DE2328158A1 - TIRE TREADS - Google Patents

Description

CRASEMANN * RAFTAY

2 HAMBURG? O

aOHLOASTRASÖEe PATENT LAWYERS:

1 «June 1973 DlPL ₁ -INa ₁ JORQENORASEMANN

DIPL.-INQ. VINOENZ ν. RAFFAY

: 1030/389

The Firestone Tire & Rubber Company Akron / Ohio 44317, U.S.A.

Pneumatic tire treads

The invention relates to a novel process for the manufacture of vehicle tires. The tire body from a liquid rubber mixture can be produced by centrifugal casting and therefore free of reinforcing elements. However, it may contain short fibers or pigments, etc., and may have an analysis typical of conventional tire bodies. The tread is not poured, but is usually placed in a mold and the tire body is placed against it. If necessary, glue can be used to bond the tire body to the tread.

The tread, which, a reinforcing agent such as carbon black or Silicon dioxide or a metal oxide etc / contains, is by chain extension of a polycarboxypolymer, which is different from the from (a) homopolymers or copolymers of conjugated dienes which contain 4 to 6 carbon atoms (e.g. polybutadiene, polyisoprene, Polychloroprene, polypiperylene, butadiene-isoprene etc.), (b) Copolymers of such a conjugated diene and an aromatic vinyl monomer (e.g. butadiene-styrene, isoprene-styrene, Butadiene-vinylnaphthalene, butadiene - ^ - methylstyrene etc.), (c) Copolymers of such a conjugated diene and a vinyl nitrile monomer (e.g. butadiene-acrylonitrile, isoprene-acrylonitrile, Butadiene - ^ - or ß-methylacrylonitrile, etc.), (d) homopolymers or copolymers of olefins (e.g. isobutylene, ethylene-propylene, etc.), (e) polyesters (e.g. polycaprolactone, polyethylene adipate etc.) and (f) polyethers (e.g. polytetrahydrofuran, polypropylene

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pylene glycol etc.) existing class. Optionally, polyamino and polythiopolymers of the same classes can be used as such or in mixtures with the. Polycarbonate polymers can be used. The polycarboxymaterial is chain extended with (1) an aliphatic or aromatic diepoxy resin, (2) an aziridine, (3) a carbodiimide, (4-) a diisocyanate or (5) a glyceride, reactions with the latter being transesterifications. £ s can be applied an additional sulfur or Peroxydvulkanisation. The preceding copolymers refer to rubbers ^ which.from monomers of the usual

/ manufactured sxnd /

Monomer percentage ranges and copolymers of other suitable monomer ranges, . the polymer of the tread can

Mixtures of the foregoing polymers or mixtures of each any one or more of the "foregoing chain extender reagents" contain.

The aliphatic or aromatic diepoxy resin may, for example, be a condensate; rion product of epichlorohydrin and bisphenol A (Epon 828), liesorcinol diglycidyl ether, epoxidized dicyclohexene, epoxidized polyolefins, 1, ^ - butanediol diglycidyl ether etc / -! Jas aziridine can rris (i- (2-meth, yl) aziridine) -phosphine oxide, TEAMG (Gyanamid), tl'S'j} (Cyanaaid), experimental co-reactants XD-7065 and .0-706 ^ (Dow), etc. be. The garbodiimide can be dicyclohexyl-carbodÜDside, polycarbodiimide PCD (Naftone, Inc.), polycarbodiimide ID-59 (Bui-ont), etc. The diisocyanate can be 2,4-toluene diisocyanate, hexamethylene diisocyanate, dianisidine diisocyanate, diphenylethane diisocyanate, etc. The glyceride may be oo etc. _t "jabohnenöl _t olive oil, palm oil.

The reactions are known in the art and specific instructions for the production of the stretched polymers are available from the manufacturers of the Heaktionsmittei.

For example, the iiealction of a liquid, carboxy-terminated Po.lvbutadiens with a diepoxy resin by the following Equiv

3 0 9883/0400

ο ο _ν

nHOOC-P-COOH + nH ₂ C-CRC-CH ₂

H H

I!
PCO-CH ₂ -CH-R-CH-CH ₂ -OC-J "

OH OH

In the equation, P denotes polybutadiene (or any of the previous polymers), 'which are carboxylated and a general formula for a diepoxy resin is given where H is a is aliphatic or aromatic half. The deeply sided For example, index η can be as low as about 4, but is preferably higher in the range of 10 or 20 up to 50 or 100 or above, with higher molecular weight polymers generally being preferred.

