Aqueous slip and mould-release agent and process for the moulding and vulcanization of tyres and other rubber articles

Abstract: An environment-friendly aqueous slip and mould-release agent for the manufacture of tyres and other rubber articles and a process for the moulding and vulcanization of tyres and other rubber articles are described. The aqueous slip and mould- release agent contains 0.5 to 6 wt.-% polytetrafluoroethylene, 20 to 40 wt.-% mineral fillers and at least 40 wt.-% water. It is sprayed onto the inside of the tyre blank prior to the moulding and vulcanization, so that the water contained therein evaporates, accompanied by development of a slip and release agent film. Apart from the environment-friendliness and good release effect, the new slip and mould-release agent leads, despite the high water content, to a quick evaporation of the water and thus a rapid development, desired in industrial operations, of the slip and release agent film. The excellent effectiveness of the slip and mould-release agent according to the invention results in a substantial prolongation of the life of the heating membrane used for the moulding and vulcanization.

Description: The invention relates to an aqueous slip and mould-release agent (abbreviated to "release agent" hereinafter) for the manufacture of tyres and other rubber articles and a process for the moulding and vulcanization of tyres and other rubber articles using this aqueous slip and mould-release agent. According to the prior art, tyres are moulded and vulcanized by introducing the tyre blanks into a spraying booth in which they are made to rotate by means of mechanical devices. A spray-gun is introduced into these rotating blanks and distributes a release agent solution on the inside of the blanks. The overspray is removed by means of vacuum or a water wall. The blank is then moulded and vulcanized in a vulcanization press by means of a heating membrane (bag, bladder) whose task is to heat the tyre blank, effect the vulcanization and press the tyre at high pressure into negative moulds (cf. the description of this procedure in DE-PS 29 25 662, DE-OS 31 46 053 and in particular the introductory part of published European patent application 0 111 100). In published European patent application 0 111 100, to avoid the disadvantages of this procedure, a process for the moulding and vulcanization of tyres and other rubber articles is proposed in which the heating membrane is provided, prior to the moulding and vulcanization, with a cross-linked, cured, firmly-adhering elastic film of release agent that is bonded to the substrate by chemical interactions. However, the full benefit of the advantages to be achieved thereby are enjoyed only if the use of a release agent between the outside of the tyre blank and the metal mould of the vulcanization press is not necessary, as the application of release agent to the inside and outside of the tyre blank is generally one operation. Many existing tyre-production plants are so designed, however, that such an outside release agent cannot dispensed with. In addition, the coating of the heating membrane as per European patent application 0 111 100 with a film of release agent calls for a very careful procedure, as otherwise the film of release agent on the heating membrane may be prematurely damaged or detached, thus possibly causing the life of the heating membrane to be shortened and reject tyres to be produced. The internal and external spray solutions used as release agents in the conventional procedure in most cases comprise benzinous solutions of release effective substances, which contain mineral fillers and have a benzine or total organic solvents content of the order of about 70%. These release-agent solutions obviously damage the environment or require very great expenditure on apparatus if the environment is not to be polluted. Aqueous release agent solutions have thus already been proposed. The principle was that as little water as possible was used together with releases effective substances, mineral fillers, thickeners and stabilisers, so that as little water as possible has to evaporate when a film of release agent forms. Typical aqueous release agents of this type comprise, for example, about 60 wt.-% mineral fillers including thickeners and stabilizers and about 40 wt.-% aqueous silicone oil emulsion (about 5-20 wt.