DE1795205A1 - Two-wheel pneumatic tires - Google Patents

Description

two-wheel pneumatic tires [elimination from patent ... .... (patent application P 16 20 789.9)] The present invention relates to pneumatic tires, in particular pneumatic tires, where no reinforcement fabric is built into their structure.

According to the invention, a fabricless pneumatic tire comprises a pair of im Spaced beads and a molded flexible composition that is extending from one bead to the other, around the side wall parts and the tread part of the tire, this flexible composition having the following components comprises: (A) an interpolymer of ethylene with a vinyl alkanoic acid ester, a alkyl acrylate, an alkyl methacrylate or an unsaturated acid in which the olefin part in a An amount of at least 60% by weight of the interpolymer is present, or mixtures of such interpolymers with natural or synthetic rubbers, (B) a mixture of a crystalline olefin homopolymer or copolymer with a Natural or synthetic rubber or with a rubber-like homopolymer one α-olefin or with copolymers of an α-olefin, or (c) a plastomer Copolymer of ethylene and an α-olefin, at least 50 mol% of ethylene contains, and in which parts of the molecular chain contain blocks of polyethylene, or a mixture of such a copolymer with a crystalline Polymexen or Copolymers of ethylene or α-olefin, the crystalline materila in one Contains amount of up to 40% by weight of the mixture.

The invention also includes a method for producing a non-woven fabric Pneumatic tire, which consists in using a flexible composition (A) mentioned above, (B) or (C) for the shape of the side walls and the air surface parts of a pneumatic tire, comprising a pair of spaced apart bead wires. In case of non-crosslinked compositions (A), (B) or (C), a process captivates the composition to form the shape of half-hoops, each with a side wall and half of the tread portion, and a pair of respective half-tires to be brought together in a mold and to each other inserting a pair of Uniting bead wires and alternative methods include injection or compression molding (Transfer molding) a complete tire by injection molding it into a closed one Shape, the already the bead wires using rubber or plastic strips or blocks or any clamps in their position. For networked compositions the preferred method is to use multipoint gates on the side wall dec Tires. or by injecting a ring gate in the middle of the running surface or pre-inject.

The invention provides a pneumatic tire that does not have a reinforcing fabric built into the tire, and the tire can be used more quickly and economically than conventional pneumatic tires. Those used in the present invention Compositions are particularly suitable for the manufacture of bicycle tires, and for This purpose should be the composition, after shaping into the shape of a tire, a Young's modulus of at least 31.6 kg / cm2 (4.5 x 102 psi) and an elongation (Creep) of no more than 15% in length when loaded with 7.03 kg / cm2 (100 psi) Cross-section at a temperature of 30 ° C over a period of one month to have. The compositions should have a flex fatigue strength of at least Have 1 million bends and preferably at least 4 million bends.

The method for determining the flexural fatigue strength is in it, a practically "U" -shaped piece of assembly into which the depth dos "U" bears about 2 "(5.08 cm) between this depth and a depth of 2.54 om (1 ") to bend.

The pneumatic tire made of a composition A, B or Q, as above mentioned, formed. Any of the masses (A), (B) or (C) can be suitably used Crosslinking agents or vulcanizing agents, such as organic peroxides, e.g. dicumyl peroxide, and sulfur, or if desired by radiation. the usage However, thermoplastic mass has the advantage of removing waste and other scraps can be used again.

Composition A that can be used comprises an interpolymer of ethylene with a Viylalkansäuresster, an alkyl acrylate, an alkyl methacrylate or an unsaturated acid wherein the olefin portion is at least 60% by weight of the interpolymer matters. Mixtures of various interpolymers of this type can be used will. Typical interpolymers that can be used are an interpolymer of ethylene and vinyl acetate and a copolymer of ethylene and ethyl acrylate. In the case of ethylene-vinyl acetate copolymers, copolymers are preferably used with a vinyl acetate content of 5, the 30% by weight, in particular from 10 to 25% by weight, used.

There can be two or more copolymers of vinylsOST and ethylene, which contain different proportions of en vinyl acetate, are mixed to the to give the final desired vinyl acetate grade. For ethyl acrylate-ethylene copolymers similar contents of ethyl acetate to vinyl acetate are preferred.

In the case of copolymers of ethylene and unsaturated acids preferably unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, Crotonic acid and sorbic acid are used, but dibasic acids, e.g. Maleic acid can be used. Mixtures of different dicarboxylic acids can be used and metal salts of the acid in which the metal has a valence of 1 to 4 , e.g. sodium or zinc salts, can be used to form terpolymers with the Ethylene and a free acid to form. A typical interpolymer is a terpolymer of ethylene with acrylic acid and sodium methacrylate or a terpolymer of ethylene, unsaturated acid and other monomers such as vinyl alkanoic acid esters, in which a part of the acid is present as a metal salt.

The interpolymers can contain up to 40% by weight of the unsaturated carboxylic acid, based on the weight of the mixed polymer, contain, but contain precautionary up to 20% by weight. If a metal is used as an acid, the metal will lie usually in an amount of at least 10%, preferably at least 50%, of the stoichiometric equivalent to the carboxylic acid. the interpolymers are thermoplastics and usually have a lower softening point than homopolynes of olefin.

