DE2835202A1 - Moulding glass articles into a blank - Google Patents

Abstract

The moulding is effected by contact with the surface of a blowing mould without relative rotation between the glass and the moulds. Specifically one of the surfaces defining the moulding cavity and forming the glass is a solid layer consisting of a solid lubricant dispersed in an organopolysiloxane as binder, and is coated with a solid layer consisting of (i) non-colloidal graphite in sufficient amt. to provide a good demoulding of the glass wrt. the layer, (ii) polysiloxane and (iii) <=15 wt% of a hardener for the siloxane. The coating provides improved surface protection and lubrication during glass moulding while not contributing to the atmospheric pollution.

Description

The invention is in the field of glass manufacture

and is particularly concerned with an improvement in the glazing cores Use of hot iron or hot metal molds is not recommended.

Glass objects are not used in the glass industry after one of two analogue techniques. That means the shaping can be done according to the technique the pasted forms are used or according to the non-analog process which hot iron or hot metal molds are used. The latter process is referred to herein as the hot metal mold technique.

Regarding the difference between the pasted form technique and the hot metal mold technique and a description of the techniques for Forming of glass articles is referred to "Glass Engineering Handbook" by E.B. Shand, MoGraw Hill Book Company 1958 and the Handbook of Glass Manufacture, Vol. 1, Ogden Publishing Company 1953, referenced. The pasted form technique includes Rotational speed differential between the mold and the glass, i.e. the pasted shape and the glass rotate relative to each other, with the glass in the Form circulating through the use of water in a moist state. The paste itself is usually some form of adherent carbon that is porous and thereby is able to absorb water, It is commonly said that using both technique Pasted form the glass molded against a vapor boundary layer that acts as an icing will. One of the properties of glass objects, according to the technique made with a peened shape is that they are a result of the rotation of shape and glass do not have a molded seam relative to one another. In U.S. Patent 2,573,337 is the use of a cured organopolysiloxane on a pasted form when e.g., glass bulbs are made on a piston or belt machine.

In the non-analogous technique of forming glass objects through the use of hot metal molds, molten glass becomes malleable first Shaped into a parison or blank by touching the glass with a glass contact or glass-forming, cavity-defining surface of a parison or blank mold brings into contact and then this parison or blank in a blow mold by contact with a glass-forming or glass-contacting, cavity-delimiting surface in transferred the finished item. The shape of the parison or blank and the Shaping of the finished object from the parison or blank takes place without rotation of shape and glass relative to each other. Examples of the glass forming devices, which work with hot metal molds are the IçS operated either by a blow-and-blow process or oinem press-and-blow process as well as the Owens glass forming apparatus. As with the Te-chulk A steam cushion cannot be used in a hot metal mold, is generally considered drawn that with this molding technique the glass with the glass forming, the cavity delimiting surface of the form -in Touch comes. The subject @@ un is the definition of the properties, e.g. the surface that delimits the bright space aware of a hot metal mold for the proper execution of the molding process. The june surface, i.e. the one that touches the glass or forms the cavity delimiting the cavity Curses must have properties, such as suitable heat transfer.

suitable separation of glass, so that undesired quality damage be avoided. The hot motor molds must also run hot enough to cause sudden Avoid cooling the glass, otherwise cracks will appear. The hot metal molds Also, the Laufon must not be too hot, because the glass then tends to adhere to the cavity delimiting Glue surface of the mold, resulting in a finished product with quality defects, which are typical for this gluing leads. In an attempt to complete the overall work of the It is common practice to improve forming the glass using hot metal molds Practice making shapes with materials such as oil, graphite, grease, sulfur, rubber, to impregnate or coat old shoe heels and the like in order to To facilitate separation or detachment of the glass. This kind of brushing or Xmpregnating has its shortcomings and limitations that can be quickly recognized. E.g. the impregnation or painting generally based on the subjective evaluation of independent Glass machine operators, which is not conducive to reliability is. Another disadvantage of this technology is that these materials in a volatile organic carrier, these carriers after contact evaporate with the hot metal mold and the whole molding surface with Pre-contaminate incineration products.