More than 2 carboxy groups can be linked to the -olybutadiene units. Regardless of the number of carboxy groups, an equal number of epoxy (or other chain extender) groups are required to complete the reaction, as shown in the equation, and this is true whether the elastomer is polybutadiene or any other elastomer. The relationship; of epoxy / oil, as represented by the formula, is at least 1.00 and this applies regardless of the number of carboxyl groups present, and regardless of the epoxy used in carrying out the ^ ea ^{1 tion.} The epoxy / C • .rboxy-V'erhäitnis may be 1.0 or bir to;>, 5, or 3.5, or perhaps be about ris be talysatoren generally K-, such as D / I.BCO, üimethylamino-methyl- pnenol, 2,4,6-'l ¹ ri (dimethylaminoethyl) -phenoi, ^, ^ - "- Jiisopropyl-salicylato-CnromClII) etc. for

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used the carboxy-epoxy reaction. In general, the The tendency for epoxy resin to self-polymerize is even more so the higher the epoxy / COOH ratio is. Higher concentrations von Äminbe accelerate this autopolymerization to favor. In cases where other chain extenders are used, the ratios of chain extenders drop agent to carboxyl group in the same ranges as described for the epoxy / COOH ratio. There can be additional Sulfur or peroxide vulcanizations using 1 to 4 or up to 8 parts per 100 parts of polymer can be used to advantage.

The amount of diepoxide (or other chain extender) to be used depends on the following factors: (1) the molecular weight of the polymer, (2) the functionality of the polymer, (3) the molecular weight of the chain extender, (A-) the functionality of the chain extender, (5) the amount of reactive impurities; (6) the reactive sites on the surfaces of the fillers used, such as carbon black, etc. Therefore, it is impossible to accurately suggest the amount of such chain extenders to be used.

The extension of carboxy-terminated polymers with other extenders is known in the art and, in general, the reactions are catalyzed by known catalysts.

Solid rubber, scrap rubber, reclaimed rubber etc. can be put into the Tread compound are mixed in. The tread of the invention contains every essential part of a vulcanizate, which comes from a polymer with a main chain (backbone), which 2 or more carboxy, amino or thio groups, extended as described, contains, and the elastomer of the tread can contain any amount of it up to 100%.

There are many in the manufacture of tires by centrifugal casting elastomeric fabrics have been used. These substances are selected because of their pourability properties with subsequent

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_ 5 -

Bender cures to a rubbery state which is suitable for use in vehicle tires, either pneumatic or solid tires. However, it has been found that the properties desired for the tread of a tire, such as slip resistance, etc., are not compatible with the properties required in sidewall areas, such as strength and high modulus. Accordingly, composite tires have been proposed in which different materials are used for the tread portion and the tire body. Such a construction uses a pre-formed tread part made of a mixture of natural or synthetic solid rubber, which is brought into a mold, with sidewalls made of a polyurethane mixture being pressed centrifugally thereon to form a composite tire, see GB-PS 1 118 4- 28. The main difficulty with this type of structure is to obtain good adhesion between the tread and the tire body, since these substances are chemically very different. ^ · - -.

There may be several of the approaches described here as known Approaches can be viewed similarly, but it is worth bearing in mind given that the use of such approaches when separate Manufacture of tire treads and tire bodies is new and not close.

The invention .

Tread Materials - for use in practicing the invention must be distinguished from other tire materials because they have good traction, both wet and dry, and Must have slip resistance. It is important that when sliding the tread of a tire is not heated to such an extent that that the rubber is melted so far that the tire loses its good slip resistance. Tread materials must Be abrasion-resistant so that they have a long service life. Uncured tread materials can also be much stiffer than those used in the body of a tire.

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The tread material can be a mixture of different here mentioned polymer and can be small amounts of other elastomers contain. It contains at least 25 or 50% or more a polycarboxy, thio or amino polymer. The polymer can have more than 2 reactive groups per chain, in some Cases up to 5 or more. However, the average functionality should usually no more than 3.0 ", functionality is made up of carboxy, thio or amino content values (e.g. obtained by KOfI-Ti tr at ion) and molecular weight values (e.g. VPO molecular weight, molecular weight determined from viscosity in dilute solution, gel permeation chromatography, etc.), and there are considerable difficulties in obtaining partially accurate functionality in this.

