Method for producing pneumatic vehicle tyres

Abstract

The invention relates to a method for producing a pneumatic vehicle tyre, comprising the following method steps: a) producing or providing a pneumatic vehicle tyre blank, comprising: i) a carcass blank, comprising a plurality of reinforcing supports embedded in a first vulcanisable rubber mixture, ii) a tread blank arranged above the carcass blank in the radial direction, and iii) an inner layer blank arranged below the carcass blank in the radial direction, comprising a second vulcanisable rubber mixture, comprising at least one butyl rubber and / or halobutyl rubber, b) applying an aqueous dispersion onto the surface of the inner layer blank to obtain a prepared pneumatic vehicle tyre blank, wherein the aqueous dispersion comprises one or more dispersed polysiloxane particles, c) vulcanising the prepared pneumatic vehicle tyre in a vulcanisation mould to obtain a pneumatic vehicle tyre, wherein the surface of the tyre inner layer obtained from the inner layer blank is at least partially covered with polysiloxane particles, and d) applying a sealant composition onto an application region of the surface, covered with polysiloxane particles, of the tyre inner layer.

Description

[0001] Process for the production of pneumatic vehicle tires

[0002] Description

[0003] The invention relates to a method for producing a pneumatic vehicle tire and a pneumatic vehicle tire produced thereby.

[0004] A vehicle's tires have a significant impact on its driving safety. Tire defects while driving have always been a major safety risk in road traffic. A complete perforation of a conventional pneumatic tire can lead to an unintentional loss of pressure, forcing the driver to change the tire, which often has to be done in the dangerous environment of the roadway.

[0005] To circumvent this problem, so-called self-sealing pneumatic vehicle tires were developed, which are now commercially available from various suppliers. In these self-sealing pneumatic vehicle tires, an additional layer of sealant, sometimes also referred to as a "sealant", arranged inside the pneumatic vehicle tire below the tread, ensures that if the pneumatic vehicle tire is perforated in the tread area, the resulting opening is sealed, preventing air from escaping and at least slowing down the associated pressure loss. General information on the technological background is disclosed, for example, in US 4287928 A, EP 3175975 B1, EP 3085523 B1, WO 2022237250 A1 or US 4263075 A.

[0006] Self-sealing pneumatic vehicle tires and the sealants used therefor are comprehensively familiar to those skilled in the art from the prior art. In the prior art, the sealant composition is usually applied to the already vulcanized pneumatic vehicle tire. It is important to those skilled in the art that there is sufficient adhesion between the sealant composition and the interior of the pneumatic vehicle tire, i.e., in particular, the tire inner layer. For this purpose, the prior art usually involves separate pre-cleaning of the tire inner layer before the sealant composition is applied in order to maximize the adhesion of the resulting composite and prevent, for example, contaminants from locally reducing the composite strength.

[0007] With growing awareness of the need for more sustainable economic activity and more careful use of fossil resources, the recycling of pneumatic vehicle tires has increasingly come into focus in recent years, with various approaches and concepts for recycling old pneumatic vehicle tires being known. However, with regard to self-sealing pneumatic vehicle tires, most relevant recycling processes have in common that, for efficient recycling, the sealant composition usually has to be removed from the pneumatic vehicle tire before it can be recycled.

[0008] The stronger the bond strength between the sealant composition and the tire inner layer, the more difficult it becomes to remove the sealant composition from the pneumatic vehicle tire. Thus, the high adhesion between the sealant composition and the tire inner layer, which is desirable in the production of new, self-sealing pneumatic vehicle tires, has a negative impact on their recyclability at the end of their service life. Thus, in the area of ​​self-sealing pneumatic vehicle tires, there is a conflict of objectives between the performance properties of new, self-sealing pneumatic vehicle tires, which are expected to firmly adhere the sealant composition below the tread, and recyclability after the end of their service life.

[0009] The primary object of the present invention was to eliminate or at least reduce the disadvantages of the prior art.

[0010] In particular, it was the object of the present invention to provide a method for producing a vehicle tire and a corresponding vehicle tire which, when used on the vehicle, has excellent self-sealing properties, in particular with regard to a reliable hold of the sealant composition on the inside of the tire, but at the same time is also particularly time- and cost-efficient to recycle, since the sealant composition can be removed as easily as possible during typical recycling processes.