The interpolymers which have the composition (A) preferably contain a number of thermally labile cross-links to the hardness and stiffness of the so formed solid mixture to increase. this can be achieved by using a terpolymer with a metal salt of the acid as described above is used and / or a metal salt can be mixed with the interpolymer at elevated temperatures No need to implement the volatile components before using the interpolymer removed. the compositions that make up the thermally labile crosslinks Contained remain thermoplastic, despite the viscosity of the molten composition is greater than that of a composition that is not thermally unstable Contains networking. the thermally labile (thermolabile) crosslinked composition has an increased hardness and toughness compared to a non-crosslinked mass.

That to introduce the thermolabile cross-links into the interpolymer agent used is an inorganic metal compound, which enables se that the metal ions combine with the recative carboxylic acid groups in the polymer, and typical metal compounds that can be used are acetates, oxides, Carbonates and hydroxyde. Monovalent or divalent metal compounds are preferred used, and examples of suitable compounds are the acetates of sodium and Potassium or the oxides of calcium, magnesium and zinc. There can also be connections Trivalent and tetravalent metals such as aluminum or lead can be used.

The lack of thermolabile crosslinking agent associated with the interpolymer is usually such that the total amount of metal ions, including of metal ions the metal salt of the acid, less than the stoichiometric Is equivalent to that defined above. If desired, two or more different thermolabile crosslinking metals are used.

The interpolymers or copolymers that make up the composition (A), In addition to ethylene, other higher olefins such as propylane and butylene can also be used, and can also be used as mixtures with natural or synthetic rubbers will.

Composition B comprises a mixture of a crystalline olefin homopolymer or copolymers with a natural or synthetic rubber or with a rubber-like one Homopolymers of an α-olefin or copolymers of an α-olefin. Typical Masses are those based on polyethylene or mixed polypropylene with a natural or synthetic rubber or similar mixtures, which are mixed polymers of e.g. ethylene and propylene or ethylene and butene instead of polyethylene or Contains polypropylene. It came from any of the well-known types of synthetic rubber be used. Rubber-like copolymers of ethylene and propylene can are mixed with the crystalline olefin homo-olymers or copolymers.

Usually the mixture consists of at least 15 to 70% by weight crystalline homopolymers or mixed polymers, based on the total weight of the mixture including any additional mixing ingredients If the mixtures than thermoplastics are used, preference is given to those which contain 40 to 60% by weight of the crystalline homopolymer. However, if they are networkable or vulcanizable, those with a content of 20 to 50 wt.% preferred. A particularly useful blend will be obtained when using a copolymer of polypropylene with a small amount of ethylene as a crystalline material in Mixture with a rubbery misoh polymer of ethylene and propylene used, since such mixtures show an improved fatigue strength in comparison with blends containing crystalline polypropylene. In a corresponding way are advantageously copolymers of ethylene and butene or higher olefins processed into mixtures with butyl rubber instead of homo-polyethylene.

The third type of composition that can be used is the mass (0), which is a plastomeric copolymer of ethylene and an α-olefin containing at least 50 mol% ethylene, and in which parts of the molecular chain Containing blocks of polyethylene. Such copolymers can be used with crystalline Homopolymers or mixed polymers of ethylene and α-olefins Since becoming real, wherein the crystalline material makes up to 40% by weight of the mixture. As a precaution The ethylene content of the plastomeric copolymer is 70 to 90 mol%. If this is mixed with its crystalline homopolymers or mixed polymers, then amounts to The amount of crystalline homopolymer or micropolymer is preferably no more ale 25% by weight of the mixture. The mass (C) can by means of peroxides or by irradiation networked be, and in this case plastomeric copolymers with a content of 60 to 80 mol% ethylene is preferred.

In masses, which mixtures of 1.) crystalline homopolymers or Copolymers of α-olefins with 2.) natural or synthetic rubber (i.e. Wet B), or with 3.) plastomers, copolymers of ethylene and higher α-olefins (i.e. mass C) it is essential that the temperature of mixing of the Components of the mixture during the entire Nisoharbeitsganges above the melting point of the crystalline component.

It has been shown to be possible to reduce the mass by subsequent Rolling the prepared mixture at a temperature below the melting point of the crystalline component to orient, which is a fibrous orientated poly-α-olefin structure within the matrix. This material has vastly different physical properties Properties in the direction of and across the direction of orientation. This orientation can also be produced if the mass is made with either vulcanizing ingredients is mixed or calendered or injection molded, provided that the processing temperatures be formed below the melting point of the crystalline component. Excessive However, rolling and the like of such mixtures at low temperatures should be avoided werdon, since this causes a degradation of the crystalline phase.

If orientation is not required, thermoplastic is an alternative Mass the mixing and molding operations at temperatures above the softening point the crystalline component carried out, and for vulcanizable or crosslinkable Vulcanization components are added on the cold mass Roller to avoid scorching, but the final shaping must be at such a temperature that it destroys any orientation will.

There are now three methods of manufacturing the bicycle tires according to of the invention described as an example, reference being made to the accompanying drawings is taken, wherein: Fig. 1 is a cross-section through a shape at an early stage Represents stage in the manufacturing process; Figure 2 is a cross section through a mold of Fig. 1 at a subsequent stage in the manufacturing process; Fig. 3 is a Section through a mold showing the formation of the pneumatic tire; Fig. 4 is a Diagram showing the shape of the blanks to form a pneumatic tire after a different method shows; Figure 5 shows a further stage in the method; and Fig. 6 shows a section through a mold during transfer molding of a pneumatic tire.

