Process for making a branch stub

p0001The invention relates to a method for producing a socket for connecting a fluid line to a container of thermoplastic material, wherein the nozzle comprises a first nozzle-like, at least single-layer material arrangement and a second nozzle-like, at least single-layer material arrangement, of which the first material arrangement thinner than the second material arrangement is and have both than at least the predominant part of thermally deformable material and a fusible link go together.

p0002Such a method is known from DE 199 53 746 C2. There, the first material arrangement of two adjacent thin layers and the second material arrangement of an outer layer, which is thicker than the two-layer first material arrangement and essentially determines the mechanical strength of the nozzle. The three layers are to be injected in Koinjektions- or Monosarldwich process. Here, however, it is extremely difficult to form the single first material arrangement considerably thicker than the second material arrangement because then form two layers of a total of three-layer wall of a neck ei ne thin one- or two-piece skin layer whose entire wall thickness is generally less than the de core layer is. The skin layer has in a Koin usually jection a maximum thickness of about 2 mm Then, when the wall thickness of the neck for reasons of strength for example, about 10 mm and the thickest layer to be on the outside, such a layer arrangement can not be practical in Koinjektions- or monosandwich manufacturing process.

p0003On the other hand, can be a lot of materials not in egg nem injection process multilayered splash, either extrusion process in Ko or in rapid succession, as long as the previously sprayed layer is still molten, for example an aluminum layer and unmittelba first: then, as long as the aluminum layer is still molten , a plastic layer, because aluminum has a much higher melting temperature than plastic, which would not withstand the plastic. The same applies to materials with different flow characteristics.

p0004The invention is based on the object of specifying a method of the aforementioned type, wherein the thickness and relative position of the layers for a given wall thickness of the neck independently of the function of the layers is largely arbitrary.

p0005This object is achieved in that in a first step the first material arrangement is formed in an extrusion or injection molding to a plane film or plate or a hose that in a second step the film or sheet by deep drawing or the hose by blow is formed a first preform with neck contour, that the second material arrangement is applied in injection molding, Koinjektions- or monosandwich process with short contour in a third step, on one side of the first preform, and that in the case of the first formed from the film or plate preform whose bottom before, is cut out in or after the third step.

p0006In this solution, the thicker material arrangement can form the radially outer or inner material structure of the connection piece, depending on whether the first preform to the application of the second material arrangement on the correspondingly shaped inner surface of the outer wall of a injection-molding tool or the correspondingly shaped outer surface of a core by injection -Formwerkzeug is arranged. To achieve the desired thickness of the second material arrangement, the thickness of the intermediate space between the first preform and the inner side of the wall or the outside of the core of the molding tool is then selected accordingly. The thickness of the first preform is selected during thermoforming or blow molding according to the desired wall thickness of the sleeve. The material of the second material arrangement can be chosen according to the desired strength and function of the second material arrangement, so that the second material arrangement will operate as an institution of the first preform and on the other hand a solid melting or welding connection with the material of the container, preferably a fuel tank of a motor vehicle, and the first preform is received. Conversely, the material of the first preform may be chosen such that with the arrangement of the second material undergoes a solid melting or welding.

p0007Further, it is possible that a first layer and a second layer and optionally a third layer which undergo fusion bonding, the coextrusion or layer by layer by injection molding are stacked in the first step to form the film, the panel or the tube.

p0008This can be ensured that one of the layers formed in the first step is a bonding agent or a diffusion barrier layer against hydrocarbons and at least one of the materials PA, EVOH, PE, PET, PBT, PBN, PEN, POM, PP, fluorine thermoplastic PPS comprising metal, and the second material arrangement is applied to the second layer and at least one of the materials PE, PP, PA, PBT, PET, PBN and POM.

p0009Another of the layers formed in the first step preferably comprises one of the materials PA, EVOH, PE, PET, PBT, PBN, PEN, POM, PP, fluorothermoplastic, PPS and is made conductive by an electrically conductive additive thermoplastic layer.

p0010The second material arrangement can be applied to the inside or the outside of the first preform.

p0011Alternatively, it is possible that the second material arrangement comprises a core layer and a skin layer, which are manufactured in or Koinjektions- monosandwich process, and that the skin layer and the first material arrangement fusion bonding enter (are compatible). If one chooses, in this embodiment, a predetermined thickness of the second material arrangement, then, the core layer - with a wall thickness of the sleeve, for example 10 mm and a thickness of only about 2 mm for the first material arrangement or the first preform - a thickness of 4 mm and the skin layer or located on both sides of the core layer two layers of the skin (when the skin layer is divided through the core layer into two layers of skin) each having the maximum thickness of 4 mm and 2 mm per skin layer on both sides of the core layer.

p0012The material of the skin layer (s) can PE and the core layer may be a diffusion barrier layer against hydrocarbons, which comprises at least one of the materials PA, EVOH, PET, PBT, PBN, PEN, POM, fluorothermoplastic and PPS.

p0013The diffusion barrier layer may comprise a reinforcement material, in particular glass fibers have. The core layer may also comprise a reinforced material, such as PE or PP, reinforced by glass fibers, glass beads or mineral particles.

p0014It is then possible that the (one-piece) skin layer is applied on the outside or inside of the first preform and the second material arrangement is externally formed in a to be connected to the container first end portion as a flange and in a second end portion having at least one holding rib, and that the core layer is injected into the ribbed end portion and up to or into the flange. Trained as a diffusion barrier layer core layer formed in this way at the same time a reinforcement layer at least in the area between the rib end portion and the flange, because around this area, deferred to him fluid line is clamped generally by means of a hose clamp, so that this intermediate region the clamping pressure of the hose body must withstand, without deforming.

p0015Alternatively, the first material arrangement having a first layer and a second layer, which are formed in each case according to the first step and the second step to the first preform and a second preform, and in a third step, a first layer of the second material arrangement in the injection molding process between the first and second preform injected and in a fourth step, a third layer are injected into the still formable core of the first layer of the second material arrangement, so that the first layer of the second material arrangement a skin layer and the third layer forms a core layer.