[0011] Accordingly, it was the object of the present invention to identify, by means of suitable means or process controls, an optimal solution to the existing conflict of objectives between the durability of the produced composite of pneumatic vehicle tires and sealant composition and the subsequent removability of the sealant composition.

[0012] The inventors of the present invention have now discovered that the above-described objects can surprisingly be achieved if, during the vulcanization of the pneumatic vehicle tire, a silicone-based dispersion is applied to the tire inner layer, resulting after vulcanization in a surface at least partially coated with polysiloxane particles when the sealant composition is applied directly to this surface coated with polysiloxane particles, as defined in the claims. The invention is based on the finding that, to resolve the above-described conflict of objectives, a technical aid can be utilized in a synergistic manner, which in some cases is actually used for a different purpose in tire production.

[0013] This involves the use of an aqueous dispersion of polysiloxane particles, which, along with other compositions with a comparable effect, sometimes referred to by those skilled in the art as "lubricants," are used in some pneumatic vehicle tire manufacturing processes to optimize the boundary layer between the unvulcanized green vehicle tire and the vulcanization mold used for vulcanization. The corresponding aqueous dispersion serves, in particular, to promote efficient removal of the vulcanized vehicle tire from the vulcanization mold after vulcanization and, in particular, to prevent the adhesion of rubber residues to the vulcanization mold.

[0014] In the prior art, when using lubricants, it is generally customary to remove the residues of the lubricant remaining on the surface of the vehicle tire after vulcanization, in particular using material-removing methods such as strong brushing or laser-based cleaning, whereby in the case of self-sealing tires the intention is in particular to optimize adhesion as described above.

[0015] The inventors of the present invention have now found that, surprisingly, it is possible to resolve the conflict of objectives described above, contrary to the existing prejudice, by dispensing with this cleaning step and applying the sealant composition directly to the surface coated with polysiloxane particles, provided that a specific aqueous dispersion based on polysiloxane particles is used as the lubricant.

[0016] Surprisingly, sufficient adhesion is achieved between typical sealant compositions and the tire surface coated with polysiloxane particles, enabling reliable operation and the production of high-performance, self-sealing pneumatic vehicle tires. At the same time, the self-sealing pneumatic vehicle tires produced in this way achieve excellent recyclability, as the sealant composition can be easily and thus time- and cost-effectively removed during recycling processes, for example, using typical mechanical separation processes.

[0017] The above-mentioned objects are thus achieved by the subject matter of the invention as defined in the claims. Preferred embodiments of the invention emerge from the subclaims and the following statements.

[0018] Such embodiments, which are designated as preferred below, are combined in particularly preferred embodiments with features of other embodiments designated as preferred. Combinations of two or more of the embodiments designated as particularly preferred below are thus very particularly preferred. Likewise preferred are embodiments in which a feature of an embodiment designated as preferred to any extent is combined with one or more further features of other embodiments designated as preferred to any extent. Features of preferred pneumatic vehicle tires result from the features of preferred methods.Where mass fractions are specified below, these are usually stated as combined mass fractions of one or more components, as is customary in the industry, thereby expressing that the mass fraction of the correspondingly formed components taken together meets the corresponding criteria. The phr (parts per hundred parts of rubber by weight) specification used here is the quantity specification commonly used in the rubber industry for mixture formulations, which indicates the mass fractions of the components in the rubber mixture based on the mass of the high-molecular-weight rubbers (weight-average molar mass Mw according to GPC greater than 60,000 g / mol) present in the rubber mixture, with the combined mass fraction of the high-molecular-weight rubbers corresponding to 100 phr.

[0019] The invention particularly relates to a method for producing a pneumatic vehicle tire, comprising the method steps: a) producing or providing a pneumatic vehicle tire green body, comprising: i) a carcass green body comprising a plurality of reinforcement members embedded in a first vulcanizable rubber mixture, ii) a tread green body arranged radially above the carcass green body, and iii) an inner layer green body arranged radially below the carcass green body, comprising a second vulcanizable rubber mixture comprising at least one butyl rubber and / or halobutyl rubber, b) applying an aqueous dispersion to the surface of the inner layer green body to obtain a prepared pneumatic vehicle tire green body, wherein the aqueous dispersion comprises one or more dispersed polysiloxane particles,c) vulcanizing the prepared pneumatic vehicle tire blank in a vulcanization mold to obtain a pneumatic vehicle tire, wherein the surface of the tire inner layer obtained from the inner layer blank is at least partially coated with polysiloxane particles, and d) applying a sealant composition to an application area of ​​the surface of the tire inner layer coated with polysiloxane particles.