With the first method of manufacturing bicycle tires according to The present invention, as shown in Figures 1, 2 and 3, becomes the Wet, from which the tire is to be formed, with further components, depending as desired, blended and mixed. The method described is special Value for making tires from thermoplastic materials.

As shown in Fig. 1, a mold for forming oval half-shells or semi-tires consisting of a sidewall region together with a bead region and one half of the tread part, two separate mold halves 1 and 2. the upper mold half 1, as shown in Fig. 1, has a mold surface 3 with a shape that is practically the same as the inner shape of the desired half-tire, and is provided with an annular projection 4 around a slot in the bead area of the semi-mature to be formed. The lower mold half 2 has a mold surface 5 in the form of a circular recess which is shaped so that it matches the outer shape of the desired half tire matches, and the upper mold half 1 has one central circular stop 6, which is located within a central recess 7 in de lower mold half 2 can slide.

As shown in Fig. 2, the mixed mass 8, which is used to produce of the half tire is to be used, either in sheet form or in granular form introduced into the recess 5 formed in the lower mold half 2, and the upper mold half 1 is lowered onto the lower mold half 2, to the porning of the Effect mass to the Gewilnechten half tire 9 su. The projection 4 has a slot 10 in the vulat area of the half tire 9. During this molding operation the mold is heated to allow the thermoplastic material to flow to the desired level To effect shape.

Two half-hoops are then formed together in a tube shown in FIG. This mold comprises an upper half 11 with an annular mold surface 12, which corresponds to one half of the outer shape of the tire, and a lower mold half 13 with a ringförm.n mold surface 14, which in its shape is similar to that of the upper mold half 11 is.

A central annular molding 15 with a molding surface 16, which corresponds to the inner surface of the desired finished tire is on clamping parts 17, 18 held together by a number of screws 19. A tire 9 is applied to the mold surface 14 of the lower mold half 13, Another half tire 9 is applied to the molding 15, and the various Parts of the porn are brought together to join the two half letters to be effected by heat and pressure. Before the mold halves 9 in the form in their position are brought, bead wires 20 into the slots 10 in each half-hoops are introduced, and during the final molding the slots are made closed around the bead wires that lie in them.

An alternative method of making a bicycle refien is in 4 and 5 shown, this method being particularly useful for the manufacture of tires suitable from oriented masses. the oriented mass becomes after mixing ait the desired Dioke taken from the roller, and a number of blanks 30 is, like shown in Fig. 4, cut. The blanks are somewhat barrel-shaped when viewed from above, so that they can be placed on an annular, practically cylindrical shaped part or core 31, as shown in Fig. 5 can be taken care of. the blanks 30 are after Application to the solid annular metal core on the Dasis 32 of the blanks with Give away bead wires 33 and a block of a hardened rubber compound to the Complete the shape of the bead part and hold the bead in a position. The formtei @ 32 can then together with the blanks and the bead wires between mold halves of a similar shape; as shown in Fig. 3, brought about solidification and formation of the fabric-free bicycle tire through the application of heat and pressure cause.

An alternative method for forming bicycle tires according to the invention is shown in Fig. 6, which deretellt a transfer mold. the form exists in wea @ nlichen from a circular Mold insert 40 with a molding surface 41, which is formed according to the inner profile of the desired tire is. The annular mold insert 40 is held by rinkglemmenteile 42, 43, which are connected by means of a number of screws 44. The cavity becomes wider unlimited by molded parts 45, 46, 47, 48, which are easily detachable from one another allow the tire to be easily raked up after molding. The molding 47 is provided with a chamber 49 with a number of fuel inlets 50, the open into the mold cavity, and a number of injection inlets 51 each in correspondence with an injection inlet 52 ii poriteil 48. The mold 48 is still given away with a number of spray inlets 53 next to the Side wall parts of the mold cavity lie, which are closed if desired can if the mold for the production of fabricless tires from oriented material should be used. The injection inlets 50 lie approximately on the circumferential center plane of the tire to be formed in the mold cavity.

The one in Pig. 6 also includes an upper part 54, which delimits a ring-shaped spray pot 55, in which a sliding ring-shaped Piston 56 mounted int, the movement of which is determined dasu, the mass to be formed to press into the mold cavity. The transition from the spray pot 55 au molding compound is effected by a number of injection openings 57, the respective with an injection port 51 to match. Furthermore or optionally can material for cavity mold through the injection openings 53 by means of an injection channel 58 and a number of injection openings 59 are transported, each in a socket part 60, which is held in this molded part 48. if you have a Wants to produce grooves from an oriented material, and the socket parts 60 fixed sockets without injection opening 59, and as shown in Fig. 6, is ggde socket 60 full, although the spray opening 59 is indicated by dashed lines to avoid unnecessary duplication of the drawings.

When using it, the desired amount of the wet to be molded 61 placed in the annular pot 55 and the piston 56 lowered to the contact the mass through the openings 57.

51 and 50 to effect in the molding chamber. the heated so convicted Mass is molded to the shape of the tire. before transferring the Bead wires 61 are massed into the molding chamber by means of rubber strips or rubber blocks used, and this. become into a unitary structure during the transfer molding process molded.

