chlorinated isobutylene-isoprene co
`polymeric rubber (Cl-IIR), brominated isobutylene
`isoprene copolymeric rubber (Br-IIR) and the like are
`included.
`Particularly, the present invention is characterized in
`that the surfaces of the vulcanized rubbers of natural
`rubber (NR), styrene-butadiene copolymeric rubber
`(SBR), polybutadiene rubber (BR), polyisoprene rub
`ber (IR), isobutylene-isoprene copolymeric rubber,
`halides of these rubbers (Cl-R, Br-IIR) and copoly
`mers (EPDM) of olefins with non-conjugated dienes,
`which are poor in the adhering ability, are improved to
`provide them a high adhering ability. Of course, the
`present invention can be applied to the other rubbers.
`All these rubbers may be kneaded with compounding
`agents conventionally used for compounding with rub
`ber, for example, fillers, such as carbon black, silica,
`calcium carbonate, lignin and the like, softening
`
`3,968, 198
`8
`agents, such as mineral oils, vegetable oils, synthetic
`plasticizers prior to the vulcanization and then vulca
`nized.
`The vulcanized rubbers, the surface of which has
`been improved according to the present invention, can
`be easily adhered to the other materials.
`As these adhesives, mention may be made of polyure
`thane resins, epoxy resins, phenol aldehyde resins,
`polyhydric phenol aldehyde resins, phenol furfural
`resins. xylene aldehyde resins, urea formaldehyde res
`ins, melamine formaldehyde resins, alkyd resins, poly
`ester resins and the like.
`These resins have electrophilic groups and when
`these resins are added with an agent having nucleo
`philic groups, that is a compound having an active
`hydrogen, for example, an amine compound, a reaction
`occurs between the electrophilic groups and the nu
`cleophilic groups and the two dimensional or three
`dimensional intermolecular reaction gradually pro
`ceeds and the curing occurs.
`Among the above described adhesives, polyurethane
`resins and epoxy resins which have a relatively similar
`elasticity to the tensile elasticity of the vulcanized rub
`ber are preferred.
`Since it has been known that these polyurethane
`resin and epoxy resin adhesives are effective for adher
`ing various materials, for example, inorganic materials,
`such as metals, ceramics, earthenwares, porcelains,
`glasses and the like and organic materials, such as natu
`ral fibers, synthetic fibers, papers, natural leathers,
`synthetic leathers, synthetic resins and the like, it has
`become possible to adhere the vulcanized rubber to the
`above described materials through the above described
`adhesives. Furthermore, the same kind of vulcanized
`rubbers or different kind of vulcanized rubbers can be
`adhered mutually.
`As the adhesives in the present invention, other than
`the adhesives having such a property that the curing
`proceeds owing to the reaction of the electrophilic
`group with the nucleophilic group, the adhesive con
`sisting of a chain extended thermoplastic resin obtained
`by the reaction of the electrophilic group with the nu
`cleophilic group, has also a high adhesive effect.
`An embodiment of adhesive which is not effective in
`the method of the present invention, is an adhesive
`which has been used as a hot melt type adhesive, for
`example, a non-reactive type adhesive, such as ethy
`lene-vinyl acetate copolymer (EVA).
`It is possible to mix various extenders, softening
`agents and other compounding agents to the adhesives
`to be used in the present invention prior to curing as
`long as the object is not deviated. For example, carbon
`black, silica, calcium carbonate, calcium sulfate, clay,
`sulfur, various metal powders, metal oxide powders,
`inorganic fiber powders, organic fiber powders, plastic
`powders, wood powders, cork powders, stone powders,
`rubber powders, corn powders, vegetable oils, mineral
`oils, petroleum fractions, petroleum series softener,
`synthetic plasticizers, asphalt, coal tar, various antioxi
`dants, ozone crack preventing agents may be com
`pounded conveniently,
`The further surprising facts have been found by the
`inventors.
`Namely, the vulcanized rubbers, the surfaces of
`which have been improved by the method of the pre
`sent invention, can be easily adhered only by contact
`ing mutually these surfaces tightly and then pressing
`and heating them. In this case, the pressure to be up
`
`45
`
`55
`
`60
`
`65
`
`MacNeil Exhibit 2059
`Yita v. MacNeil IP, IPR2020-01139
`Page 10
`
`

`

`5
`
`2
`
`35
`
`3,968, 198
`9
`10
`plied is sufficient at higher than (), () Kg/cm and the
`benzene, toluene, xylene, etc., and paraffinic hydrocar
`heating temperature is sufficient at higher than 40°C
`bons, such as hexane, pentane, octane, etc., may be
`but the preferable pressure and temperature are 2.0
`mixed to the solution of iodine isocyanate in ether. The
`Kg/cm' - 100 Kg/cm and 88°C-200°C, respectively.
`concentration of iodine isocyanate, when dioxane or
`The more preferable temperature and pressure are
`tetrahydrofuran is used as a solvent, is not less than
`130°C-180°C and 5 Kg/cm-50 kg/cm, respectively.
`0.01% by weight. However, when the concentration of
`The heiting time is sufficient at 2-5 minutes.
`iodine isocyanate becomes not less than 5% by weight,
`The surface of the vulcanized rubber treated with the
`the reaction in the treatment is too violent and numer
`method of the present invention cannot be distin
`ous fine cracks are formed on the surface layer of vul
`guished by the naked eye in the appearance from the
`canized rubber, and deterioration may be observed.
`surface of the untreated vulcanized rubber. It is quite
`This tendency is often observed in NR and BR, but is
`surprising that such bodies which are solid and do not
`not observed in EPDM. Accordingly, iodine isocyanate
`show fluidity even at a raised temperature, are adhered
`is used within the concentration range in a solvent of
`strongly in a very short time by the above described
`0.01 to 15% by weight, preferably 0.1 - 5% by weight.
`simple process.
`Particularly, it is surprising that even when the surface
`Similarly, the vulcanized rubber treated with the
`of vulcanized rubber is treated with a very diluted solu
`method of the present invention can be adhered
`tion of about 0.1% by weight, such diluted solution is
`strongly to usual elastomers hardened by curing in the
`still effective.
`same manner as described above without using any
`The inventors further have found that if there is a
`adhesives.
`fear of the deterioration of rubber surface, the surface
`It is further surprising that if the