In the CS-PS 128 236 with the title "Schmicm @ ittel for glass forms" and the report of this patent in Chemical Abstracts, Vol. 70, 1969, page 195, Abstract-Mr, 108868r, is a glass molding lubricant (lubricant) made from an organopolysiloxane and celloidal graphite. The report in Chem. Abstr. Vol., 60, abstract no. 763D, titled "Coatings T.Thich Prevent Sticking of Molten Glass to a Mold ", in which a collidal graphite and a colloidal graphite Silicone are disclosed. / is a stable suspension of finely ground natural or artificial graphite, dispersed in a liquid vehicle and usually becomes as a dispersion or suspension of a graphite concentration of about 10-20 Weight percent brought to market. The particle size of this colloidal graphite is on the order of a micron or less; it is to be noted that this is an extremely small material with a large surface area. Wio from the following Examples can be seen, the use of colloidal graphite is not so far satisfactory than the wear rates using such a material Stand in no comparison to the need in the glass industry when the hot metal molding technique is applied and high quality glasses are used at high speeds made to graze at low cost. Regarding a description of colloidal graphite is referred to Kirk-Othmer, Encyclopedia of Chemical Technelogy, Vol. 4, 1964, p. 325.

In U.S. Patent 3,347,650, some of the drawbacks are recited Shapes exposed. In this Putentschritf a lubricant is in the form of a Proposed solid film on the form, for example from lead monoxide powder in a mixture is formed with graphite. The Facbaann. will quickly learn that one Lubricant film is unsuitable because of the toxicity of lead.

DE-OS 2 303 861 relates to a sprayable Scllmierw bz0 Lubricant for glass container molds that are sprayed on after each molding cycle got to. In the case of the sprayable lubricant, the graphite is in finely divided solid polymer used, the ratio of graphite au organic polymer about 1: 0.1 to 1:15. However, the OS does not show that a permanent or solid lubricant film on the mold as a glass-contacting or glass-forming, cavity-delimiting surface is formed, as according to the OS, the lubricant after Is sprayed on every cycle.

The invention is based on the object of a method for molding of glass according to the technique with hot metal molds, in which the forming stages proceed without rotating the glass and the mold relative to each other, to create, with a glass release agent or lubricant on the cavity-delimiting surface the form that does not pose any toxicity problem. The procedure should be with high production speed and high quality Products It should also not run the risk of pollution at low cost by releasing larger amounts of contaminants into the environment.

The task is desired by a method for shaping a glass object, in which a malleable hot glass by contact with a glass forming, a Cavity-delimiting surface of a hot metal blank mold into a blank is formed and the blank by contact with a glass forming, a cavity limiting surface of a blow mold is transferred into the object, wherein the blank and article molding without rotation of the glass and mold relative is made to each other and one of the glass-forming, cavity-delimiting surfaces with a solid layer of a solid, in an organic @ polysiloxane binder dispersed lubricant is provided, characterized in that the glass-forming, cavity-delimiting surface of the blank mold by applying a dispersion of substantially non-colloidal graphite in an amount sufficient to the Layer to give glass-releasing property, an organopolysiloxane and up to about 15 percent by weight, based on the organopolysiloxane, of a siloxane curing promoter, and hardening is provided with the solid layer.

The invention provides an improved method for the formation of Glas Gegenstailden created in which the glass after the Tochnik with a hot metal mold and the surface defining the cavity Blank mold with a layer of a glass-contacting, cavity-limiting lubricant or glass release agent in the form of a solid film is provided by this layer the disadvantage of the prior art is eliminated by providing the desired Possessing properties, taking on improved production capacity in glass molding Maintaining better quality at lower cost leads and, if any, then causes minimal contamination in the molding areas.

So it is an improved method of forming glass objects, at which malleable hot glass to a blank or egg by touch with a glass-forming, cavity-delimiting surface of a hot metal blank or Parcel shape is formed and the blank is then molded into a finished glass article, e.g. Glass container, by contact with a glass-forming, cavity-delimiting surface is overfilled in a blow mold. The improvement consists essentially in: that as the glasformondo or glass-contacting cavity-delimiting surface of the hot metal blank mold a layer or film of a solid slide or Glass cleaning agent is used, the layer being essentially non-colloidal Graphite dispersed in hardened thermosetting organopolysiloxane binder and the graphite is present in an amount sufficient to detach the layer from glass or to confer separating property.

That is, instead of forming the parison or blank in one Külbel- or loop shape through contact with the cavity-delimiting metal surface of the According to the invention, this surface delimiting the mold space is given a shape with a layer of lubricant provided in the form of a solid film. This layer is made by applying a dispersion made of non-colloidal graphite in an organic solution of a solvent-soluble, further curable, thermosetting organopolysiloxane on the cavity delimiting Metal surface of the forra made to form a layer delimiting the cavity to create a free surface for contact with glass during glass molding is used. The non-colloidal graphite contemplated here has a weight percent particle size distribution where practically all, e.g.