The mixing ingredients in the tread material can be any Type of reinforcing agent, e.g. carbon black, such as GPF, JS.AF, SuF etc., precipitated silica, etc. include. It can be any: · Kind of Emollient oil, "such as paraffinic, naphthenic and aromatic oils, dioctyl phthalate, etc. can be used. The higher aromatic oils appear to have some advantages over the others.

The word "pigment" used herein includes reinforcing pigments _t antioxidants, antiozonants, fillers, sulfur peroxide, etc.

There can be different types of antioxidants, antiozonants and the like, as suggested in the art for the use of such compounds in rubbers. However The hindered phenols are likely the most useful as they are likely to be less reactive with chain extenders are.

Any of the common peroxides can be used to supplement vulcanization be used.

Other polymers with different ends, such as aminoter-

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mined (but not tert-amino) polymers with main chains (backbones) derived from polyethers, polyesters, polybutadiene, butadiene / fc-tyrene copolymer, etc., and thiol-terminated Polymers with the same types of main chains by themselves or in mixtures with carboxy-terminated polymer chains The same chain extenders that are used for the carboxy polymers can be used with the amino and Thiol polymers can be used.

The process for making tread materials usually includes ?. stages. In the first stage, the polymer and all components of the mixture, except for the chain extenders, are premixed and finely ground, preferably on a three-roller mill, tttiritor-ivlihle, a Braben & er mixer, etc., so that the reinforcing and other pigments are finely divided. This material is labeled as a finishing compound and has an unlimited shelf life. The chain extender is mixed into the base mix and the resulting tread mix is poured into the mold just prior to pouring the tread body onto the tread. Mixing is expediently carried out on the same device as was used to produce the basic mixture, or in a different mixing chamber, such as a Buker-Perkins mixer. The time between adding the chain extender to the base mix and pouring the hoop body onto the tread material should be as short as [soluble. Adhesion of the tread to the r.ürper depends on the slight chain extension of the tread material before the body becomes clogged with the mold. The rate of chain elongation can also be controlled by changing the amount of catalyst.

The above statements are exemplary and can other methods and devices may be used if there is is desirable. -

The drawing shows a section of one produced according to the invention Tire The tread can be a desired thickness

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have and the dividing line between the tread and the The body of the body can vary depending on its location and configuration.

The invention creates a tread compound on which a Tire body can be centrifugally compression molded. The treads and Side wall parts have different properties, but are nonetheless solid for use; connected to a one-piece structure. An adhesive can be used to bond them together.

■ The tire is usually formed by changing the tread material brings into a mold and then brings the mixture forming the tire body against the tread, for example by a liquid mixture by centrifugal casting against the running surface brings, ds can also a conventional tire body against the L uffache be laid. The tread and tire body mix.vn are then vulcanized together, creating a strong bond is formed between them, ils can if necessary an adhesive can be used.

We can add reinforcement cords or inserts to the shape over the Tread can be laid before the tire body is cast, but no reinforcement is necessary. If desired, can short reinforcement threads are mixed with the tread material.

When adjusting the tread material, polycarboxy, thio or aluminum polycarbonate, interior can be freely mixed or exchanged, and the chain lengthening can be achieved by mixing together chain lengtheners. ^r ; sraitten take place.

Determination; optimal amount of Letten Extender is done comfortably by vulcanizing small quantities of a basic mixture different amounts of chain extender '(different Ratios of chain extender to reactive Ends) and choosing the ratio which -the 'desired Vulcanizate properties he: ibt.

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Tires division;

The technique describes devices which can be used in the casting of Heifen, for example those described in Beneze 3,555,141. Such devices, or improvements to the same, can be used in making belts from the tread compounds of the present invention. The vials are held in the mold cavity in any suitable manner. The tread is placed appropriately in the tread part of the mold and .the Heifenk body can be cast against it or brought against it in another way. A conventional tire body can be used. Mixtures for casting the body are known in the art, s'. for example GB-PÜ 1 139 643V. .

Description of a preferred execution form

The presence concerns the production of tread compounds in a form. The .Keifen] 'or per can be in the form be made by centrifugal casting on the tread plastic. The tread mix is usually so viscous that it does not flow easily during casting of the body. Üie can with a spatula or the like. be brought to the form and it can a teaching similar to that described in Beneze 3 555 141, but a longer one, can be used.