[0020] The method according to the invention serves to produce a pneumatic vehicle tire, in particular a self-sealing pneumatic vehicle tire. The pneumatic vehicle tires produced can, in principle, be pneumatic vehicle tires for a wide range of applications, including, for example, motorcycles. However, the method according to the invention is particularly relevant for the production of pneumatic vehicle tires for cars or trucks. Thus, a method according to the invention is preferred in which the pneumatic vehicle tire is a car or truck tire, preferably a car tire.

[0021] In the method according to the invention, a green pneumatic vehicle tire is first produced according to a typical method. For this purpose, the person skilled in the art can resort to methods known from the prior art. The green pneumatic vehicle tire to be produced also initially corresponds to a typical green pneumatic vehicle tire in terms of its structure. This means, in particular, that the still unvulcanized green pneumatic vehicle tire has a carcass green with reinforcements embedded in a vulcanizable rubber mixture, above which the unvulcanized tread is arranged, while the inside of the green pneumatic vehicle tire is covered by the inner layer green, from which, after vulcanization, the tire inner layer is to be obtained, which is largely responsible for the impermeability of the produced pneumatic vehicle tire.

[0022] For the first vulcanizable rubber mixture, i.e., the vulcanizable rubber mixture used for the rubber coating of the reinforcement members, the skilled person can, as well as for the vulcanizable rubber mixture used in the tread blank, draw on any vulcanizable rubber mixture known from the prior art. However, the nature of the tire inner layer, which the invention is based on, is crucial for the interaction between the subsequent tire inner layer, the lubricant used, and the sealant composition. According to the inventors, this must comprise at least butyl rubber or halobutyl rubber, both materials being thoroughly familiar to those skilled in the tire manufacturing field.

[0023] In practice, the inner layer blank will line the entire inner-facing surface of the vehicle tire blank in order to achieve the most complete sealing effect possible in the subsequent pneumatic vehicle tire. Therefore, a method according to the invention is preferred, wherein the radially inner surface of the pneumatic vehicle tire blank is essentially completely covered by the inner layer blank.

[0024] The inventors have succeeded in identifying particularly suitable materials for the composition of the second vulcanizable rubber mixture used in the inner layer blank, which, in conjunction with the subsequently applied aqueous dispersion, result in a good balance between the adhesion of the sealant composition and its removability. A process according to the invention is preferred, wherein the second vulcanizable rubber mixture comprises the butyl rubber and / or the halobutyl rubber in a combined mass fraction in the range of 70 to 100 phr, preferably in the range of 80 to 100 phr, particularly preferably in the range of 90 to 100 phr. Additionally or alternatively, a process according to the invention is also preferred, wherein the second vulcanizable rubber mixture comprises halobutyl rubber, preferably chlorobutyl rubber or bromobutyl rubber.Additionally or alternatively, a process according to the invention is also preferred, wherein the second vulcanizable rubber mixture comprises one or more fillers, preferably in a combined mass fraction of 30 phr or more, preferably of 40 phr or more, particularly preferably of 60 phr or more, wherein the filler is preferably selected from the group consisting of carbon black and amorphous silicon dioxide, for example precipitated amorphous silicon dioxide, preferably carbon black.

[0025] In process step b), a so-called "lubricant", which is sometimes also referred to as a "tire release agent", is applied to the surface of the inner layer blank, i.e. before vulcanization. According to the inventors' knowledge, however, not just any tire release agent can be applied in order to achieve the desired advantageous effect on the good removability of the sealant composition during the recycling of pneumatic vehicle tires. Rather, it is necessary to use an aqueous dispersion as the tire release agent which is "silicone-based" and comprises accordingly dispersed polysiloxane particles. Based on the inventors' experiments, it is assumed that the advantages of the process according to the invention do not depend on the choice of a specific polysiloxane because of the generally very similar macroscopic properties of polysiloxanes in this context.