-% silicone oil, remainder water). Quite apart from the environmental disadvantages of silicone oils, it has been shown that, after the application of these aqueous release agents, a skin forms, as a result of which the water evaporates only relatively slowly when the film of release agent develops. US-A-3 872 038 also discloses an aqueous release agent for tyre manufacture. The aim of the invention was thus to provide an environment-friendly aqueous slip and mould-release agent for the manufacture of tyres and other rubber articles and a process for the moulding and vulcanization of tyres and other rubber articles which avoid the aforementioned disadvantages of the prior art, further use of the existing production plants being possible without major modifications. To achieve this aim, an aqueous slip and mould-release agent for the manufacture of tyres and other rubber articles is proposed which is characterized in that it contains (a) 0.5 to 6 wt.-%, preferably 1.5 to 4 wt.-%, polytetrafluoroethylene, (b) 20 to 40 wt.-%, more particularly 25 to 35 wt.-%, mineral fillers, and (c) at least 40 wt.-%, preferably 50 to 75 wt.-%, water. A further subject of the invention is a process for the moulding and vulcanization of tyres and other rubber articles in which negative moulds are pressed in a press into the blank with the help of a heating membrane under high pressure and vulcanization is effected, which is characterized in that, prior to the moulding and vulcanization, the aqueous slip and mould-release agent according to the invention is sprayed on the inside of the tyre blank and the water contained therein is allowed to evaporate, to develop a slip and release agent film. Preferred embodiments of the slip and mould-release agent according to the invention and of the process according to the invention will become apparent from the subclaims and the following description. The invention is based on the surprising discovery that, in the case of slip and mould-release agents with a high water content, skin formation largely fails to occur following application on the inside of the tyre blank, so that, because of the large surface present, the water evaporates quickly and there is thus a rapid development of the desired slip and mould-release agent film. According to the invention, polytetrafluroethylene is used in a quantity of 0.5 to 6 wt.-%, more particularly 1.5 to 4 wt.-%, as release effective substance. Polytetrafluoroethylene is known as a slip agent and lubricant and as a substance with a release effect in many fields of use. So-called polytetrafluoroethylene micro-powders (also called "polytetrafluoroethylene waxes") are particularly preferred according to the invention. These low-molecular-weight polytetrafluoroethylenes generally have a molecular weight of 30,000 to 200,000 and an average particle size of 1 to 20 µm. Their manufacture and properties are familiar to one skilled in the art (cf. e.g. "Kunststoffe", Vol. 76, 1986, No. 10, pages 920-926 and the Hoechst AG brochures relating to Hostaflon TF micro-powder, e.g. Hostaflon Information 23 dated October 1984). Commercially available polytetrafluoroethylene dispersions which contain finely dispersed polytetrafluoroethylene with a particle size of about 0.2 µm are also very suitable, particularly when combined with polytetrafluoroethylene micro-powders. The molecular weight of the polytetrafluoroethylene is normally in the range of 5,000,000 to 10,000,000 in this case. These dispersions contain, for stabilization, dispersion agents and where appropriate further additives in small quantities, such as e.g. ammonia (cf. the Hoechst AG brochures relating to Hostaflon TF 5032, e.g. Kunststoffe Hoechst Sales Information VM 394 dated October 1983). The effectiveness of the polytetrafluoroethylene can frequently be increased by also using silicone oils known from conventional release agents. Accordingly, up to about 50% of the polytetrafluoroethylene can be replaced by silicone oil, although this is not absolutely desirable from environmental points of view. Naturally, small amounts of other conventional substances with a release effect can also be used, although this is not necessary according to the invention and, at best, offers additional advantages in special applications. The mineral fillers are the materials known from the prior art for slip and release agents. Talc, kaolin and mica are preferred according to the invention. If talc and kaolin are used jointly, the weight ratio of talc to kaolin is about 1:1 to 4:1 and more particularly 2:1 to 3:1. The total mineral fillers content is 20 to 40 wt.-%, particularly 25 to 35 wt.-%, and preferably 27 to 32 wt.-%. The release agent according to the invention may also contain carbon black and/or graphite in a quantity of up to 10 wt.