Much of the compositions of the present invention are thermoplastic, and waste material can be used easily.

The following examples explain the invention but also limit it.

Example 1 A copolymer of ethylene and vinyl acetate, the 18th Contains% by weight vinyl acetate, and a melt flow index according to ASTM D. 1238 of 2.5 g / 10 minutes and an intrinsic viscosity (intrinsic viscosity) of 0.57 in decalin at 135 ° C, and contained 5% by weight of the copolymer of titanium dioxide, found a maximum creep of 7% and a Young's modulus of 443 kg / cm2 (6.3 x 103 pei). the mass also had flex fatigue strength of 5 million bends or more.

Half-shells of a two-wheeled tire with a shaped groove around the beaded steel wire to keep was. by molding according to the previously described method using a temperature of 17500 produced. Two half-shells with bulging wires inserted into the molded grooves were made solid by molding at 175 ° C Fitting in a tire mold with an end profile and then cooling the mold connected before opening.

The molded two-wheel tire was applied to a spoke wheel, inflated to 2.1 kg / cm2 (30 psi) with standard butyl tubing and against a 18 "diameter smooth drum with a peripheral speed of 24 km / h (15 aph) under a load of 50.8 applied to the axle of the wheel kg (112 lbs) run. The tire had run a distance that corresponded to 644 km, before the Verauche canceled became. Appropriate tires were made applied to a bicycle. inflated to 2.1 at (30 psi) and it was thereby driven, which was found to have properties similar to common ones Had two-wheel tires.

Example 2 In the case of a copolymer of ethylene and vinyl acetate, containing 16% by weight vinyl acetate and a melt flow index (D. 1238) of 1.5 g / 10 minutes and an intrinsic viscosity of 0.79 in decalin at 135 ° C and contained 5% by weight of the copolymer of titanium dioxide, it was found that it a maximum creep of 6% and a Young's modulus of 464 kg / cm2 (6.6 x 103 psi). The mass also had a flex fatigue life of 8 million Bends or above. A tire was molded as described in Example 1 2.1 at inflated and driven 1448 km before the attempts were canceled, Example 3 In the case of a copolymer of ethylene and vinyl acetate, the 15% by weight of vinyl acetate and a melt flow index (D.1238) of 2.5 g / 10 minutes and an intrinsic viscosity of 0.9 @ in decalin at 135 ° C. and 5% by weight of the copolymer of titanium dioxide was found to have a maximum creep of 4% and a Young's Module of 577 kg / cm2 (8.2 x 103 psi). the crowd also had one Flexural fatigue strength of 3 million bends or more.

A satisfactory tire was made as described in Example 1 shaped, inflated to 2.1 at and driven 161 km before the tests were canceled Example 4 In a mixed polymer of ethylene and ethyl acrylate, the 15th Containing wt.% Ethyl acrylate, and a melt flow index (D.1238) of 2.5 g / 10 Minutes and an intrinsic viscosity of 0.52 in decalin at 135 ° C eye and 5 wt.% of the mixed polymer contained titanium dioxide, it was found that there was a maximum Had a creep of 5% and a Young's modulus of 598 kg / om2 (8.5 x 103 psi). the mass also had a flex fatigue strength of 5 million flexures or above.

Tires molded in a manner similar to Example 1 were made on 2.1 at pumped up and drove 97 km before the attempts were aborted.

Example 5 A copolymer of ethylene and methacrylic acid with a content of 9% by weight of the acid, mainly in the form of the zinc or magnesium salt which had a melt flow index (D.1238) of 0.75 g / 10 minutes and an intrinsic viscosity from 0.21 in decalin at 13500 and 5% of the weight of the Containing copolymers of titanium dioxide, had a maximum creak of 2% and Young's modulus of 2530 kg / cm2 (3.6 x 104 psi). the crowd had one too Flex fatigue strength of 1 million flexures or more.

Hin tire was molded as described in Example 1, to 2.1 at inflated and driven 80 km before the attempts were aborted.

Example 6 A copolymer of ethylene and acrylic acid containing 14% by weight Acrylic acid, and a melt flow index (d.1238) of 20 g / 10 minutes and had an intrinsic viscosity of 0.2 in decalin at 135 ° C. and 5% by weight of the copolymer of titanium dioxide had a maximum creep of 3% and a Young's 1900 kg / cm2 (2.7 x 104 psi) module. The mass also had flex fatigue strength 1.5 million bends or more.

Hin Reifen was gated as described in Example 1, to 2.1 at inflated and driven 161 km before the attempts were aborted.

Example 7 60 parts by weight of a copolymer of ethylene and vinyl acetate, containing 10 wt% vinyl acetate and a melt flow index (D, 1238) of 4 g / 10 minutes and an intrinsic viscosity of 0.87 in decalin at 135 ° C 40 parts by weight of a similar copolymer containing of 28% vinyl acetate with a melt flow index of 3.5 g / 10 minutes and an intrinsic viscosity of Og61 in decalin at 135 ° C in an internal mixer at a temperature of 130 ° C mixed, and 5% by weight of the mixture of titanium dioxide was added. It was determined, that the mass has a maximum creep of 8% and a Young's modulus of 534 kg / cm2 (7.6 x 103 psi) and a fatigue strength of 3 million bends or above and was very suitable for the production of two-wheeled tires.