V-ann when Fornpressen a tire en prove to be desirable, a release agent, to use such as a poly (methyls.ilikon) oil, .the is .gebracht as an aerosol spray on the inner surfaces of the mold to the separation of the to support molded product from the mold.

The following examples illustrate the invention. The .calls are not limited to this. -.

In the following examples, label names and designations are used. f!> s used for oils, the composition of which is given below is.

3 Ö S a S 3/0 A 0 0

Adiprene L-167

DaBCO

Diaziridine XD-7063.

Diaziridine XD-7064 DiCup 4OG

Enjay EMD-590

Epon 828

-Spoxy resin / carbon black-1-.ai s chung "V-780.

Ethyl 702

Flexol EPO plasticizer

ISA? - "Black

Jeffamine D-2000 MOGA

SaF soot

= liquid polytetrahydrofuran, isocyanate-terminated, 6.3% NGO, tjpez. Wt 1.07-02 obtained from DuPont

= 1,4-diazabicyclo (2,2,2) octane = Experimental polymeric diaziridine having a typical amine equivalent weight of 300 sold by The Dow Chem. Co. = Same as XD-7063 except for typical amine equivalent weight of 560 = 40% dicumyl peroxide, sold from Hercules

= Garboxy-terminated liquid polyisobutylene, sold by En ₁ I ay

= Condensation product of J-spichlorohydrin and bisphenol a sold by Shell

= 10/90 ituss (epoxy resin paste: sold by the Color Division of Ferro Corp.)

= 4,4'-methylenebis (2,6-di-t-butyl-phenol), an antioxidant manufactured by Ethyl Corp. = Epoxidized Soybean Oil, sold by Union Carbide. = intermediate, highly abrasion-resistant C-I-Q carbon black

= amino terminated liquid polyoxypropylene sold by Jefferson Chem. Co.
= Methylene-bis-o-chloroaniline, sold by. DuPont
= highly abrasion-resistant furnace soot

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copy

232 * 158

Shell Dutrex 916 ^ rubber softening oil, sold by Shell UiI Co.

■ Silicone üil DC-200 = ^ l of the silicone type for mold lubrication, manufactured by Dow-Corning Company "

Thiokol HC-434 = carboxy terminated liquid

.Polybutadiene sold by Thiokol

The properties listed below were replaced by the following recognized tests determine:

DOT shelf life '. = Dept. of Transportation MVSS109

Endurance Test Permanent Deformation = Aw-L ¹ M D-395 Method B

Liability = ..LiJTM U-41V39, machine method

de, "btreifenmustar

100/9 or $ 00. liodul,
Tears,

Elongation at break. = Α / ΊΊ.1 i) -41.? 6? ^r J The "C"

Hing-pulling test

(kidney shaped test ^{piece) = A ^ 1} DM D-6P4-54 'The "B ^Ir Lhore" A "hardness = ASTM D-2240-64T

• Ltahlku.-el-Iiückprall = J.H.Dillon, 1.3. Prettyman

and G.L. .lall, J..ippl.Phy.1 ^, 309

In the following examples 1 and ?. There are two kinds of properties: the vulcanization properties of the laboratory and the results of tire tread durability. In most cases none of the results come from vulcanizing the same tread compound. Exceptions to this are noted for specific examples.

Since many chevrons are made for each example Average results for vulcanizate properties of the laboratory recorded.

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■ - ΛΖ -

The examples that relate to the making of an oven , contain results of tests on tires which run areas, as listed separately, and tire bodies, like fol ^ t:. '

Parts by weight

Adiprene L-167 100

Silicone Oil DC-200 0.1

Epoxy resin / kissing.

Mixture ("V-700" -) ^ 2.5

Di (2-eth, ylhexyl) phthalate 20

MOGa "19, 20 or 21

In some cases the bar body was not given a specific color, and in these examples the epoxy resin / cast iron mixture V-7S0 was omitted. The fluctuation in the MOG ^ content is a consequence of fluctuations ?! in the -.- "percent value KOO in the Adiprene L-167 from one batch to another, whereby more MOC _{5 was used} for the materials with a higher NGO content.

The recipe is only an example and other materials can be used in which other elastomers with reactive Share that with those present in the tread compounds reactive sites are reactive, are present.