[0026] In the inventors' opinion, it is expedient for the aqueous dispersion to consist as largely as possible of water with regard to its liquid phase, and the inventors have also been able to identify suitable ranges for the solids content of the aqueous dispersion. Preference is given to a process according to the invention wherein the liquid phase of the aqueous dispersion consists of 70% or more, preferably 80% or more, particularly preferably 90% or more, and most particularly preferably 95% or more, water, based on the mass of the liquid phase. Additionally or alternatively, preference is given to a process according to the invention wherein the aqueous dispersion has a solids content in the range from 30 to 60%, preferably in the range from 40 to 50%.Additionally or alternatively, a process according to the invention is also preferred, wherein the solid phase of the aqueous dispersion consists of 70% or more, preferably 80% or more, particularly preferably 90% or more, very particularly preferably 95% or more, of polysiloxane particles, based on the mass of the solid phase.

[0027] In the inventors' opinion, it is advisable to agitate the aqueous dispersion immediately before application, for example by stirring, in order to achieve the best possible coverage of the surface with polysiloxane particles. Application can in principle be carried out using a variety of methods, for example using a brush, although the inventors have achieved particularly good results with regard to the quality of the resulting surface coated with polysiloxane particles when application is carried out using a spray gun. Accordingly, a method according to the invention is preferred in which the aqueous dispersion is homogenized prior to application. Additionally or alternatively, a method according to the invention is also preferred in which the aqueous dispersion is applied by means of a spraying method, preferably using a spray gun.

[0028] Even though the advantageous effect of the aqueous dispersion on optimizing the adhesion of the sealant composition is primarily relevant in the areas to which the sealant composition is later applied, it is recommended, for synergistic utilization of the advantageous release effect of the tire release agent, to apply the aqueous dispersion over as much of the surface of the inner layer blank as possible, thereby ensuring excellent vulcanizability in the vulcanization mold. In this respect, a process according to the invention is preferred, wherein the aqueous dispersion is applied to 70% or more, preferably to 80% or more, particularly preferably to 90% or more, very particularly preferably to 95% or more, especially preferably to substantially 100% of the surface of the inner layer blank.

[0029] The degree of coating of the tire inner layer with the polysiloxane particles depends significantly on the application of the aqueous dispersion to the tire inner layer blank. In this respect, the inventors have succeeded in specifying particularly suitable ranges with which particularly advantageous results can be achieved, both with regard to the release effect from the vulcanization mold and with regard to the adhesion of the sealant composition to the formed surface. A process according to the invention is preferred, wherein the aqueous dispersion has a basis weight in the range of 5 to 25 g / m 2 , preferably in the range of 10 to 20 g / m 2 , is applied.

[0030] The appropriately prepared pneumatic vehicle tire blank is vulcanized in process step c), whereby the tire inner layer is formed from the inner layer blank, which is at least partially coated with polysiloxane particles as a result of the prior coating with the aqueous dispersion. In their own experiments, the inventors have identified suitable vulcanization temperatures with which excellent results can be achieved in the process according to the invention, particularly with regard to the quality of the surface of the tire inner layer that is at least partially coated with polysiloxane particles. A process according to the invention is preferred in which the vulcanization takes place at a temperature in the range of 130 to 200°C, preferably in the range of 150 to 180°C.

[0031] The surface of the tire inner liner is partially coated with polysiloxane particles within the meaning of the above definition. This expresses that it would be at least theoretically conceivable not to coat the entire surface of the inner liner blank with the tire release agent, even if this is less preferred, as explained above. In principle, to optimize the adhesion of the sealant composition, it would be sufficient to provide a coating of polysiloxane particles in the application area, i.e., the area of ​​the tire inner liner to which the sealant composition is to be applied. Analogous to the above statements, however, it is preferred if the surface of the tire inner liner is coated with polysiloxane particles over as entire a surface as possible.A method according to the invention is preferred, wherein the surface of the tire inner layer obtained from the inner layer blank is at least partially covered with polysiloxane particles to 70% or more, preferably to 80% or more, particularly preferably to 90% or more, very particularly preferably to 95% or more, particularly preferably to substantially 100%, based on the surface of the tire inner layer.