-%, preferably up to 5 wt.-%, the mineral fillers content being reducible accordingly in case of high carbon black and/or graphite contents. The use of small quantities of iron stearate, i.e. up to 1 wt.-%, preferably 0.3 to 0.7 wt.-%, has also proved advantageous. This clearly improves the slip effect of the release agent according to the invention. The use of wetting and dispersing agents is also desired in order to guarantee the dispersion of the solids. Non-ionic surfactants manufactured by copolymerization of propylene oxide and ethylene oxide are particularly suitable for this purpose. These are usually block polymers in which polypropylene oxide forms the central molecule section. These surfactants are commercially available under the name Pluronic PE with various molecular weights and percentage polyethylene oxide contents in the total molecule. Suitable wetting and dispersing agent quantities are up to 2 wt.-%, preferably 0.5 to 1.5 wt.-%. In order to prevent or at least reduce settlement of the solids, it is also advantageous to use normal stabilizers in quantities of 0.1 to 1.0 wt.-%. Montmorillonite derivatives such as high-purity magnesium layered silicates, e.g. smectite (commercially available under the name "Bentone", cf. e.g. Roempps Chemie-Lexikon) are suitable, among others. Biopolymers such as xanthan are also good stabilizers. It is generally undesirable that the release agent adversely affect the colour of the tyre or rubber article to be manufactured. The release agent according to the invention may accordingly contain small amounts of dyes. Quantities of up to 1 wt.-%, preferably about 0.5 wt.-%, are generally sufficient. Depending on the product conditions in question and the desired product properties, the release agent according to the invention may also contain other conventional additives. However, these are not essential to the invention, and therefore need not be discussed in detail. As already mentioned above, a high water content is an essential feature of the release agent according to the invention, and it accordingly contains at least 40 wt.-%, particularly at least 60 wt.-%, and preferably 65 to 75 wt.-%, water. It has been shown that only very small quantities of the release agent according to the invention need be used to produce the desired effect. It is thus generally sufficient to introduce it into the tyre blank in such quantities that the solids content remaining after the evaporation of the water is about 3 to 15 g and particularly 3 to 10 g per car tyre (with truck tyres, the solids content increases according to the greater surface to be treated). This economical consumption, advantageous in itself, leads to the further advantage that the manufactured tyre has a better quality, i.e. runs truer, because it has smaller quantities by weight of substances that may possibly be unevenly distributed on the inside of the tyre. In order to guarantee the large surface needed for rapid evaporation and distribute evenly the relatively small quantities of release agent, the inside spray solution according to the invention is applied by the so-called air-mix process with the inside spray solution in constant circulation, in order very largely to avoid a settlement of the solids. Alternatively, it can also be applied by means of air atomization. The spraying of the release agent according to the invention under high pressure leads to the development of an open film and thus permits the desired rapid evaporation of the water. The inside spray solution according to the invention dries well, so that drying times of about 6 to 12 minutes at temperatures in the range 18 to 22°C are generally sufficient. The release agent according to the invention produces a good slip effect, good venting effect and good release effect. Overall, the release agent according to the invention is so effective that the life of the heating membrane is substantially prolonged, which naturally leads to simplifications and cost advantages in the production process. The release agent according to the invention can be sprayed without problems and evenly with minimal plant contamination. Cleaning the plant poses no difficulties. Finally, the agent according to the invention is characterised by ease of stirring and does not lead to bonding problems in the tyre. Apart from the use of the release agent according to the invention and its application in a suitable manner (see above), the process according to the invention is implemented in conventional manner, so that further explanations are to that extent unnecessary. However, it has surprisingly been shown that the process according to the invention can be combined in an extremely advantageous manner with the process known from the published European patent application 0 111 100, i.e. the use of heating membranes coated with a film of release agent in combination with the release agent according to the invention produces additional advantages in terms of the quality of the manufactured tyres and the life of the heating membrane. Example 1 An aqueous inside spray solution comprising 19 wt.