p0016Further, it is possible that in the first step three layers of the first material arrangement are formed to the slide plate or tube, in order to form the first preform according to the second step, and that a by repeating the steps 1 to 3 formed the second three-layer preform is arranged together with the first three-layer preform in a mold under control systems of a gap between the preforms and injected into the space, the second material arrangement in the form of a skin layer and a core layer in Koinjektions- or monosandwich process.

p0017If the piece has a first nozzle-like, three-layer material arrangement which is at least mainly made of thermoplastic material in Koinjektions- or monosandwich process, the object is achieved according ensured according to a second solution that the skin layer of the first material arrangement with a second material arrangement at least predominantly composed of thermoplastic material, which forms a fusion bond with the skin layer of the first material arrangement is fused.

p0018This eliminates the thermoforming or blow molding, to form the first preform of the first material arrangement. Nevertheless, the first material arrangement can be formed as a preform thinner than the second material arrangement.

p0019The second material arrangement can be applied here on the first material arrangement in the injection molding process, so that it has the required thickness to give the piece the required stiffness.

p0020Then it is possible with the second solution, that the first material arrangement is arranged as a preform in a mold that a third material arrangement has at least produced in three shifts in Koinjektions- or monosandwich process mainly made of thermoplastic material and in the mold as a second preform having a space for first preform is arranged and that the second material arrangement is injected into the intermediate space and with the skin layers of both preforms forms a fusible link.

p0021Further, the second material arrangement can be single, mostly have PE or PA and largely comprise the same thickness as the two preforms together or be thicker to give the piece the required strength and rigidity.

p0022Furthermore, in the second solution, the second material arrangement between the two preforms can be three layers formed in Koinjektions- or monosandwich process and do their skin layers with the skin layers of the preforms a fusion bond.

p0023The skin layers of the first material arrangement can be a PE and its core layer having a diffusion barrier layer for hydrocarbons.

p0024Also, the skin layers of the second material arrangement can have a PE, and its core layer may comprise a diffusion barrier layer for hydrocarbons or reinforcing material.

p0025The diffusion barrier layer of the second material arrangement preferably comprises PA or EVOH, and the core layer of the second material arrangement has preferably substantially the same thickness as its two skin layers together or is thicker.

p0026From DE 199 53 746 C2 is also known a process for producing a connecting piece for connecting a fluid line with a container of thermoplastic material, wherein the connecting piece a first, a second and a third rotationally symmetric material arrangement has, for the most part consist of thermoplastic material, wherein the first material arrangement is at least one layer and the second material arrangement surrounding the third material arrangement surrounds the first material arrangement, the first, second and third material arrangement are connected by a fusion bond and form a flange of the socket on the side of the container and the first material arrangement and the second material arrangement extend to a to be connected to the container surface of the flange.

p0027Also in contrast, there is a solution provided by the invention is that in a first step the first material arrangement is formed in an extrusion or injection molding to a plane film or plate or a hose that in a second step, the film or sheet by deep drawing or the hose is blow molded into a parison that in a third step, the second material arrangement is applied to one side of the preform injection molding that the third material arrangement to one of the remote to the container to be connected surface end portion of the first material arrangement in a fourth step injection molding process in the area of ​​the flange douse and that is cut out in the case of the preform formed from the film or plate the bottom before, in or after the third step.

p0028Here, the novel process is carried out in the region of the flange of the sleeve.

p0029In this third method, the first material arrangement can in turn have a diffusion barrier layer, a diffusion barrier layer, the second material arrangement polyethylene and the third material arrangement. The material of the diffusion barrier layers may in turn be at least one of the above-cited materials with diffusion barrier capability for hydrocarbons. Preferably is PA.

p0030Then, the first material arrangement and the third material arrangement comprising electrically conductive particles in the third solution. It is thereby achieved that the connecting piece (when the third material arrangement substantially comprises PE) over its entire length is electrically conductive to prevent electrostatic charging of the nozzle.

p0031Furthermore, can be produced multilayer in the first step of the third solution the first material arrangement in the coextrusion process, wherein at least one of the layers is electrically conductive. Since these electrically conductive layer is in contact with the third material arrangement, an electrical conductivity of the nozzle also arises in this case over its entire length.

p0032A fourth solution of the mentioned task, starting from the aforementioned known method, is that in a first step one of the two material structures is formed in a first Formwerkzeugkavität in a preform with neck contour that in a second step, the other of the two material arrangements is molded in a second Formwerkzeugkavität to the first preform and that the plastic is one of the two material structures that comes to the fluid line when connecting in contact comprises an electrically conductive additive.

p0033In this solution, the entire piece can be formed in the first step of the first preform and the second step. When the fluid line to prevent an electrostatic charge during filling of the container - for example a tank of a motor vehicle with a hydrocarbon such as gasoline or diesel fuel - via the fluid line is electrically conductive would have the entire joint, consisting of the fluid line and the immediately connected to the container Pruning, protected from electrostatic charging.

p0034Here, the plastic material of an arrangement for hydrocarbons may be capable of blocking diffusion and enter the plastic material of the other arrangement with the plastic of the container a fusion bond.

p0035It is particularly favorable if the plastic of the thinner material arrangement comprises the diffusion barrier capability. Since diffusion-blocking enabled plastics, such as those listed above received, with usually at least predominantly PE container having no melting compound, it would be sufficient if only the fusible with the PE of the container thicker material arrangement entered into by the connection to the container, because their connection surface on the container side end the connecting piece is correspondingly larger and thus enables a secure connection.

p0036An alternative to using diffusionssperrfähigem plastic for one, especially the thinner material arrangement, one of the two material arrangements may in at least one diffusion barrier capable of hydrocarbons, for more than 50%, preferably more than 90%, the length of the relevant material structure extending layer coinjection - be injected or monosandwich process and enter into the plastic of the material arrangement or any material arrangement, in which the diffusion barrier layer capable is injected, with the container material is a fusible link. The diffusion barrier layer may be made very thin, so that that material arrangement or both material arrangements, which is provided with the diffusion barrier layer capable or are, forms a firm fusion bonding to the container or received.