95 percent by weight of the particles are over a miicron in size in contrast to colloidal graphite, in which practically all particles or at least the majority, e.g., 50 to 70 percent by weight, are less than 1 micron in size.

According to a further preferred embodiment of the invention in addition to the blank mold, also the blow mold with a layer of a solid film of lubricant, in the same way as described above, provided, the particle size of the graphite in the layer on the blow mold is not larger than the particle size the graphite used to form the layer on the blank mold; preferably in order to obtain an extremely smooth surface on the glass object, graphite a smaller particle size for the production of the layer on the blow mold than for the production of the layer used on the blank mold.

As stated generally above, the lubricant layer is used in Ferm a solid film on the blank mold or the blow mold produced by application a dispersion of the graphite in a solution of the thermosetting, further hardening Organopolysiloxane in organic solvent on the contour of normally glass-contacting, cavity-delimiting metal surface of a conventional blank or Blow mold. When machining the cavity-delimiting metal surface of the blow mold as well as the blank shape for accepting the dispersion are preferably conventional techniques applied. According to a preferred embodiment, the mold surface is through Sandblasting and priming processed, when priming, common primers are used used, e.g., the phosphates; Particularly preferred primers are the amino-organo-siloxane compounds. Examples of suitable primers are those described in US Pat. No. 3,088,847 and US Pat in GB-PS 952 992 are disclosed. Particularly preferred primers are Amino-organo-silicone compounds, as described in GB-PS 952 992, Table 1, to be removed are, e.g. the amino silicone D as well as combinations of these amino-organo-silicone compounds with the epoxy compounds listed there. The application of the dispersion of the graphite in the solution of the further curable thermosetting curable organopolysiloxane in organic solvent can also be made using conventional techniques as by brush or spray coating. It should also be noted that, if herein of the graphite particle size the talk is about the Size to the size of the graphite added to the organopelysiloxane solution for formation of dispersions. After applying the dispersion to the end of the hollow rim Metal surface of the blow mold and after evaporation of the solvent is the finished Curing of the organopolysilexane carried out so that a layer in Ferm one solid lubricant film is formed in which the graphite in the thermosetting hardened Organopolysiloxane binder is dispersed or bound and a void-delimiting contact with the glass Surface has. The solid lubricant layer that defines the contour and configuration of the original void-delimiting metal surface generally has a balanced thickness.

The film, on the one hand, is not so thick that it will remain in use during use and glazing peeled off, on the other hand not so thin that the film due to breakage failed prematurely. It has been found that a thickness of the finished layer in on the order of about 0.0508 to about 0.0889 mm, preferably about 0.0508 to about 0.0762 mm, e.g. from about 0.0635 to 0.0762 mm for excellent results in the case of the blank or parison shape. The blow mold has a film thickness of about 0.0254 to 0.050S mm, preferably from about 0.0254 to about 0.0381 mm, is suitable. Some general considerations regarding shapes and application of solid sliding or. Lubricants are the work "Solid Lubricants" by M.E. Campbell at al, NASA, Washington, D.C. May 1966, pages 7 to 17 to be found.

The organopolysiloxanes that can be used are the solvent-soluble ones further curable, curable, thermosetting organopolysiloxanes. These materials are known. They are the hydrolysis and condensation products of the hydrolyzable Silanes, i.e. it is the hydrolysis and condensation products of silanes that carry hydrolyzable groups, e.g. halogen, such as chlorine, or alkoxy groups, their Alkyl radical have 1 to about 5 carbon atoms. The preferred thermosetting, solvent-soluble, further curable organopolysiloxanes are organopolysiloxanes in which the organic The remainder are lower alkyl groups, e.g. C1 to C alkyl groups or phenyl groups. These Compounds can ize by hydrolyzing and condensing a hydrolyzable Silane can be produced or they can be the hydrolysis condensation products of Mixtures of hydrolyzable silanes, or one can simply use the organopolysiloxanes Mix in 2 or more further curable thermosetting organopolysiloxanes. The preferred Organopolysiloxanes are the heat-curable, curable, further curable (post-curable) Methylphenylsiloxanes. It is known that these further hardenable (post-hardenable), thermosetting organopolysiloxanes are described by their R: Si ratio, where R is the moles of organic resi that are directly bound to the silicon atoms, designated. In the preferred embodiment of the method according to the invention Organopolysiloxanes with an R: Si ratio of 1s1 or above to below are used used about 2: 1. The organopolysiloxanes with a ratio greater than 2: 1 are oils and not the next hartbaron.

hits-curable polysiloxanes, which are preferably used in the execution of the According to the invention are used. Particularly good results will be when using a further curable thermosetting organopolysiloxane having an R: Si ratio from ot about 1: 1 or above to about 1.6: 1, i in particular from about 1.2: 1 to 1.6: 1 obtain.