Example 8 An interpolymer containing 81% ethylene, 7.5% methacrylic acid (of which 1.1% was present in the form of the sodium salt) and 11.5% vinyl acetate and had an intrinsic viscosity of 0f53 in decalin at 135 ° C, had a maximum Creep of 6%, a Young's Moudl of 3940 kg / cm2 (56 x 103 psi), a flexural fatigue strength of s0 million bends or more and was also more suitable for making fabricless two-wheeled tire Example 9 A mixture of 70 parts by weight of a mixed polymer of ethylene and methacrylic acid, as used in Example 5, at 30 parts by weight one modified with Acrylsdure Copolymers of butadiene and acrylonitrile of the Mooney viscosity (Ml 4 at 100 ° C) 55-75, which is 35-37% of the Mixed polymer weight of acrylonitrile was contained in an internal mixer 130 ° C. It was found that the mass has a maximum creep of 5%, Young's modulus of 647 kg / cm2 (9.2 x 103 psi), and flex fatigue strength of 5 million bends or more, and very useful for fabric less Two-wheeled tires.

Example 10 100 weight percentages of a copolymer of ethylene and Vinyl acetate, as used in Example 2, was mixed with 5 parts by weight of dicymyl peroxide mixed in an internal mixer at 120 ° C for 10 minutes. One 1,587 mm (1/16 ") thick foil earth at 1800C for 2Q minutes and cross-linked from this Foil cut test pieces showed that the mass had minimal creep of 6%, YoungX modulus of 295 kg / cm2 (4.2 x 103 psi), and flex fatigue strength of 10 million bends or more and was more Alsatian and better Has temperature resistance than similar uncrosslinked copolymers.

A tire was injection molded into the sidewalls of the tire, between the plates according to the method shown in Figure 6 and previously described a press heated to 15,000. The networking was carried out through 15 minutes Heating to 180 ° C. ended and the mixture was then cooled under pressure and then removed a satisfactory tire.

Example 11 Prong Mixture of 50 parts by weight of a copolymer of ethylene and methaoryl acid as used in Example 5 at 50 parts by weight of a cis-1,4-polybutadiene with a cis content of 97% and the Mooney viscosity (ML-4 at 100 ° C) 50 was prepared in an internal mixer at 150 ° C, and the following Quantities (in parts by weight) of detergent added: Bletoarbonate 1 a, 5 titanium dioxide 4.0 zinc oryda 13.0 After cooling to 120 ° C., 3.25 parts by weight of dicumyl peroxide were obtained was added and mixing was continued for an additional 5 minutes.

A 1.587 mm (1/16 ") thick sheet of this mass was passed through for 30 minutes Molds crosslinked at 160 ° C and were found to have a maximum Creep of 4 4, a Young's modulus of 429 kg / cm2 (6.1 x 103 psk) and a Flex fatigue strength of 7 million flexures or more and was very suitable for the production of fabric-free two-wheeled tires.

Example 12 A blend of 45 tils of isotactic polypropylene of melt flow index 0.3 g / 10 minutes (BS.2782, 105 ° C, 2.16 kg / 230 ° C) UM one Intrinsic viscosity of 1.24 in decalin at 135 ° C, with 55 parts of butyl rubber of Mooney viscosity (ML-4 at 100 ° C) 74.0, containing 1.52 mol% unsaturation and 5 parts titanium dioxide, all parts being parts by weight, was mixed in an internal mixer and heated to 180 to 20,000 for 15 minutes. You material got hot between cold calender rolls eu a sheet with a nominal thickness of 4.76 mm (3/16 ") shaped.

The mass had a maximum creep of 3.0% and a Young's Module of 1970 kg / cm2 (@@ x 104 psi). The mass also had flex fatigue strength of 12 million bends or more.

Two-wheeled tires were molded according to the first rubbed method, shown in Figures 1, 2 and 3 of the accompanying drawings, using a temperature of 220 ° C and subsequent cooling of the mold before opening, resulting in a satisfactory tire.

Alternatively, a film of 19 now (3/4 ") thickness can be made and can be formed as a thick half-shell by using spacers the mold does not close completely. The bead wires will be in the final Form inserted, by attaching small wire clamps of suitable thickness will. Me shaped Ralbsohale is then placed in the top half of the endofrm and by heating to 200 ° C and then applying pressure to the second Half of the final shape is press-flow molded so that the bead wires are centered in the finished product section lying. The mold is cooled to take out the finished tire, which is satisfactory in every respect.

Further riding was made by the mixed mas-be into a compression molding, similar to that shown in Fig. 6, through a single injection port is injected in the side wall area. In this way of working, a preheated Strips of the mixture are fed into a heated extruder that is perpendicular across the injection opening of the heated mold is arranged.

The form is clamped together, leaving a sheet with bead wires on each side of the central core to be tested, and wire clips are used and the pressure is maintained until the mold is full and cooled again with a satisfactory tire being formed.