p0037Another possibility is the fourth solution is that the thicker material arrangement has a depth to the container fusion bonding plastic and in they injected, diffusion-blocking enabled layer extends over less than 100% of the length of the thicker layer, and that the thinner material arrangement in fused to the second step on the entire inside of the thicker material arrangement to about the remote from the container to be connected face end of the thicker material arrangement addition and is formed into a over the outside of the thicker material arrangement beyond retaining rib for the fluid line and having the conductive additive. The thicker material arrangement can then be of conductive additives, such as particles of graphite, metal or carbon, for example, carbon black, or an addition of electrically conductive, so-called nano-tubes, which do not undergo fusion bonding to the container, but a relatively large ratio of length have diameters such that they ensure a vertical plane passing through the entire piece electrically conductive connection, be kept free. Further, to be joined to the container surface of the thicker material assembly remains relatively large, so that it forms a firm connection with the container.

p0038Preferably, it is ensured that both material arrangements PE, in that a first layer is injected in Koinjektions- or monosandwich process in the PE at least one of the two material arrangements, which undergoes a melting connection with PE and a diffusion barrier performance for hydrocarbons plastic, and that in the first layer a second layer is injected in the Koinjektions- or mono-sandwich method, which comprises the diffusion barrier performance for hydrocarbons plastic. In this way it is ensured that the Diffiusions or the resulting at higher temperatures the vapor pressure of hindurchdiffundierenden by the PE hydrocarbon, such as fuel in the form of gasoline or diesel oil, the PE may not stand out from the diffusion-blocking enabled layer so that it would eventually peel off. Likewise also the different swelling behavior of the diffusion barrier layer capable of PE and would not result in the PE apart from the diffusion barrier layer enabled. As far as the diffusion barrier-layer-is injected only or also in the radially external material arrangement of the nozzle, would be avoided by forming a fusion bond between the diffusion barrier capable layer and the surrounding PE is a risk that the PE is lifted and removed by mechanical forces of the diffusion-blocking enabled layer becomes.

p0039To achieve a firmly as possible fusion bonding between the first layer and the polyethylene of the relevant material structure and the diffusion barrier performance layer, it is advantageous if the diffusion barrier capable of hydrocarbons plastic PA or EVOH, and the first layer comprises an adhesion-modified by means of maleic anhydride PE and when the diffusion barrier capable PA plastic is, the amino terminal group concentration is equal to or greater than 40 milliequivalents per kilogram.

p0040In this construction it is advantageous if the first and the second layer of material extending an arrangement more than 50%, preferably more than 90%, the length of this material arrangement. The diffusion barrier capability of the socket is then ensured over a very large part of the length of the neck.

p0041If this extend, the first and the second layer of thicker material arrangement has less than 100%, but still more than 50%, preferably more than 90% of the length of the thicker material arrangement, a relatively large joint surface is also used in this embodiment of the connecting piece ensured between the thicker material arrangement and the container, thus achieving a firm connection between the nozzle and the container.

p0042In cases where no high demands are placed on the diffusion barrier capability of the socket, the first and the second single-material structure made of plastics, not only each other but also with the container enter into a cohesive fusion bond. It then takes turn only one material arrangement to have the electrically conductive additive, preferably the radially inner material arrangement which may be thinner than the radially outer material arrangement. When the container PE or HDPE, in both material arrangements may also comprise predominantly PE.

p0043Since only a material assembly having the conductive additive, the entire piece can cost-effectively than with single-layer design of the entire nozzle are made with a conductive additive in spite of the material costs increasing conductive additive. The other material arrangement has then due to lack of conductive additive provides greater chemical resistance and stress cracking resistance. Since both material arrangements form a cohesive fusion bond with the container, the molten resin of the conductive material arrangement can not penetrate between the different material structure and the container and interfere with their communication with the container.

p0044Furthermore, the thicker material arrangement should be formed in the first step. The thicker material arrangement then determines not only the mechanical strength of the socket and its connection to the container, as long as it does not have electrically conductive additive, but at the same time also forms the support for the thinner and thus less mechanically robust material arrangement.

p0045The invention and its developments are described below with reference to the accompanying drawings of preferred embodiments in more detail. Therein show in:<dl id="dl0001"><dt>Fig. 1</dt><dd>a nozzle manufactured according to a first embodiment of the inventive method, </dd><dt>FIG. 2</dt><dd>a nozzle manufactured according to a second embodiment of the inventive method,</dd><dt>Fig. 3</dt><dd>a nozzle manufactured according to a third embodiment of the method according to the invention,</dd><dt>Fig. 4</dt><dd>a nozzle manufactured according to a fourth embodiment of a method according to the invention,</dd><dt>Fig. 5</dt><dd>a nozzle manufactured according to a fifth embodiment of a method according to the invention,</dd><dt>Fig. 6</dt><dd>a nozzle manufactured according to a sixth embodiment of the method according to the invention,</dd><dt>Fig. 7</dt><dd>a nozzle manufactured according to a seventh embodiment of a method according to the invention,</dd><dt>Fig. 8</dt><dd>a piece produced according to an eighth embodiment of an inventive method,</dd><dt>Fig. 9</dt><dd>a piece produced according to a ninth embodiment of an inventive method, </dd><dt>Fig. 10</dt><dd>a nozzle manufactured according to a tenth embodiment of a method according to the invention,</dd><dt>Fig. 11</dt><dd>a nozzle manufactured according to an eleventh embodiment of the inventive method,</dd><dt>Fig. 12</dt><dd>a nozzle manufactured according to a twelfth embodiment of the inventive method,</dd><dt>Fig. 13</dt><dd>a nozzle manufactured according to a thirteenth embodiment of the method according to the invention,</dd><dt>Fig. 14</dt><dd>a nozzle manufactured according to a fourteenth embodiment of the method according to the invention,</dd><dt>Fig. 15</dt><dd>a piece produced according to a fifteenth embodiment of the inventive method,</dd><dt>Fig. 16</dt><dd>a nozzle manufactured according to a sixteenth embodiment of the method according to the invention,</dd><dt>Figure 17</dt><dd>a nozzle manufactured according to a seventeenth embodiment of the inventive method, </dd><dt>Figure 18</dt><dd>a nozzle manufactured according to an eighteenth embodiment of the inventive method and</dd><dt>Figure 19</dt><dd>a nozzle manufactured according to a nineteenth embodiment of the method according to the invention.</dd></dl>