As noted, the preferred organopolysiloxane is a methylphenylsiloxane. As can be seen from the R: Si molar ratios above, these become siloxanes preferably produced by hydrolyzing the appropriate hydrolyzable silanes, to get the desired R: Si ratio.

For example, these materials are hydrolyzed and condensed a condensable and hydrolyzable monomeric mixture of methyltrichlorosilane, Phenyl trichlorosilane and dimethyldichlorosilane can alternatively be obtained through Hydrolysis and condensation of methyltriethoxysilane, phenyltriethoxysilane and dimethyldiethoxysilane getting produced. Other alkoxysilanes can of course also be used, as indicated above and halosilanes as well as mixtures thereof can be used. Also, how can mentioned above, the R: Si ratio could be 1: 1, indicating that the organopolysiloxane may be a lower alkyl polysiloxane, e.g.

Methylpolysiloxane, made from methyltrichlorosilane or methylaikoxysilanes such as methyltriethoxysilane or the organopolysiloxane can be a phenylorganopolysiloxane be made from e.g. a phenyltrichlorosilane or a1 phenyltrialkoxysilane, such as phenyltriehoxysilane or mixtures thereof.

The organic solvent for the further curable, thermosetting (curable, thermosettable, hardenable) Organopelysiloxane used to form the solution can be used and in what time the graphite is dispersed9 can easily selected by a professional. Examples of suitable solvents are Ethyl alcohol, propyl alcohol, benzene, ether, ketones, e.g. acetone, mixtures thereof, Mixtures of e.g.

White spirit, iscbutyl acetate and ethylene glycol monomethyl ether, and aromatic Solvents such as xylene and toluene.

Particularly good results are obtained when using xylene. The concentration of the further curable, thermosetting organopelysiloxane in the organic solvents can also be quickly determined by a person skilled in the art, but particularly good work is achieved by using e.g.

about 10 to 35 percent by weight, in particular about 25 to 35 percent by weight Organopolysiloxane solutions achieved. About 30 percent by weight is very particularly preferred Organopolysiloxane solution in xylene.

Dry parting non-colloidal graphite becomes with the solvent intimately contacted to create a dispersion of the graphite in the solvent to obtain. The weight ratio of graphite to solid organopolysiloxane is preferred on the order of about 0.8: 1 to about 2: 1, in particular. about 1: 1 to 2: 1. Particularly good results are achieved when using a ratio of about 1: 1 to about 1.75: 1, in particular 1.5: 1. With Relation to the particle size of the graphite is attached to the graphic representation referenced. It's a common semi-logarithmic curve different graphites with weight precent @ eilchen (ordinatenaches), whose D @@@@@@ knives is larger than a given particle diameter (@@ szissenachse) in Hikron. For reasons of expediency, there are also ordinate lines in the graphic representation (dashed), the points for 90 weight percent and the points for 10 percent by weight of particles above the specified particle diameter of the Connect curves B to F. (In the following these lines are called "Lines of 90 and 10 weight percent larger particles"). The curves are based on a Coulter Counter particle size analysis and, if used herein, on the Particle size is referred to as a Coulter Counter particle size analysis meant. The graphite, surprisingly the most beneficial for forming the solid lubricant film layer on the glass-contacting or glass-forming, cavity-delimiting Area of the blank shape is used, is a graphite of a particle size distribution curve, those between the 90 weight percent and aen 10 weight percent in the area falls, which is approximately limited by (i) curve B, (2) curve F and (3) the line the 90 percent by weight and (X) of the line of 10 percent by weight larger parts, and preferably in the area which is approximately limited by (1) curve C, (2) curve E, (3) line of 90 percent by weight and (4) line of 10 percent by weight larger Particle. Particularly good results are achieved if you have a graphite Particle size advantage curve sets in, which falls within the range that is approximately limited is given by the curves B and F, preferably about through the curves C and E, a graphite with a particle size distribution k @ rve of about curve D is particularly preferred. Above is generally described in the graphite, which is used for the layer of solid lubricant film on the blank mold. In the embodiment of the method according to the invention in which the blow mold is likewise with a layer of solid lubricant film made of graphite, dispersed in the thermosetting, hardened organepolysiloxane is provided, graphite is used, which is no larger is preferably smaller than the graphite used to form the layer on the blank mold was used.