Example 13 Binding mixture of 45 parts of a crystalline copolymer of propylene and ethylene (with ethylene only as a minor component, with less as 5 Nol%) of melt flow index 0.2 g / 10 minutes (BS.2782 at 230 ° C) and an intrinsic viscosity of 2.97 in decalin at 135 ° C with 55 parts one Ethylene and propylene copolymer rubbers (with a Mooney viscosity ML-4 at 100 ° C of 35), which contains 55 mol% ethylene, and 5 parts of titanium dioxide, all of which Parts are parts by weight in an internal mixer heated to 180 to 2000C Made for 15 minutes. The material turned light between cold calender rolls formed into a skin with a nominal thickness of 4.76 mm (3/16 ").

The mass had a maximum creep of 7% and a Young's 1830 kg / cm2 (2.6 x 104 psi) module. the mass continued to have flex fatigue strength of 12 million bends or more as opposed to that of a similar one Mixture based on a crystalline homopolymer of propylene, as described in Example 12 was used, which only had a flex fatigue strength of 2 million Had bends. There have been satisfactory two-wheeled tires in a manner similar to prepared in Example 12.

Example 14 A mixture of 45 parts of a high density ethylene copolymer with butene-1 (the butene-1 being present in an amount of less than 5 Nol%) from Melt flow index 0.3 g / 10 minutes (BS.2782 at 190 ° C) and an intrinsic viscosity of 1.13 in decalin at 13500 with 55 parts of the butyl rubber wasted in Example 12 and 5 parts of titanium dioxide, all parts being parts by weight, was made in one 160 at 160 ° C internal mixer for 15 minutes.

The material turned into a skin when hot between cold calender rolls molded to a nominal thickness of 4.76 mm (3/16 ").

The mass had a maximum creep of 2% and a Young's 1410 kg / cm2 (2.0 x 104 psi) module. The mass also had flex fatigue strength of 2 million bends as opposed to a similar mix on the base of a high-density homopolymer of ethylene and similar Sohmel index, which is only one Flex fatigue strength of 500,000 flexures.

From experience with other materials it can be assumed that from a satisfactory two-wheeled tire can be produced from this mass.

Example 15 A mixture of 50 parts of isotactic Polybute-1 from Melt index 0.3 g / 10 minutes (ASTM D.1238, 5 kg / 190 ° C) and the intrinsic viscosity 1.5 in decalin at 135 ° C with 50 parts of butyl rubber, as used in Example 12 was, and 5 parts of titanium dioxide, where all parts are parts by weight, was in one Prepared for 15 minutes on 140 to 16,000 internal mixers heated. The material became hot between cold calender rolls to a skin with a nominal thickness of 4.76 mm (3/16 ") molded.

The mass had a maximum creep of 3X and a Young'ache Module of 914 kg / cm2 (1.3 x 104 psi). The mass still had flex fatigue strength of 12 million bends or above.

Satisfactory tires were described similar to the second in Example 12 Method made.

Beisiei 16 A propylene polymer was made according to the British patent specification 1,024,179 using a vanadium trichloride / titanium tetrachloride catalyst in a ratio of 1: 2 parts by weight, and aluminum triethyl, the ratio of Catalyst to alkyl 3: 2 parts by weight suspended in Be @@@@. The catalyst was prepared by adding titanium tetrachloride with aluminum triethyl was reduced, vanadium tetrachloride was mixed with the reaction mixture, and this was reduced to the trichloride with aluminum trityl. Propylene gas was in at an amount of 36 l / minute 1 hour and 35 minutes at 350C. The reaction was stopped by purging nitrogen gas through the reaction vessel and adding the polymer was precipitated with isopropanol and concentrated Annwniak. That so educated Polymers were examined by X-ray crystallography, and it was found that that it was 18.5% crystalline. You polymers, you an intrinsic viscosity of 1.11 in decalin at 135 ° C contained 50% material which is soluble in one edging heptane was.

The polymer was made with 5 parts of titanium dioxide per 100 parts of polymer mixed, found to have a maximum creak of 2% and a Young's modulus of 1550 kg / cm2 (2.2 x 104 psi). the polymer mass had also a flex fatigue strength of 12 million bends or more and was suitable for the production of fabric-free two-wheeled tires.

Example 17 A mixture of 50 parts isotactic polypropylene, as used in example 12, with 50 parts natural kautachuk (emoked eheet) was prepared as in Example 12.

The mass had a maximum creep of 4% and a Young's Moudl of 2460 kg / cm2 (3.5 x 104 psi). Furthermore, the mass had flex fatigue strength of 12 million bends or more and is suitable for fabricless two-wheeled tires.

Example 18 Bine mixture of 50 parts isotactic polypropylene, as used in Example 12 with 50 parts of styrene-butadiene rubber with a styrene-butadiene ratio of 23t77 (Intol 1500) was as in Example 12 manufactured.

The mass had a maximum creep of 4% and a Young's 2040 kg / cm2 (2.9 x 104 psi) module. furthermore, the mass had a flexural fatigue strength of 12 million bends or more and is suitable for fabricless two-wheeled tires.

Example 19 A mixture of 40 parts of a crystalline high density Ethylene homopolymers with a melt flow index of 0.9 g / 10 minutes (BS.2782, method 105 C at 190 ° C) and an intrinsic viscosity of 0.87 in decalin at 13500 with 60 Share an ethylene-propylene copolymer rubber as used in Example 13 was, and 5 parts of titanium dioxide, all parts being parts by weight, was in one Internal mixer made at 18000 for 15 minutes. The mix was up to 12,000 cooled and 3.5 parts by weight of dicumyl peroxide was added and more was added Mixed for 5 minutes.