p0046The nozzles shown in FIGS. 1 to 12 are a multilayer structure and serve to connect one (only in Fig. 13, 15 and 18 shown) fluid conduit, such as a tube of diffusion-proof plastic, with a predominantly made of plastic container 1 for hydrocarbons, here a motor vehicle tank of gasoline or diesel fuel, of which only a wall 2 is shown with a filling opening. 3 The fluid line may additionally include an electrically conductive additive to an electrostatic charge. Each nozzle is also at least predominantly made of a thermoplastic plastic and is materially connected with the edge of the filling opening 3, here welded, so that a fusion bond between the connector and the container 1 results. In each piece of the container-side end portion with a peripheral flange 4 and the end portion facing away from the container 1 is provided with a circumferential holding rib fifth In the area between flange 4 and retaining rib 5 shown in FIGS. 1 to 12 of the nozzle is slightly thinner. When connecting the fluid line which is pushed down to the thinner portion on the supporting rib 5 across the neck and clamped in this area by means of a hose clamp.

p0047While the container 1 comprises essentially HDPE (high density polyethylene) with a diffusion barrier capable of hydrocarbons (not shown) intermediate layer of PA or EVOH, has the nozzle of FIG. 1 outside a single first material arrangement 6, which primarily consists of a thermoplastic material, here one of the diffusion barrier materials capable PA, EVOH, PET, PBT, PBN, PEN, POM, fluorothermoplastic, PPS. Internally, the stub to a second single-layer material arrangement 7, which are mainly composed of thermoplastic material, here PE, the compatible with the plastic of the container 1 and the first material arrangement 6, ie, can be welded and fusion bonding is received. Where necessary, the second material arrangement 7 may be adhesion-modified accordingly to achieve the fusion bonding. The thermoplastic material of the first material arrangement 6 can additionally electrically conductive particles, for example made of graphite or metal exhibit. The second material arrangement 7, however, is preferably reinforced, for example with glass or carbon fibers.

p0048The connecting piece according to Fig. 1 is produced in such a manner that in a first step, the first material assembly 6 is formed in an extrusion or injection molding process into a flat film or sheet or a tube, that in a second step, the film or sheet by deep-drawing or the tube is blow molded in a first preform with neck contour, that the second material arrangement 7 is applied by injection molding with short contour in a third step, on one side of the first preform, and that in the case of the first preform formed from the film or plate the bottom thereof, before, cut out in or after the third step.

p0049The two material arrangements 6 and 7 can in this case, while maintaining the desired wall thickness of the sleeve, different thicknesses, ie for example the first material arrangement 6 very thin, as it is sufficient for a diffusion barrier layer, and the second material arrangement 7 are chosen according to thick, so that they as a carrier can serve for the first material arrangement 6 and to achieve the desired strength of the socket and its connection to the container. 1

p0050A particular advantage of this method is that even material structures can be joined together in this way, which is not only an injection process can be connected (in co-extrusion), for example, an axially continuous metal layer with a layer of plastic, because of their very different melting temperatures. Metal has a much higher melting temperature than thermoplastic material so that the plastic would decompose at the higher melting temperature of the metal.

p0051In the embodiment of FIG. 2, the first material arrangement 6 is contrary 6b of a first layer 6a and a second layer which undergo fusion bonding, are stacked in coextrusion or layer by layer by injection molding to the sheet, the plate or the tube to form, and then again - in the case of flat sheet or plate - deep drawn or - be blow molded to form the nozzle-like first preform - in the case of the hose. The first preform is injected behind the second material arrangement 7 in the same manner as in the embodiment of FIG. 1 turn. The thickness ratios can be selected similarly to the first embodiment. While the materials of the second material arrangement 7 are in turn selected as the first embodiment, the materials of the layers 6a and 6b of the first material arrangement 6 are chosen differently, the outer layer 6a in turn by a diffusion barrier layer of the same materials as the first material arrangement 6 Fig. 1 and the middle layer 6b can be formed of an adhesion promoter. However, it is also possible for the layer 6a 6b to produce a diffusion barrier layer and the outer layer, for example made of PE or PA, wherein the middle layer 6b again with the layers 6 and 7 must be compatible (fusible).

p0052Instead of the first material assembly 6 for forming from the layers 6a and 6b by deep drawing or blow molding, to the first preform, it is also possible to first preform the layers 6a and 6b in the multi-component injection molding process (one layer after another) in a mold produce.

p0053In the embodiment of FIG. 3, the first material arrangement 6 from three layers 6a-6c, the materials are selected so that they form a fusion bond to the respective adjacent layer. Similarly, it appears, the layer 6b a fusion bond with the second material arrangement 7 a. The layers 6a-6c are first stacked in co-extrusion molding process or layer by layer by injection molding into a flat sheet or plate or a hose. From this layer arrangement, the first preform is formed by thermoforming or blow molding in turn, is then placed in an injection mold and back-injected with the second material arrangement. 7 From the deep-drawn, cup-shaped first preform is before, during or after the insert molding of the second material arrangement 7 excised the ground.