If e.g. the graphite, which is intended for the layer on the blow mold has a particle size larger than that corresponding to curve D, it is expediently, the surface of the layer on the solid lubricant film by rubbing with Smooth sandpaper before use.

The dispersion of the graphite in the solution of the further hardenable, thermosetting Organopolysiloxane in organic solvent applied to the cavity delimiting Metal surface of the blank or the blow mold is applied, can also be further Including materials, e.g. materials that increase the rate of cure the organopolysiloxane increase. In this case, the hardening promoter will be in a Amount used sufficient to promote hardening.

For example, hardening promoters are used in amounts below about 15 percent by weight, based on organopolysiloxane solids used. Suitable curing accelerators let yourself be by easily determined by a professional. There are materials which are usually used for curing further curable organopolysiloxanes. Particularly good promoters. known to be used for curing organopolysiloxanes are used are the melamine-formaldehyde precondensate resins, the alkylated Melamine-formaldehyde precondensation resins are included here. These alkylated Melamine-formaldehyde resins are melamine-formaldehyde resins that are made with lower alkyl alcohols or mixtures thereof, e.g., alkylated with C1 to C5 alkyl alcohols. One such suitable resin is a butylated melamine-formaldehyde precondensate (Koprez 70-10 de Koppers Chem. Comp.).

For example, if the melamine-formaldehyde precondensate resins for Promoting the hardening of the organopolysiloxanes are used in particular good results using from about 0.5 or 1 weight percent to about 14 or less 15 weight percent resin, based on the organopolysiloxane solids obtained. Excellent Results with no detrimental impact on the rate of wear or performance During the glass forming process, about 13 to 14 percent by weight of melamine-formaldehyde precondensate resin, achieved based on organopolysiloxane solids. Other particularly suitable hardening promoters are the phosphonic acids such as those described in US Pat. No. 3,654,058, with phenylphosphonic acid it is particularly preferred, for example, in an amount of about 5% by weight on organopolysiloxane.

In addition, the dispersion can contain customary auxiliaries, e.g. common thixotropes that are used to improve the flow properties of the dispersion to adjust that they have the best flow behavior for the method, after which they are applied to the metal surface of the mold that delimits the hollow shape should have. These thixotropes are used in fairly small amounts, e.g. below about 2 to 3 percent by weight based on organopolysiloxane solids. The thixotropes are known. A suitable material is hydrogenated castor oil (Thixin R from Baker Ca Der Oil Comp.). Further suitable thixotropes are brought onto the market by Kelcc CompO under their trademark "Soloid" Products.

After the dispersion of the graphite in the organopolysiloxane solution applied to the cavity-delimiting surface of a conventional blow mold or blank mold the solvent is allowed to evaporate and then the organopolysiloxane is heated at a sufficiently high temperature long enough to turn it into a hard hardened transfer heat-cured organopolysiloxane. This results in the formation of the Layer or coating, which is a glass-contacting or glass-forming, cavity delimiting Has surface that acts as a solid lubricant film and the layer of which is graphite dispersed in the cured organopolysiloxane binder. Of course contains the binder if a hardening promoter and / or a thixotrope is used has been, even these materials. In general there is at least a binder about 80, for example at least about 85 weight percent of the thermoset cured organopolysiloxane.

Although the invention is sufficiently explained above to provide a To enable one of ordinary skill in the art to practice the invention Several examples are given which further the invention with respect to blank shapes explained.

For the sake of simplicity, the designation "R-630 resin" for the solution of a curable bit-curable organopolysiloxane resin (60 weight percent resin solids in xylene) used; the organic groups of Resin are methyl and phenyl, It is a methyl-phenyl-polysiloxane, with the ratio he organic groups, i.e. the ratio of methyl and phenyl to Si atoms (R: Si ratio) about 1.4 is ur, the ratio of methyl to phenyl on a mole basis about 3.3: 1 is. Both values are based on analysis results. In addition, for those in the Examples used graphite abbreviations used 007-S is a graphite one Particle size analysis corresponding to curve G, A-98 is a graphite, its Particle distribution curve corresponds to curve D and UC-38 is a graphite which corresponds to the Curve 1D corresponds. These curves represent the averages of two separate Coulter Counter particle size analyzes for each graphite.