-% talc, 7 wt.-% kaolin, 5 wt.-% graphite, 1.7 wt.-% polytetrafluoroethylene micro-powder, 0.5 wt.-% iron stearate, 1.3 wt.-% non-ionic surfactant (Pluronic), 0.5 wt.- % dye and 65 wt.-% water was prepared by intensively mixing all the constituents and used in a production test in which about 10,000 car tyres were manufactured. It was applied to the inside of the tyre blanks by the air-mix method with constant circulation. The solids content of the inside spray solution applied per tyre was 3 to 10 g. The performance of the release agent according to the invention was very good. The same applied to the quality of the manufactured tyres. Furthermore, some 600 demouldings were carried out - a substantial and totally unexpected increase compared with the figure obtained using conventional release agents. The spraying of the inside spray solution proceeded without problems and with minimal contamination. The expenditure on cleaning the used plant was also minimal. Example 2 An aqueous inside spray solution comprising 32.63 wt.-% talc, 6.50 wt.-% graphite, 2.40 wt.-% polytetrafluoroethylene micro-powder, 1.95 wt.-% non-ionic surfactant (Pluronic), 2.00 wt.-% silicone oil in form of a 30% aqueous emulsion, 0.26 wt.-% Bentone and 54.26 wt.-% water was prepared by intensively mixing all the constituents, and used in a production test. It was applied to the inside of the tyre blanks by air atomization. Like in Example 1 again excellent results were achieved.

Claims: Aqueous slip and mould-release agent for the manufacture of tyres and other rubber articles, characterized in that it contains (a) 0.5 to 6 wt.-%, preferably 1.5 to 4 wt.-%, polytetrafluoroethylene, (b) 20 to 40 wt.-%, particularly 25 to 35 wt.-%, and preferably 27 to 32 wt.-%, mineral fillers, and (c) at least 40 wt.-%, particularly at least 60 wt.-%, and preferably 65-75 wt.-%, water. Slip and mould-release agent as in Claim 1, characterized in that the polytetrafluoroethylene is polytetrafluoro-ethylene micro-powder, combined where appropriate with a polytetrafluoroethylene dispersion. Slip and mould-release agent as in Claim 1 or 2, characterized in that it contains, in addition to polytetrafluoroethylene, silicone oil as a substance with release effect. Slip and mould-release agent as in one of Claims 1 to 3, characterized in that it contains talc, kaolin and/or mica as mineral fillers. Slip and mould-release agent as in one of Claims 1 to 4, characterized in that it contains up to 10 wt.-% carbon black and/or graphite. Slip and mould-release agent as in one of Claims 1 to 5, characterized in that it contains up to 1 wt.-% carbon black and/or graphite. Slip and mould-release agent as in one of Claims 1 to 6, characterized in that it contains up to 2 wt.-% non- ionic surfactant as wetting and dispersing agent. Process for the moulding and vulcanization of tyres and other rubber articles in which negative moulds are pressed, in a press, into the blank with the help of a heating membrane under high pressure and vulcanization is effected, characterized in that , prior to the moulding and vulcanization, the aqueous slip- and mould-release agent according to one of Claims 1 to 7 is sprayed on the inside of the tyre blank and the water contained therein is allowed to evaporate, accompanied by development of a film of slip- and release agent. Process as in Claim 8, characterized in that the inside of the tyre blank is sprayed with such a quantity of slip- and mould-release agent that the solids content remaining after the evaporation of the water is 3 to 15 g and preferably 3 to 10 g per tyre. Process as in Claim 8 or 9, characterized in that the aqueous slip- and mould-release agent is applied to the inside of the tyre blank by the so-called air-mix process, or by air atomization.

Inventors: WAGNER HERBERT, WAGNER, HERBERT
Applicants: RHEIN CHEMIE RHEINAU GMBH
Application year: 1991
Main classification: B29C33
IPC codes: C08L27, B29C35, B29L30, C08K3, B29C33, B29K21, B29K105