p0054The layers 6a-6c are a maximum as thick as the second material arrangement 7, when the wall thickness of the sleeve in turn is equal to the first embodiment. Of the three layers 6a-6c are made from at least two different materials, one with the second material arrangement 7 is fusible. For example, the radially outer layer 6c by an additional electrically conductive, the medium layer 6, a barrier layer and the radially inner layer 6b, an adhesion promoter, enables the connection between the intermediate layer 6a and the second material arrangement 7, which in turn comprises PE in order to the container 1 combine by melting, but with a barrier layer as a middle layer 6a, for example, PA or EVOH having no fusible link is received, if the PE of the second material arrangement 7 is not as adhesion-modified, that with PA or PE fusion bonding received.

p0055Alternatively, the outer layer 6c adhesion modified PE, the middle layer 6a can turn PA or EVOH and the second material arrangement 7 have also adhesion modified PE. The PE outer layer 6c would then offset the 7 compared to the second embodiment of FIG. 2 somewhat lower thickness of the second material arrangement to achieve the same strength of the socket at the same total wall thickness.

p0056In the embodiment according to Fig. 4, the two material structures 6 and 7 are reversed to those of FIG. 1. That is, the first material arrangement 6 is radially inward and the second material arrangement arranged externally, while the production in the same manner as in the first embodiment of Figure 1 is carried out. First, the material arrangement 6 as a first preform from a flat sheet or plate by deep drawing or produced from a tube by blow molding. To the first preform, the second material arrangement 7 is then sprayed around the outside the injection molding process, wherein the bottom of the deep-drawn form before, during or cut out after around spraying the second material arrangement 7 is. The materials of the two material structures 6 and 7 may be again the same as in the first embodiment.

p0057Also in the embodiment of FIG. 5, the position of the two material arrangements 6 and 7 is only against the swapped the first and second embodiment. However, the manufacture and the materials are again the same as in the second embodiment.

p0058In the embodiment according to FIG. 6, only the order of the materials is also 6 and 7 with respect to the reversed to Fig. 3, during the manufacturing process and the materials of the material assemblies 6 and 7 with respect to FIG. 3 are unchanged.

p0059In the embodiment of FIG. 7, the order of the materials 6 and 7 is reversed also in relation to the FIG. 1. The second material arrangement 7 however, consists of two layers, a skin layer 7 and a core layer 7b, which is injected into the still formable core of the skin layer 7a in Koinjektions- or mono-sandwich method, after the skin layer 7a to the first, as well as in the first embodiment preform produced material forming assembly 6 has been sprayed around the injection molding process. may 7b The core layer, a reinforcing material such as glass or carbon fibers, exhibit or if the inner material arrangement 6, a diffusion barrier layer of, for example, PA or EVOH forms, form an additional barrier.

p0060The core layer 7b extends from the end portion of the holding rib 5 of the connecting piece over the thinner middle portion of the connecting piece to the flange 4 to higher form in formation of the core layer 7b as a reinforcing layer the middle, slightly thinner area against the clamping pressure of the hose clamp loads. The core layer 7b may alternatively also be constructed as an additional diffusion barrier layer, when the first material arrangement 6 is also formed as a diffusion barrier layer to increase the diffusion barrier capability of the nozzle.

p0061The embodiment of Fig. 8 differs from that of FIG. 7 only in that the core layer 7a is formed longer so that it extends into the flange 4 in order to increase the strength or diffusion barrier capability of the sleeve still further.

p0062In the embodiment of FIG. 9, the first material arrangement 6 on a first layer 6a and second layer 6b, each by the same method as the first preform of the first material arrangement 6 in the embodiment according to Fig. 1 in the first and second step to a first preform and a second preform are formed. The two preforms 6a and 6b are then each disposed with one of the desired thickness of the second material arrangement corresponding distance in a suitably shaped injection molding die, and then a first layer 7a of the second material arrangement 7 is injection molded between the first preform and the second preform, ie between the layers 6a and 6b, sprayed and injected into the still formable core of the first layer 7a of the second material arrangement 7 a third layer 7b of the second material arrangement 7 in Koinjektions- or monosandwich process.

p0063Here, the outer layer may have 6a thermoplastic material with electrically conductive particles and the inner layer 6b diffusion barrier capable PA or EVOH, while the layer 7a modified PE and the middle layer 7b in turn may comprise a reinforcing material, but all adjacent layers may be heat-fused with each other. Since the layer 7b is included in the material of the layer 7a, but it is not necessarily required that the layer 7b with the fusible layer 7a (compatible). Furthermore, the layer 7b can axially further be up to or into the flange 4, is injected, for example.

p0064In the embodiment according to Fig. 10, of which only one half is shown, because the other as in the preceding embodiments to the one half is symmetrical, the connection piece from a first nozzle-like material arrangement 6, which comprises three layers 6a, 6b and 6c , a second nozzle-like, however, single-material arrangement 7 and made of a third nozzle-like material arrangement 8 with three layers 8a, 8b and 8c. All assemblies consist at least predominantly of thermoplastic material.

p0065The first material arrangement 6 is produced in Koinjektions- or monosandwich process the first preform so that its outer layers 6a and 6b form a skin layer and inner layer 6c forms a core layer, which is about as thick to about twice as thick as each of the layers 6a and 6b.

p0066The layers 6a and 6b have PE, while the layer 6c, a PA or EVOH comprising forming a diffusion barrier layer for hydrocarbons. The second material arrangement 7 also includes PE, so that it is received by a fusion bond with the layer 6b.

p0067The third material arrangement 8 is also produced in Koinjektions- or monosandwich process as a second preform so that its outer layers 8a and 8c form a skin layer and inner layer 8b forms a core layer. The layers 8a, 8c also have PE, while the inner layer 8b a PA or EVOH, such that the latter forms a diffusion barrier layer for hydrocarbons. Thus, the layer 8c goes with the material arrangement 7 a fusion bonding, since they have both PE. While the layers 8a and 8c are approximately the same thickness, the layer 8b is about as thick to twice as thick as one of the layers 8a, 8c. This is the same as in the layer 6c made possible in that the maximum thickness of material assemblies 6 and 8 by appropriately thin formation of the cavity of the mold in which the Koinjektions- or mono-sandwich method for producing the material assemblies is carried out 6 and 8, the same is selected to 2 to 4 times the skin layers, the thickness of which is constant at 1 to 2 mm at a Koinjektions- or mono-sandwich method generally.