[0032] In the parts of the surface primarily covered with polysiloxane particles, the density of the polysiloxane particles, i.e., the mass of polysiloxane particles in the upper volume layer of the surface, can in principle vary, depending in particular on the application of the aqueous dispersion and the solids content. In this respect, the inventors propose that it is advantageous to achieve the densest possible coverage, ideally a complete coating, with polysiloxane particles, so that the surface of the tire inner layer is preferably formed essentially entirely by a layer of polysiloxane particles, particularly in the application area relevant for the adhesion of the sealant composition.A method according to the invention is preferred, wherein the surface of the tire inner layer obtained from the inner layer blank is covered with polysiloxane particles to 70% or more, preferably to 80% or more, particularly preferably to 90% or more, very particularly preferably to 95% or more, particularly preferably to substantially 100%, based on the surface of the areas covered with polysiloxane particles, in the areas covered with polysiloxane particles, in particular in the application area.

[0033] In process step d), a sealant composition is then applied to the application area. The application area is any area to which the sealant composition is applied, with the proviso that this application must be made to the surface coated with polysiloxane particles. In practice, this will usually be a process according to the invention, with the application area located on the inside of the pneumatic vehicle tire blank facing away from the tread blank.

[0034] According to the inventors' assessment, typical sealant compositions known from the prior art, which are commercially available from various manufacturers, can advantageously be used as the sealant composition. However, the inventors have succeeded in identifying sealant compositions which, in interaction with the surface coated with polysiloxane particles, exhibit particularly good adhesion while simultaneously offering advantageous removability. A method according to the invention is preferred, wherein the sealant composition comprises, based on the mass of the sealant composition: i) one or more first rubbers selected from the group consisting of butyl rubber and halobutyl rubber, preferably in a combined mass fraction in the range of 9 to 23%, particularly preferably in the range of 10 to 20%, and / or ii) one or more second rubbers,which are selected from the group consisting of diene rubbers different from the first rubbers, preferably polybutadiene rubber, preferably in a combined mass fraction in the range of 50 to 70%, particularly preferably in the range of 55 to 65%, and / or iii) one or more inorganic fillers, wherein the inorganic fillers are preferably selected from the group consisting of carbon black and magnesium oxide, preferably in a combined mass fraction in the range of 3 to 9%, particularly preferably in the range of 4 to 8%, and / or iv) one or more crosslinking agents, wherein the crosslinking agent is preferably selected from the group consisting of peroxides and oximes, for example p-benzoquinone dioximes, preferably in a combined mass fraction in the range of 0.5 to 3%, particularly preferably in the range of 1 to 2.5%.

[0035] A method according to the invention is preferred in which the sealant composition is applied as a formless mass. Alternatively, a method according to the invention is preferred in which a sealant layer is formed using the sealant composition.

[0036] In addition to the use of a specific tire release agent, the special feature of the method according to the invention is that the sealant composition is applied to the application area with the polysiloxane-coated surface. This means that, in contrast to the prior art, the tire release agent is not removed, but rather the polysiloxane particles remain between the surface of the tire inner layer and the applied sealant composition. Accordingly, unlike in the prior art, for example, no material-removing cleaning takes place, such as would be carried out with brushes or lasers. Preference is given to a method according to the invention wherein the surface of the tire inner layer at least partially coated with polysiloxane particles in the application area is not treated with a material-removing process between process steps c) and d).A method according to the invention is preferred, wherein the surface of the tire inner layer at least partially covered with polysiloxane particles in the application area between the method steps c) and d) is in particular not processed by brushes or lasers.

[0037] The inventors' experiments have shown that the surface provided with polysiloxane particles can be superficially cleaned using non-material-removing methods without excessively restricting the advantages of the method according to the invention and resulting in pneumatic vehicle tires that would be disadvantageous in terms of recyclability. Accordingly, it has proven advantageous to dispense with such cleaning and, in particular, to dispense with wet cleaning steps. Accordingly, a method according to the invention is preferred for essentially all embodiments, wherein the surface of the tire inner layer at least partially coated with polysiloxane particles in the application area is cleaned between method steps c) and d) using a non-material-removing method, wherein the non-material-removing method is preferably compressed air cleaning.A method according to the invention is also preferred, wherein the surface of the tire inner layer at least partially covered with polysiloxane particles in the application area is not contacted with a cleaning substance between process steps c) and d).

[0038] In particularly preferred embodiments of the process according to the invention, the sealant composition is thus applied directly to the tire inner layer coated with polysiloxane particles, as obtained after vulcanization. In other words, a process according to the invention is particularly preferred in which the sealant composition is applied directly to the surface of the tire inner layer produced in process step c).