The body material was manufactured in a stainless steel pressure vessel equipped with a high-performance stirrer, a heating and cooling jacket, connections for supplying nitrogen and for applying a vacuum to the free space of the container and a valve-equipped extraction line at the bottom of the container was. The prepolymer and all the ingredients with the .'Lusnahae ^ Oua were charged together under nitrogen into the container and this vorschlossen, sis then a vacuum of 3-5 mm abs. placed on the container and the contents loaded. away and heated to 162 ° * (72 ° J) for 2 hours, after which the

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- ■ 13 -

Container opened and the free space in the container was flooded with nitrogen. The MOGA was melted, ^{supercooled to 99 0} S ¹ (37 C) "and uj ^ e ^^ RH tubes added to the container. The vacuum was then applied and the mixture stirred for 3 minutes. Then nitrogen pressure was added to the container and the contents through the extraction line into a mold against the tread material, which in. the running surface of the mold had been previously placed, blown out. the centrifugal rotation of the mold and the furnace temperature was maintained at 25Q ° F (12.1 ⁰ C) for 2 hours ,, after which the rotation was resumed to air-cool the fojjm, at the end of which the rotation was stopped and the helper stripped from the mold.Most tires will be fully vulcanized during this cycle.

JSs example, ^L:; Surface mixtures of the following composition can be used:.

example 1 . Thiokol HG 434 Recipe: 100 Parts ISAF 50 Il Shell Dutrex 916 .5 II- Ethyl 702 ' 1 II. DABOO ■:; ■. ■ -3 H-" Epon 828 ¹ 23 , 3 "

All ingredients except the Epon 828 were mixed on a three-roll paint mill to make a master batch. The base mix and Epon 828 were mixed in a ^ m Baker-Perkins mixer (for tires) and hand spread into molds and cured for 3 hours at 100 ^° G (212 ^° F).

Physical Properties;

Tensile strength: 1775 ρsi (125 kg / cm ² ) at

23O? A stretch Tensile strength at

100 ⁰ C. 750 psi (53 kg / cm ² ) at

15O ', 6 elongation

Ring tear strength at 100 ° C: 97 lbs./in.

3UÖ883 / CU0Ö

Rebound at 23 ° C: '60%

Rebound at 10ü ° C:,

Shore ^gr A ^M hardness: 87

Permanent deformation (22 Btdn.

at 7O ⁰ G): 76%

Adhesion to cast body material: 75 lbs./in. at 23 ° C

Permanent deformation and adhesion tests were carried out on an identical one Laboratory batch determined.

HeifenlaufflächeneJK features: (Size E 78-1 * 0 DOT durability - 580

Tread vulcanization process

The tread was brought into the tire mold with a heated bpatel (71-77 ° C) and pre-cured at 107 ° G for 30 minutes. Were allowed to tread during 59 minutes to cool down, while various Zuaammenbauoperationen were carried out, and then it was again for 8 minutes at 107 ⁰ G heated · At this .Peer was geßossen the body within 2 minutes (Heitapparäte still at 107 ° G) and heating continued at "107 ° C for a further 20 minutes. Then, the Häuptvulkanisation was (x 2 hours at 121 ⁰ C), after which the tire was during 1 hour spin cooled.

Example 2

Recipe: 100 parts of Thiokol HG-434

50 "IüaF carbon black 10 "Lhell Dutrex 916 oil

1 "ethyl 702

3 "MBCO 22.98" kpon 828 ...

309β83 / 0400

Physical properties (all samples vulcanized 3 hrs. At 100 ° C..

Normal tensile strength:

Aged (4 days at 100 ° C) Tensile strength:

Hot ring (kidney-shaped test piece) at 100 ⁰ C -Zerreißfes-ACTION: Rebound at 23 ° C: Rebound at 100 ° G ... Shore "A" Hardness: Compression set - btdn 22nd i> ei.70 ^o C:

350 psi (25 kg / cnr) at 47Oo elongation

1425 psi (100 kg / em ² ) at 400% elongation

25 lbs./in*

27% 72

26%

Tire tread properties (size E 78-14)

DOT durability - 10 m *., Tread separate from the body

Tread vulcanization process:

This vulcanization cycle was the same as in Example 1 with the exception that 92 minutes for the various assembly operations were needed »

Example 3

Recipe:

Parts ünjay 5IAD-590 "ISAF soot

"DABOO
30.6 "Epon 828

Physical characteristics:

Tensile strength (vulcanized psi (82 kg / cm ^) at 160% strain

Rebound (vulcanized 55 '/ 149 ⁰ C) at 23 ⁰ C:

at 10 ° C: 27% iJhore "xt" hardness (vulcanized

309 & 83 / Q400

Permanent deformation - 22 iitdn. at 70 ° G (vulcanizations

Example 3 shows the use of carboxy terminated liquid Polyisobutylene in a barrel recipe.

example 4th Hurry Thiokol Hu-434 Reviewer: 100 'x' Il Ib , ¥ kiss 50 ti iühell Dutrex 916 oil 5 Il Ethyl 702 1 Il ΐλ-νβου 3 Il Epon Ü28 17, 5 Phy sikai »
Characteristics:

Normal tensile strength (vulcanized 55 '/ 1 ^ 9 ° C): 1 ^ 00 psi (84 kn / cin ² ) at 540%

strain

Aged (4 ia ^ e at 100 ⁰ G) Tensile strength (vulcanized 55 '/ 149 ⁰ O): 1625 psi (114 kg / cm ² ) at 280 ^

strain

100 ⁰ C tensile strength (vulcanized 55 '/ 149 ⁰ O) 6Ou psi (42 ky / cra " ⁵ ) at

100 ⁰ O Rin * (kidney-shaped test) Tensile strength (vulcanized 55 '/ 149 ⁰ G): 185 lbs./in. Steel back impact (vulcanized 72 '/ 149 ° C). at 23 ⁰ C 52> ^ at TOU ⁰ C y6 "o ühore" A "liörte (vulcanized 72 '/ 149 ⁰ O): permanent deformation - 2.2 ütdn.

at 70 ^o C (vulcanized »

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Example 4 is similar to Examples 1 and 2 except that less iipon 828 is used. Attention should be paid to the improvement in the 10O ⁰ C tensile strength.

Recipe:

example Parts ThiokoiHG-434 00 M. iS.OP iiuss 50 It bhell Dutrex 916 5 Il Ethyl 702 1 .5 " DABCO - ' 0, .5 " Upon 828 10,

Physical aiK

, Normal tensile strength

(vulcanized 80 '/ 160 ^ e) 170 psi (12 kg / cm ² ) at 310% elongation

Aged (4 days at 100 ⁰ C)

Tensile strength (vulcanized 80 '/

160 ⁰ C): 1050 psi at 27Ö / 0 elongation "

titahlkussel rebound (vulcanized 104 '/ 160 ⁰ C),,

at 23 ° C '31%

at 100 ⁰ C 18%

lihore "a" hardness (vulcanized
104 '/ 160 ⁰ C) 55

Consistent Verformun _e r - ßtdn 22nd
70 ⁰ C (vulcanized 104 '/ 160 ⁰ C): 76%

Example 5 contained only 10.5 phr Epon 828 to provide autopolymerization, tion of the iipoxy resin as low as possible.

Example 6

Recipe: 100 parts Thiokol HC-434 '.: ■

50 ISaF ii
5 "Ühell Dutrex 916

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Parts

1 , 5 - Ethyl 702 O , 5 ^ir DABCO 2 , 5 DiCup 400 10 Epon 828

Physical properties: Normal tensile strength (vulcanized 80/160 ⁰ G):

Aged (4 days at 100 ° C) Tensile strength (vulcanized 80 '/ 160 ⁰ C):

Steel ball rebound (vulcanized 104 '/ 160 ⁰ C)

at 23 ⁰ C

at 10O ⁰ C

Shore "λ" hardness (vulcanized 104 '/ 160 ⁰ G):

psi (56 kg / cnr) at 380% strain

psi (98 kg / cm ² ) at 210% elongation

26%

60

Permanent deformation - 22 hours
70 ⁰ C (vulcanized 104 '/ 160 ⁰ C) 52%

Example 6 is identical to Example 5 except that an additional peroxide vulcanization was applied. Noteworthy are the improvements in all physical properties.