p0068Alternatively, however, the material assemblies 6 and 8 are also in the co-extrusion injection molding or their layers successively layer by layer in the extrusion molding process on each sprayed to a film or sheet or a tube, and then the sheet or plate by deep drawing or the tube by blow molding to the first and second preform are formed, after which the two preforms are in turn arranged with a space therebetween in a correspondingly shaped injection mold and the second material arrangement 7 is injected into the gap. In the case of deep-drawn preforms her soil can turn before, during excised or after injection of the second material arrangement 7 in order to obtain the open at both ends Stutz form. It is also possible, 10 the first material arrangement 6 or the third material arrangement 8 omit in the embodiment of FIG..

p0069In the embodiment of Fig. 11, not only the material assemblies 6 and 8 as in the embodiment of FIG. 10 in the Koinjektions- or mono-sandwich method, but also the second material assembly 7 after the completion of the first and second preform in a mold in the intermediate space between these two preforms in Koinjektions- or mono-sandwich method to be injected, so that the outer layers 7a and 7c of the second material assembly 7 also form a skin layer of PE, and the inner layer 7b forms a core layer made of PA as a diffusion barrier layer and support layer. In contrast, the first material arrangement 6 forms on both sides of the core layer 6c is a skin layer comprising PA, and having a core layer 6c, the EVOH, and thus a further diffusion barrier layer. The third material arrangement 8 may then comprise skin layers 8a and 8c made of PE and a core layer 8b of EVOH as an additional diffusion barrier layer.

p0070Since the PA-containing core layer 7b of the second material arrangement 7 is not complete, as shown, is injected into it up to the bottom, to be welded to the container 1 end of the skin layer (s) 7a and 7c forming PE in the PE, is a sufficiently large surface made of PE available, which can undergo a solid weld or fusion bond with the PE of the container. 1 Again, the thickness ratios of the layer can be selected so that the skin and core layers of the material arrangements 6 and 8, while maintaining the required wall thickness of the neck, are about the same thin, however, the carrier layer 7b is relatively thick, about as thick as your skin layer ( s) 7a, 7c (together) or thicker.

p0071Similarly, the first material arrangement 6 or the third material arrangement 8 can be omitted in this case.

p0072Fig. Figure 12 illustrates one half of a flange 4 of a connecting piece produced according to a further embodiment of a method according to the invention in axial section. The not shown, the container 1 facing away part is also provided with a holding rib, as in the previous embodiments. The nozzle also has a first material arrangement 6 that. Radially inside or outside, or, as shown, located on either side of a second material arrangement 7, and a third material arrangement 8, which consist predominantly as in the piece described above of thermoplastic material The first material arrangement 6 is single ply, and has a relatively small thickness. It surrounds the much thicker second material arrangement 7. The third material arrangement 8 surrounds an end portion 9 of the first and second material arrangement 6, 7, which is thus turned away from the to be connected with the container 1 surface 10 of the flange. 4 The material arrangements 6, 7 and 8 may in turn form a fusion bond with each other.

p0073The preparation of this connecting piece is again done in the manner that the first material arrangement 6, that the outer or inner or both, is formed in an extrusion or injection molding process into a flat sheet or plate or to a tube in a first step. In a second step, the film or sheet is in turn formed by deep drawing or the tube by blow molding a preform illustrated in Fig. 12, having angled shape. However, at least the transitions of the material arrangement 6 or the preform formed from it must not angled pass into the end section. 9 The transitions can also be round.

p0074In a third step, the second material arrangement 7 on one side of the applied from the outer or inner material arrangement 6 or both formed preform injection molding is (back-injected). In a fourth step, the third material arrangement 8 is molded around the end portion 9 of the first and second material arrangement 6, 7 by injection molding in the region of the flange. 4 Here also an uncovered by the material arrangement 6 part 11 of the second material arrangement 7 is covered by the third material arrangement. 8 In the case of the preform formed from the sheet or plate whose bottom is against cut out in or after the third step.

p0075The first material arrangement 6 has a diffusion barrier layer, the second material arrangement 7 polyethylene (PE) and the third material arrangement 8 also on a diffusion barrier layer for hydrocarbons. The diffusion barrier performance materials, it may likewise be the described in connection with the previous embodiments materials. Preferably, it is PA or EVOH.

p0076The first material arrangement 6 and the third material arrangement 8 contain electrically conductive particles, such as particles of metal, graphite or carbon. Since the first material arrangement 6 and the third material arrangement 8 are in contact, resulting in a over the entire length of the sleeve conductive layer to prevent electrostatic charging of the neck.

p0077Instead the first single-material arrangement 6 or its film or plate can be made multilayered in the first step in the co-extrusion process, wherein at least one of the layers is electrically conductive.

p0078If the first material arrangement covering 6 as shown, both the radially outer and the radially inner side of the second material arrangement 7, the largely non-diffusion-blocking enabled PE of the second material arrangement 7 is covered by a double diffusion barrier layer enabled. In contrast, the thicker second material arrangement 7 can about the large annular surface 10 with the PE also having at least the outer layer of the container 3 to enter into a high mechanical stress, solid fusion bonding by welding.

p0079Another alternative may be that, even before it is fully cured in the second material arrangement 7, a further layer is injected in Koinjektions- or monosandwich process.

p0080In the embodiment of the nozzle according to FIG. 13, of which again only one axially symmetrical with respect to the center line shown in broken lines half is shown, the thinner material arrangement 6 and inside the thicker material arrangement 7 is located outside. Although the material arrangement 6 is about half as thick as the material arrangement 7, it can be much thinner. It could also be slightly thicker than illustrated, but should in any event be thinner than the thickness 70 of the material arrangement 7 °.