The Coulter Coanter analysis was carried out using a Model T from Coulter Electronics Inc. manufactured. The technique used was general usual at the sieves (multiple apertures) of 400, 140, 50 and 30 microns and one electrolyte from about 4 grams of lithium chloride in 100 milliliters of a solution of lithium chloride was used in methanol. The 007-S and the A-98 graphite were made by the company Asbury Graphite Mills Inc. and No. 38 from Union Carbide Chem. Comp. based. These graphites can broadly be called electric furnace or synthotic graphites and are available in the form of dry, divided material. In the examples, the cure promoter or catalyst is referred to as Koprez 70-10. It is a butylated melamine-formaldehyde precondensate resin, dissolved in an organic Solvent, 80% resin solids in n-butyl alcohol. The resin is from the Koppers Chem. Comp.

put on the market.

In the following examples, the blank shapes were made by the application made of a vertical reciprocating spray. I.e. the divided forms were closed and the surfaces delimiting the cavities by means of a vertical Sprayed over 3600 reciprocating spray nozzle0 More specifically, it became a Drive provided that was pneumatically movable in the vertical direction, and this Drive carried a vertically arranged tubular body, at the lower end of which one 360 ° spray nozzle was arranged. The cavity parts of the mold were sprayed by the anhydrous dispersion, as described in the examples, through the spray nozzle the pipe body was fed during spraying, while the drive was pneumatic was moved upwards. Before spraying, the void-defining surfaces were the shape first sandblasted in the usual way and with a usual primer primed. The priming was done with the special material AP 132 from Unien Carbide Corporation. The shapes were after Curing the organopolysiloxane with a layer of graphite dispersed in the cured organopolysiloxane binder, on a glass-forming or glass-contacting, cavity-delimiting surface and were used as blank shapes in a semi-technical Plant starting with I.S. Machines for forming glass bottles, generally with GB-121 Glass bottles designated, inserted.

In the I.S. Machines became the so-rumored hot metal molds used, which were operated in a blow-blow process, although of course a press-and-blow process is also suitable; were. When forming @ became a malleable hot glassware to a parison or blank in a parison shape without rotation of Glass and mold formed relative to one another and then the parison in one Glass shape formed into the finished bottle, also without turning the shape and glass relative to each other. In these examples, the neck ring and the bottom plate not provided with the layer of solid lubricant film, but of course that too can happen.

Finally, the rate of wear or the degree of wear was determined as well as the service life of the forms-n is determined.

The degree of wear is a parameter that is used to evaluate the quality the layer of solid lubricant film was used. The degree of wear is expressed as a loss of layer thickness per unit of time in millimeters per hour.

The higher the number, the greater the degree of wear. the Blank shapes were coated and the thickness of the coating or layer was made fixed lubricant film at six points, three on each side of the open Shape.

The points were 1.45 centimeters from the top, 2.54 centimeters away from the bottom and roughly in the middle of the blank mold. The same points were made used for thickness measurement after wear by using the hot metal mold for glass molding had taken place. The coating thickness where was determined using the magnetic Thickness measuring device, Type 7000 from H. Tinsley and Comp. Ltd., Great Britain, performed. The shapes were then put into the glass forming machines, here the I.S. bottle forming machine, installed and bottles manufactured until they were no longer of the desired quality i.e. until the mold coating failed. The failure of the mold coating is the point where the metal of the mold is exposed. This exposure typically causes Gluing the glass to the metal surface of the mold, causing a defect in the glass surface evokes. The blank mold was then removed from the machine and the coating thickness measurement was taken made at the six points. The decrease in the coating thickness at every point, divided by the time the mold was in use was the degree of wear at this point.

The average of the six degrees of wear on the various.

Setting the blank shape is the degree of wear of the coating material or the layer of solid lubricant film of the particular shape. The total degree of wear the specific layer of solid lubricant film that is reproduced / given, calculated result from the average of the degrees of wear of each individual shape that comes with this Material was coated and running in dc 'glass forming machine. The number of ver turned blank molds with a given coating material was always higher than two, usually four.