Recipe:

example Parts 7th OO If Thiokol HC-434 50 Il IuAi ¹ soot 5 . Il Ühell Dutrex 916 1 Il Ethyl 702 3 , 2 " D ^ BCO 25, Flexol Ei ^J 0 plasticizer

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Physical properties: Normal tensile strength
(vulcanized 80 '/ 160 ⁰ C): 570 psi at 190% elongation

Aged (4 days at 10O ⁰ G) 'tensile strength (vulcanized

80 '/ 160 ⁰ G): 1040 psi at 210% elongation

Steel ball rebound (vulcanized 104 '/ 160 ⁰ C)

at 23 ° G:. 37% r

at 10O ⁰ G 46%

Shore .. "A" hardness (vulcanized 104 '/ 160 ⁰ C): 57

Compression set - 22 iitdn./70°C (vulcanised 104 '/ 160 ⁰ C): · 24%

Example 7 shows the use of Flexol EPO plasticizer, a epoxidized ooja. The average epoxy content is only 1.5 epoxy groups per glyceride, and chain elongation was in part by a esterification reaction.

Recipe:

example Parts 8th 100 Il 50 Il Thiokol HG-434 5 Il 1IiAP 1 1 Il Shell 3 .5 " Ethyl 2, , 2 " DABCO 25, DiCup FlexoJ i must Dutrex 916 702 4OC L EPO V / calibrator

Physical properties: Normal tensile strength
(vulcanized 80 '/ 160 ⁰ C): 8-5 psi (62 kg / cm ² ) at 160%

strain

Aged (4 days at 100 ⁰ C) Tensile Strength (cured

30 * 683/0 * 00

80 '/ 160 ⁰ C): ■ 1110 p-si (77 kg / cnT) at 120%

strain

ötahlkugelrüekpral1 {vulcanized

at 100 ⁰ C 48; i

at 23 ° C

"A" hard (vulcanized 104 - '/ 160 ⁰ C):

Permanent deformation - 22 otdn./ 7O ⁰ C (vulcanized 104 '/ 160 ⁰ C): 18-o

Example 8 is similar to Example 7 except that one additional peroxide vulcanization is applied.

Recipe:

Example 9 , 5 parts Ii Thiokol HO-434 71 , 5 Il Jeffamine D-2000 28 ,8th 11 IbAi ¹ Huss 35 11 Shell Dutrex 916 7th , 14 Il üüBOO 2 , 72 I) Ethyl 702 0 , 2- lipon 826 22nd

Physical Properties: Normal Tensile Strength (vulcanized 45 '/ 138 ⁰ C): 950 psi (67 kg / cm ² ) at

strain

Aged (4 Page at 100 ⁰ G) Tensile Strength (vulcanized 45 '/ 138 ⁰ C): 1450 psr (102 kg / cm ² ) at 330%

strain

Steel ball rebound (vulcanized 60 '/ 138 ⁰ C)

at 23 ° C 37: i

at 100 ° C 28, b

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iJhore "Λ" hardness (vulcanized 60 '/ 13O ⁰ G):.

Permanent deformation - 2,?

7O ⁰ C- (vulcanized 60 '/ 13O ⁰ G): 75 / b

Example 9 was a sharkun; ¹ ; also carboxy-terminated polybutadiene and amino-terminated polyoxypropylene, chain-extended with an epoxy resin.

Heζept;

example Parts 10 ^ · 100 ■ ti , Thiokol HG-434 50 Il 25th H Shell Dutrex 916 1 8 'i Ethyl 702 1O ₁ 2 » iPriet- "iyl amine 97 Diaziridine XD-7063

Physical Properties:

Normal strength (vulcanized 45 '/ 1 ^ 8 ⁰ C): 1100 psi (77 kg / cm) at 100%

Elongation tensile test (kidney-shaped test piece) ^{vulcanized at 23 0} G 45 ^! / 138 ^ο 0): 135 lbs./in.

ötahlkü ^ el rebound (vulcanized 45 '/ 13U ⁰ G): at 23 ⁰ G 41; ö

at 100 ⁰ G 50 >> i

Shore "^" hardness (vulcanized ■

45 '/ 130 °;

Firestone J'lodometer test (vulcanized 60 '/ 1 "') 8 ⁰ C) Running temperature ⁰ F

Stay / erforraun.:- 2? '.. tdn./ G (vulcanized 45' / 13S ⁰ G)

30988370400

Recipe;

example Parts 11 Thiokol IIC-434 100 Il IBiiF carbon black 50 11 Shell Dutrex 916 25th Il Ethyl 702 1 ,8th " Triethy! Amine 10, \ 3 " Diaziridine XD 7064 157

Physical properties: Normal tensile strength (vulcanized 45 '/ 13 ° C):

steel kissel rebound (vulcanized 45 '/ 138 ⁰ C)

at 23 ⁰ G

at 100 ^° C

Shore ' ¹ A "hardness (vulcanized 45' / 138 ⁰ C):

910 pai (64 kg / cm-) at strain

2290
62

Permanent deformation - 22 L> tdn./
70 ⁰ C (vulcanized 45 '/ 138 ⁰ C): 76%

Examples 10 and 11 show the vulcanization of carboxyteroinated Polybutadiene iait diaziridines.