p0081The material arrangement 6 comprises mainly on one of the aforementioned, to hydrocarbons such as gasoline or diesel oil, diffusion barrier mouldable plastic and includes an electrically conductive additive. In the additive, it may be particles of graphite, metal or carbon, for example carbon black, or so-called electroconductive nano-tubes. Nano-tubes have the advantage that they have a relatively large ratio of length to diameter of about 100, so that they form a whole almost certainly an over the entire length of the material arrangement 6 continuous electrically conductive connection. The amount of the additive is selected such that the electrical resistance of the material arrangement 6 in the range from 100 Ω to 10⁷ Ω, preferably about 1,000 to 10,000 Ω Ω is, so that the material arrangement 6 is not electrostatically charged during filling of the container. 1

p0082The material arrangement 7 comprises predominantly PE, which in contrast to the diffusion barrier performance plastics with the HDPE of the container 1 forms a fusible link.

p0083At least one of the two material arrangements 6 and 7 is adhesion-modified, so that they take also a fusion bond with each other. If the diffusion-blocking enabled plastic material arrangement 6 adhesion-modified in such a way that it forms a fusion bond with the PE of the material arrangement 7, it may undergo fusion bonding with the HDPE of the container. 1

p0084In the production of the sleeve of FIG. 13, the thicker material arrangement 7 is formed in a first Formwerkzeugkavität into a parison with the illustrated nozzle contour in a first step, ie with a longer cylindrical portion and the flange 4. In a second step, then the thinner material arrangement 6 is formed in a second Formwerkzeugkavität in the illustrated neck contour and formed simultaneously to the first preform of the material arrangement 7, in such a way that the thinner material arrangement 6, the thicker material arrangement 7 at the entire inside about to be joined to the container 1 surface 10 remote from the end of the material arrangement 7 also is melted and formed into the over the outside of the material arrangement 7 projecting holding rib. 5

p0085, Via the conical annular surface of the retaining rib 5 of time then, after the spout has been sealed to the outside of the wall 2 of the container 1 in the region of the surface 10, for example by friction or mirror welding, the fluid conduit 12 in the form of a hose to behind the supporting rib 5 is pushed onto the socket and, if necessary, be clamped with a hose clamp. 13 When the fluid line 12 also includes an electrically conductive additive, the entire connection from a fixed to the end of the fluid line 12, not shown, filler neck via the fluid conduit 12 and the material arrangement 6 is up to the container 1 electrically conductive, so that they are of the filling container 1 can not become electrostatically charged. When the container 1 has in addition an electrically conductive layer covering its opening 3 and its outer side from the opening up to the inner edge of the surface 10, the conductive connection a fusion bond of the material arrangement also reaches up to the container 1. This conducting layer would indeed 6 hinder or prevent the container. 1 Due to their electrically conductive additive, the material arrangement 6 would, however, even without the conductive layer of the container 1 hardly connect with this. However, since the material arrangement 7 re compared to the material arrangement 6 is relatively thick, the large-area connection between the material arrangement 7 and the container 1 essentially alone can determine the strength of the connection between the connector and receptacle. 1 For the same reason, the material arrangement 7 is to ensure as a carrier of thin material arrangement 6 alone capable of a sufficient mechanical strength of the nozzle. The electrical connection between the fluid conduit 12 and the supporting rib 5 of the material arrangement 6 also allows the material arrangement 7 to hold of an electrically conductive, fusible link between the material arrangement 7 and the container 1 at least debilitating additional dates.

p0086In principle, it would also be possible, the material arrangement 7 thinner than the material arrangement 6 and consists essentially of a diffusion barrier moldable plastic, with an electrically conductive additive, however, the material arrangement 6 much thicker than the material arrangement 7 consists essentially of a with the plastic of the container 1 form fusible plastics, without the overall contour of the neck would change thereby. The electrically conductive connection would then lead over the material arrangement 7 to the vessel. 1 In this modification, a conductive layer of the container 1 from its opening 3 under the container-side edge of the material arrangement 6 passes would only not to at or below the container-side edge of the material arrangement 7 advisable because then the material arrangement 6 would badly connected to the container. 1 The order of production of the preforms of the material arrangements 6 and 7 would be merely reversed: In the first step of the preform of the material arrangement 6 and the second step of the preform would molded from the material arrangement 7 and simultaneously fused to the material arrangement 6, ie melted in yet state formed.

p0087The embodiment of the nozzle according to Fig. 14 - the container 1 and the fluid line 12 have been omitted in this illustration - 13 differs from that of FIG only in that the thinner material arrangement 6 to an inner first layer 6c made of the same. material as the thicker material arrangement formed 7 and injected into the inside, by the injection molding still molten region of the material arrangement 6 of the pointed end ago the layer 6c from one of the aforementioned diffusion barrier performance plastics, preferably PA or EVOH in Koinjektions- or monosandwich process becomes. The layers 6a and 6b form a skin layer, and the layer 6c over the entire length of the connecting piece extending thinner core layer of the second preform. The skin layer is again provided with an electrically conductive additive, while the inner layer may be 6c also provided with a conductive additive and is adhesion-modified, so that it is received by a fusion bond with the PE of the skin layer 6a, 6b.

p008813 The embodiment of the nozzle of FIG. 15 differs from that of FIG. Only in that in the material arrangement 7 during the first step a first layer 7b of one of the aforementioned diffusion barrier performance plastics, preferably PA or EVOH in Koinjektions- or monosandwich The method is injected. Here, the layer 7b extends from the end of the material arrangement 7, which is averted from the to be welded to the container 1 the end and forms the gate, more than 50%, preferably more than 90% and less than 100% of the length of the connection piece until in the flange 4, so not up to the end to be welded so that the PE of the material arrangement 7 can continue to go to the surface 10 of the container 1 when welding a firm fusion bonding. In this configuration the layer 7b need not in itself a fusion bond with the PE of the (skin) layers 7a, 7c to take the material arrangement 7 because of the layers 7a, 7c of the material structure is completely enveloped 7. Since the material arrangement 6 already has a diffusion barrier moldable plastic, the layer 7b may alternatively comprise another thermoplastic material, which is not capable of diffusion barrier, but increases the mechanical strength of the material structure. 7 In particular, it may contain a reinforcing material such as glass fibers or carbon fibers.