[0039] The invention also relates to a pneumatic vehicle tire produced or producible by the method according to the invention.

[0040] The invention and preferred embodiments of the invention are explained and described in more detail below with reference to the accompanying figure. It shows:

[0041] Fig. 1 is a simplified flow diagram of the process steps of the process according to the invention.

[0042] Fig. 1 shows a schematic representation of the method steps of the method according to the invention in a flowchart. In a first step 100, a pneumatic vehicle tire blank is first produced, which, in addition to the carcass blank, the inner layer blank arranged on the inside thereof, and the tread blank arranged thereabove, may also comprise other components, for example, in particular sidewall components.

[0043] Before vulcanization, a silicone-based aqueous dispersion, such as the commercial product Rhenodiv BP-2864 from RheinChemie Additives, is applied to the inner layer blank in step 102. This dispersion has a solids content of approximately 44% and the liquid phase consists predominantly of water. The dispersion is applied over the entire surface using a spray gun at a rate of approximately 15 g / m 2 .

[0044] After this preparation, the pneumatic vehicle tire blank is vulcanized in a vulcanization mold in the next step 104, where it is provided with a profile. A surface densely coated with polysiloxane particles forms on the previously prepared surface of the inner layer blank, which is converted into a tire inner layer by vulcanization.

[0045] After removing the vulcanized vehicle tire from the vulcanization mold, a sealant composition is applied to the thus produced surface of the tire inner layer below the tread, coated with polysiloxane particles, in step 106 by applying a formless mass, without any intermediate cleaning of the corresponding surface, in particular without any material-removing cleaning, which would remove the polysiloxane particles from the surface of the tire inner layer. This results in a pneumatic vehicle tire which, in use, has sufficient bond strength between the sealant composition and the tire inner layer, but is very light in typical recycling processes, i.e.in a time- and cost-efficient manner, can be freed from the sealant composition, which can be done for example using typical cutting tools, for example a blade, whereby advantageously no or only minimal residues remain.

Claims

Claims 1. A method for producing a pneumatic vehicle tire, comprising the method steps: a) producing or providing a pneumatic vehicle tire green, comprising: i) a carcass green comprising a plurality of reinforcements embedded in a first vulcanizable rubber mixture, ii) a tread green arranged radially above the carcass green, and iii) an inner layer green arranged radially below the carcass green, comprising a second vulcanizable rubber mixture comprising at least one butyl rubber and / or halobutyl rubber, b) applying an aqueous dispersion to the surface of the inner layer green to obtain a prepared pneumatic vehicle tire green, wherein the aqueous dispersion comprises one or more dispersed polysiloxane particles, c) vulcanizing the prepared pneumatic vehicle tire green in a vulcanization mold to obtain a pneumatic vehicle tire,wherein the surface of the tire inner layer obtained from the inner layer blank is at least partially coated with polysiloxane particles, and d) applying a sealant composition to an application area of ​​the surface of the tire inner layer coated with polysiloxane particles.

2. The method of claim 1, wherein the second vulcanizable rubber mixture comprises the butyl rubber and / or the halobutyl rubber in a combined mass fraction in the range of 70 to 100 phr.

3. A method according to any one of claims 1 or 2, wherein the second vulcanizable rubber composition comprises halobutyl rubber.

4. A method according to any one of claims 1 to 3, wherein the second vulcanizable rubber mixture comprises one or more fillers.

5. A process according to any one of claims 1 to 4, wherein the liquid phase of the aqueous dispersion consists of 70% or more of water, based on the mass of the liquid phase.

6. The process according to any one of claims 1 to 5, wherein the aqueous dispersion has a solids content in the range of 30 to 60.

7. A process according to any one of claims 1 to 6, wherein the solid phase of the aqueous dispersion consists of 70% or more of polysiloxane particles, based on the mass of the solid phase.

8. The method according to any one of claims 1 to 7, wherein the surface of the tire inner layer at least partially coated with polysiloxane particles in the application area is cleaned between the method steps c) and d) using a non-material-removing method.

9. The method according to any one of claims 1 to 8, wherein the sealant composition is applied directly to the surface of the tire inner layer produced in process step c).

10. Pneumatic vehicle tire manufactured or producible by the method according to one of claims 1 to 9.

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