A 1.59 mm (1/16 ") thick sheet of this composition was at 180 ° C for 20 minutes lang preßageforwt, and it was found that this crosslinked material is a maximum creep of? %, a Young's modulus of 2530kg / cm2 (3.6 x 103 psi) and had a flex fatigue strength of 10 million flexures or more and was more elastic and had better temperature resistance than the like non-crosslinked mixture.

Satisfactory tires can be mixed from this networked Material according to a method similar to that described in Example 10, prepared will.

Example 20 A mixture of 40 parts of a crystalline high density Ethylene homopolymers, as used in Example 19, with 60 parts of an ethylene-propylene rubber, as used in Example 13, was in an internal mixer at 180 ° C for 15 minutes manufactured. the mixture was then cooled to 130 ° C. and 0.6 parts of di-tert-butyl peroxide and 3.0 parts of maleic acid were added and the mixture was allowed to take 45 minutes 190 ° C, whereupon all the peroxide decomposes and a maleic acid graft copolymer mixture was educated.

100 parts of this interpolymer blend were taken and 2.5 parts Zinc oxide and 4.0 parts of stearic acid were added on a calender at 130 ° C. (All Parts are parts by weight).

A 1.59 mm (1/16 ") thick sheet of this composition was press molded at 160 ° C and found to have a maximum creep of 8%, Young's modulus of 689 kg / cm2 (9.8 x 103 psi), and flex-fatigue strength of 5 million bends or more, and is suitable for the construction of non-woven fabric Two-wheeled letters were suitable.

Example 21 The following composition was made in an internal mixer at 190 ° C Made for 15 minutes. The numbers given in lilo are natural rubber by weight (smoked sheet) 100 isotactic polybutene-1 (see example 15) 50 HAF carbon black (highly abrasion-resistant Furnace black) 40 Mixture of arylamines (antioxidant Nonox HFN) 2 aromatic processing oil 3 stearic acid 1 zinc oxide 5 the mixture was then turned into a on a cold roller Shaped fur, and 1.0 part by weight of N-cyclohexyl-2-benzothiazolesulfenamide and 2.5 Parts by weight of sulfur were added.

A 1.59 mm (1/16 ") thick sheet of wet was passed through for 20 minutes Compression molding vulcanized at 150 ° C, and it was found that they had a maximum 7% creep in two directions at right angles to each other (no orientation), Young's modulus of 141 kg / cm2 (2.0 x 103 psi) and flex fatigue strength of 10 million bends or more.

Satisfactory tires could be made from this vulcanized mass using a method similar to that in Example 10 described is to be produced, the Vulkanisawtion by 20mintiges heating on 150 ° C has ended.

Example 22 The following was mixed in an internal mixer for 15 minutes Hardened for a long time at 190 ° C. All figures given are parts by weight. natural rubber (smoked sheet) 100 isotactic polypropylene (see example 12) 30 FEF carbon black (fast extruding furnace black) 40 mixture of arylamine (antioxidant Nonox HFN) 2 aromatic Processing Oil 3 Stearic Acid 1 Zinc Oxide 5 The mixture was then put on a cold Roll into a fur. forms, and 1.0 part by weight of N-cyclohexyl-2-benzthiazolesulfenamide and 3.0 parts by weight of sulfur were added. The polypropylene in the on the Cold roll obtained mass was oriented, and it was found that the properties a 1.59 mm (1'16 ") thick film, which was press molded for 20 minutes at 150 ° C vulcanized, if they were with and against the direction of orientation Measured were @ with maximum creep against the direction of orientation (%) 5 10 Young'sons Module kg / cm2 (psi) 217 (3.08x103) 126 (1.79x103 Flexural fatigue strength grömmer ale greater than (million) 10 10 209812/0416 For building Tire orientation can be used to advantage by ensuring that because it lies radially in the direction of the greatest stress due to the inflation More satisfactory riding was after that shown in Pigren 4 and 5 and before method described, wherein the vulcanization by compression molding at 150.00 has ended.

A tire was tested as in Example 1 and 6437 km driven at 32.2 km / h before the tests were canceled. For tires that mounted on a bicycle and ridden, they have been found to be similar Had properties like conventional two-wheeled tires.

An alternative method of making two-wheeled tires was the method shown in Fig. 6 and previously described by transfer molding by a number of injection openings on the circumferential median plane of the tire and not through the openings next to the side wall. The vulcanization was finished as before, giving a satisfactory tire.

Example 23 An ethylene-propylene copolymer was prepared index a monomer mixture of ethylene and propylene in a molar ratio of 1: 0.75 in a solution of vanadium oxychloride and Aluminum diethyl chloride was introduced in a molar ratio of 1: 11.7 in gasoline at -12 ° C. before the introduction of the monomer mixture of ethylene and propylene was the solution with Purged nitrogen gas. The monomer mixture was then in the solution for 5 minutes initiated at a rate of 18 l / minute. Any unreacted Monomers were then removed by purging with nitrogen, and another Amount of monomer mixture was sparged into the Kawalysator solution for 5 minutes. the rinsing and polymerizing procedures were repeated until the monomer mix a total of 15 minutes was passed through the solution.