According to the invention, in the manufacture of vehicle tires, a vulcanizable tread compound which contains a reinforcing agent is applied to the tread portion of a mold and then a tire body is placed in the mold against this tread. The tread is olycarb0xyhomopolymere from an elastomeric polymer selected from the pale (a) i ^Y or copolymers of conjugated dienes, (b) a conjugated lOlycarbox.ycopol.ymere Uiena and an aromatic Vi. _: yl monomers, (c) polycarboxy copolymer of a conjugated diene and a vinyl nitrile monomers, (d) olefinic polycarboxy polymer, which

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Contain 3 to 6 or 8 or more carbon atoms, and (e) Polycarboxypolyether and polyester made by making the same with (.1) an aliphatic or aromatic diepoxy resin, (2) a diaziridine, (3) a carbodiimide, (4) a Diisocyanate or (5) a glyceride (by transesterification) converts "

In addition to -fc'olycarboxypolymers, polyamino and polythiopolymers can be used from the same classes, either as such or with Garboxy polymers mixed, can be used. ·

Additional sulfur and peroxide vulcanization can be used will.

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Claims (11)

Claims Jiin «tire tread compound, characterized by a Reaction product of (1) a polymer from the class. Polycarboxy homopolymers and copolymers of conjugated dienes containing 4 to 6 carbon atoms, P.olycarboxycopolymers one such conjugated diene and a vinyl aromatic monomer, polycarboxyco.polymers of such conjugated diene and one Vinyl nitrile monomers, polycarboxy polymers of olefins, which Containing 3 to 8 carbon atoms, and polycarboxy polyethers and polyesters and (2) a reactant from the pale aliphatic and aromatic diepoxy resins, diaziridines, carbodiimides, Diisocyanates and glycerides with sufficient reinforcing agents for a tire tread. 2. Mixture according to claim »1, characterized in that the Reaction product is peroxide vulcanized. 3. Mixture according to claim 1, characterized in that the Polymer is carboxy terminated polybutadiene and the reactant is a condensation product of epichlorohydrin and bisphenol A. 4-, mixture according to claim 1, characterized in that the The polymer is carboxy terminated polyisobutylene and the reactant is a condensation product of epichlorohydrin and bisphenol U. 5. Mixture according to claim 1, characterized in that the Polymer an i.lischunp; of carboxy-terminated polybutadiene and amino terminated polyoxypropylene and is the reactant a condensation product of Cpichl. : \ hydrin and bisphenol A is. 6. Mixture according to claim 3 »characterized in that the Reaction product is peroxide vulcanized. 309883/0400 7. Process for producing a tire tread! through this characterized in that (1) a polymer from the pale Polycarb * oxyhomopolyroers and copolymers of conjugated dienes, which Containing 4 to 6 carbon atoms, polycarboxy copolymers one such conjugated diene and an aromatic vinyl monomer, Polycarboxy copolymers of such a conjugated diene and a vinyl nitrile monomer, olecarboxy polymers of olefins, which Contains 5 to 8 raw material atoms, and polycarboxy polyether and polyester and (2) a reactant from the class of aliphatic ^ and aromatic diepoxy resins, diaziridines, Carbodiimides, diisocyanates and glycerides converts for one Tire tread sufficient reinforcing agent. 8. The method according to claim 7 »characterized in that the Reaction product is peroxide vulcanized. 9. / experience according to claim 7, characterized in that the. Polymer «is corboxy-terminated polybutadiene and is the reactant a ^ onoensatio.vsprodukt of epichlorohydrin and bisphenol A. · 10. The method according to claim 7, dadruch Rek indicates that the Polymer is carboxy terminated polyisobutylene and is the reactant a condensation product of lipichlorohydrin and bisphenol 4th 11. The method according to claim 7, characterized in that the Reaction product from objection 9 or 10 is peroxide vulcanized. 309883 / OAOO Blank page