p0089In the embodiment of the nozzle of FIG. 16 is the material arrangement 6 from the same layers 6a to 6c, formed in the same step and made of the same materials as the material arrangement 6 of FIG. 14, while the material arrangement 7 in the embodiment of FIG. 16 also formed as the material arrangement 7 of the embodiment of FIG. 15.

p0090Alternatively, the material arrangements 14 6 and 7 in the embodiments according to FIGS. To 16 at least still have a further injected in Koinjektions- or monosandwich process layer.

p0091. The embodiment of the nozzle of Figure 17 differs from that of FIG 13 is substantially the fact that both material assemblies 6 and 7 in the manufacture of the connecting piece -, except for the conductive additive, in this case carbon black, in the material arrangement 6 - first PE exhibit and during the spraying of the material arrangement 6 in her still-molten core (the "soul"), while consisting of the layers 6a and 6b skin is already largely cured by lying at the pointed end of the nozzle injection point forth a first layer 6d, 6e is injected in Koinjektions- or mono-sandwich method. The first layer 6d, 6e has a maleic anhydride grafted PE. This is the layer 6d, 6e adhesion modified from a hydrocarbon such as gasoline or diesel oil, diffusion-blocking enabled PA or EVOH.

p0092In the core of the first layer 6d, 6e, a second layer 6c is then, after its skin layers 6d and 6e are substantially cured, but its core is still molten, injected in Koinjektions- or mono-sandwich method. This layer 6c has a PA or EVOH. If PA is injected as a layer 6c, the amino terminal group concentration is selected to be equal to or greater than 40 milliequivalents per kilogram. This is the layer 6d, 6e, not only with the PE of the material arrangement 6, but also with the layer 6c a solid cohesive melt connection. Since the container 1 PE or HDPE and the material arrangement 7 also has PE, both continue to expect a solid cohesive fusion bond to each other on when the piece is welded to the container. 1 Since the material arrangement 6 6a and 6b having a conductive additive in the layers, they go to the container 1 a not very firm fusible link. In particular, it goes to the container 1 no melting connection, if it has a conductive coating that covers the opening 3 of the container 1 and its outer side from the opening 3 to the radially outer edge of the container 1 facing the end of the material arrangement 6, wherein a continuous conductive connection of the fluid conduit 17 is not shown 12 6b is formed in Fig. 6a across the layer, to the tank 1. Even though the amino end group concentration of PA layer 6c is selected to be equal to or greater than 40 milliequivalents per kilogram, it proceeds with the (HD) PE of the container a no fusion bonding. However, the connection between the PA layer 6c and the PE layers 6a and 6b is fixed, if the adhesion-modified layers are provided 6d and 6e. Overall, however results from the dikkere material arrangement 7 is a very strong connection between the nozzle and the container. 1

p0093Although the diffusion barrier layer capable 6c included in the material arrangement 6 of the layers 6a and 6b, it is still advantageous to merge these layers 6a and 6b and to thereby connect. Because it is possible that gasoline or diesel fuel diffuses through the layer 6b between these and the layer 6c and through the diffusion and / or vapor pressure - the latter in particular at higher temperatures - the hindurchdiffundierenden fuel and by the different swelling behavior of PE and PA (PE swells more than PA) layer 6b lifted off the layer 6c.

p0094While it would be possible for the layers 6a and 6b to be modified with maleic anhydride, so that the first layer 6d, 6e could be omitted. Not adhesion with maleic anhydride-modified PE, like that of the layers 6a and 6b, but has the advantage that it can be more easily made conductive by an electrically conductive additive such as carbon black as an adhesion-maleic anhydride-modified PE.

p0095The embodiment of the nozzle of Fig. 18 differs from that of FIGS. 15 and 17, characterized in that the first layer 7d, 7e and that are injected into this injected diffusion barrier enabled second layer 7b in the material assembly 7. The first layer 7d, 7e has consequently the same material as the first layer 6d, 6e according to FIG. 17 and the diffusion barrier layer capable 6c 7b, the same material as the second layer as shown in FIG. 17. In this case the radially outer skin layer 7a of the material arrangement 7 is also by the adhesion modified layer 7d, 7e against lifting or peeling of the diffusion-blocking enabled layer 7b due to external mechanical forces, for example friction forces acting on the layer 7a protected.

p0096The embodiment of the nozzle according to FIG. 19 illustrates a combination of the layers of the material arrangement 6 according to Fig. 17 with the layers of material arrangement 7 according to Fig. 18. It united thus the advantages of both embodiments of FIGS. 17 and 18 and increases the diffusion blocking capability by the use of two diffusion barrier layers enabled, that is the two layers 6c and 7b.

p0097In cases where no high demands are placed on the diffusion barrier capability of the socket, both material arrangements may be made of plastics, not only each other but also with the reservoir 1 enter into a cohesive fusion bond, which in turn only one material arrangement, preferably the radially inner material arrangement that is thinner than the radially outer material arrangement 7, need not have the electrically conductive additive. If the container has 1 PE or HDPE, both material assemblies 6 and 7 can also comprise PE.

p0098Since only one material arrangement 6 having the conductive additive, the entire piece can cost-effectively than with single-layer design of the entire nozzle are made with a conductive additive in spite of the material costs increasing conductive additive. The material arrangement 7 has then due to lack of conductive additive provides greater chemical resistance and stress cracking resistance. Since both material arrangements 6 and 7 form a cohesive fusion bond with the container, the molten resin of the conductive material arrangement 6 can not penetrate between the material arrangement 7 and the container 1 and interfere with their communication with the container. 1