The polymerization was ended and the mixed polymer precipitated. Any excess solvent was removed from the polymer by rolling between it heated rollers removed.

The polymer obtained contained 15% propylene and had an intrinsic viscosity of 3.6 in decalin at 135 ° C.

The polymer had a maximum creep of 4%, a Young's Modulus of 1550 kg / cm2 (2.2 x 104 psi) and a flex fatigue strength of 12 million bends or more and is therefore suitable for fabricless two-wheeled tires.

Example 24 An ethylene-propylene copolymer was prepared as in Example 23, except that the molar Gas ratio from ethylene to propylene was 1: 1. 80 parts of these polymers were then mixed with 20 Dividing a high density ethylene homopolymer with a melt flow index of 0.9 g / 10 minutes (BS, 1972-53, 2.16 kg / 190 ° C) and an intrinsic viscosity of 0.87 in decaiin at 135 ° C. and 5 parts of titanium dioxide, all parts being parts by weight, mixed.

The mass had a maximum creep of 8.0% and a Young's Modulus of 844 kg / cm2 (1.2 x 104 psi). Further, the mass had flex fatigue strength of 12 million wrappings or above and was satisfactory for fabricless two-wheeled tires.

Example 25 100 parts by weight of an ethylene-propylene copolymer, as described in Example 23, with 2 parts by weight of 2,2,5,5-tetra-tert-butylperoxyhexane (available as a 40% solid dispersion on a white filler) in one Indoor mixer mixed for 10 minutes at 120 ° C.

A 1.59 mm (1/16 ") thick sheet of this wet was at 1880 ° C. for 20 minutes long press molded, and this crosslinked material had a maximum creep of 5%, Young's modulus of 359 kg / cm2 (5.1 x 103 psi), and flex fatigue strength of 10 million bends or more.

Satisfactory tires could be produced from this cross-linked mass a method similar to that described in Example 10 can be prepared.

Claims (10)

Claims 1. Pneumatic two-wheeled tire that has a pair of spaced apart angecrdsten beads and a flexible tire body that extends from a bead to the others forming the sidewall parts and the tread part of the tire extends, characterized in that the tire has no textile reinforcement has, and to form the flexible tire body, a flexible mass with a Young's modulus of at least 31.5 kg / cm2 (4.5 x 102 psi) and an elongation (creep) of not more than 15% in length with a load of 7 kg / cm2 of the cross-section is used at a temperature of 30 ° C for a period of one month. 2. Two-wheel pneumatic tires according to claim 1, characterized in that the molded flexible tire body has a flex fatigue strength of at least Has 1 million bends, preferably at least 4 million bends. 3. Pneumatic two-wheeled tire according to claim 1 or 2, characterized in that that the flexible mass is an interpolymer of ethylene with an alkanoic acid vinyl ester, r an alkyl acrylate, an alkyl methacrylate or an unsaturated acid in which the olefin content in an amount of at least 60% by weight of the interpolymer is present, or mixtures of such interpolymers with natural or synthetic rubber. 4. Pneumatic two-wheeled tires according to claim 3, characterized in that the flexible mass is a copolymer of ethylene with vinyl acetate or ethyl acetate and that the amount of vinyl acetate or ethyl acrylate 5 to 30 wt .-% des Copolymer is. 5. Pneumatic two-wheeled tire according to claim 3, characterized in that the flexible s # a HischPeees of 1 # len and an unsaturated acid, preferably an unsaturated monocarboxylic acid, the amount of which is up to 40% by weight of the monopolymer contains. 6. Pneumatic two-wheeled tires according to claim 5, characterized in that the copolymer is a terpolymer made of ethylene, an unsaturated one Monocarboxylic acid and a metal salt of a monocarboxylic acid, in which the metal is a Valence from 1 to 4 hawt and wherein the metal salt is preferably in an amount of at least 10% of the stoichlometric equivalent of that present in the copolymer Carboxylic acid is present, is formed. 7. two-wheeled tires according to claim 1 or 2, characterized in that that the flexible mass is a mixture of a crystalline olefin homopolymer or mixed polymers, preferably polypropylene, with a natural or synthetic rubber or with a rubbery homopolymer of an α-olefin or a copolymer of an α-olefin, the crystalline homopolymer or copolymer is preferably present in an amount of from 15 to 70% of the total weight of the mixture. 8. two-wheel pneumatic tires according to claim 1 or 2, characterized in that that the flexible wet is a plastomeric copolymer of ethylene and an α-olefin, which contains at least 50 mol% ethylene and blocks in that part of the molecular chain of polyethylene or a mixture of such a copolymer with a crystalline homopolymer or copolymer of ethylene or α-olefin, contains the crystalline material in an amount of up to 40% by weight of the mixture, having. 9. Pneumatic two-wheeled tire according to claim 7 and 8, wherein the mass is a crystalline olefin polymer and (A) natural or synthetic rubber or (B) a plastomeric copolymer of ethylene and another α-olefin Contains, characterized in that the crystalline Materila in the mass with one is oriented at an angle of 90 ° to the mid-circumferential plane of the tire. 10. Pneumatic two-wheeled tire according to one of claims 1 to 9, characterized in that that the mixture is crosslinked.