The life of a mold with the layer of solid lubricant film depends of course on the degree of wear and aucb. on the thickness of the layer away. A very important additional factor regarding the service life is the uniformity, in which the glass is placed in the mold, i.e.

in order to obtain service life times from the degree of wear, it is extremely important that the glass is brought into the shape evenly, the shape is evenly fed to localize the wear and tear on an area; to exclude.

Such a localization is, of course, an irrational one Lifetime that does not match the properties of the layer of solid lubricant film corresponds, as only a small spot or area can indicate that the service life has ended. However, if the mold was loaded evenly, it was a significantly longer service life achieved. The one shown in the examples Lifespan are the areas of certain shapes where the glass quality has deteriorated.

Example 1 (A) It makes a dispersion by intimate mixing of about 150 grains of xylene, 150 grams of the organopolysiloxane resin solution R-630, 135 grams of No. 38 graphite and 15 grams of the butylated melamine-formaldehyde resin solution Koprez 70-10 manufactured. The dispersion of the graphite in the solution of the further hardenable Organopolysiloxane in the organic solvent and the added butylated one Melamine-formaldehyde precondensate was intensively mixed and applied to the cavity delimiting Metal surface of the blank molds sprayed on. After evaporation of the solvent the system was cured for one hour at about 343 ° C ° C, causing curing of the further curable organopolysiloxane resin took place and each shape with a Layer of a solid lubricant film in which the graphite in the hardened Binder was dispersed, was provided. Instead of the metal surface, this one was used solid layer the glass-forming cavity-delimiting surface of the blank mold. The forms were then used as blank shapes in a 1.5 machine and showed a average wear rate of about 0.00289 millimeters / hour (0.114 mils / hour) and a life time of 11 to about 25.5 hours.

(B) The procedure described under (A) was repeated, except that the butylated melamine-formaldehyde resin was omitted and the curing in a cycle of about an hour at 9300, then one hour at 2600C and two Hours at about 3160C. The blank shapes were then made on the I.S. machine tested and showed a wear rate of about 0.00307 millimeters / h (0.121 mil / h) and a life of about 22 to 33.5 hours.

(C) The procedure described under (A) was repeated, except that the R-630 has been replaced by a new batch with a slightly lower viscosity would have. A wear rate of about 0.00316 millimeters / hour (0.085 mils / hour) and a service life of about 26 to 29 hours was found.

Example II (D) The procedure described under Example I- (B) was followed repeatedly except that A-98 graphite was used in place of No. 38 graphite being the weight ratio of graphite to orgailopolysiloxane solid remained practically the same, i.e. about 1.5: 1, and about 0.8 grams of a thixotrope (THIXIN R from Baker Castor Oil Comp.) Were added. The shapes showed an average wear rate of about 0.00211 millimeters / h (0.083 mil / h) and a service life of around 24 to 27.5 hours in the test facility.

(E) The procedure of Example I- (A) was repeated, except that that instead of graphite NrO 38, graphite A-98 was used, namely in a weight ratio of about 1.5: 1 graphite to organopolysiloxane, and that the Dispersion contained 0.8 grams of THIXIN R. The degree of wear of these shapes was about 0.00183 millimeters / hour (0.072 mils / hour) and demonstrated lifetime in the pilot plant from about 12 to 32 hours.

(F) The procedure of Example II- (E) was repeated; the forms showed a wear rate of 0.00173 millimeters / h (0.068 miljh) and a service life iii the test facility from 22 to 27 hours.

(G) The procedure of Example II- (F) was repeated except that the amount of butylated melamine-formaldehyde resin is reduced to a tenth became. That is, Example II- (F) was repeated using the graphite A-98 in FIG the same amount as used there, but only about 1.5 grams instead of 15 grams the solution of the butylated melamine-formaldehyde resin. These forms had one average wear rate of 0.00269 millimeters / h (0.106 wil / h) and elne Service life on the test facility of around 13 to 2595 hours.

Example III (H) The procedure of Example II- (E) was repeated, being the same weight ratio of graphite to organopolysiloxane solid was complied with, but graphite 007-S was used instead of graphite A-98. These molds had an average wear rate of 0.002553 millimeters / hour (0.1005 mil / h) and a life of about 14.5 to 19.75 hours.

Example IV The procedure according to Example II-CE), resulting in an average Wear rate of 0.00183 millimeters / h (0.072 mil / h) was repeated except that the weight ratio from graphite to organopolysiloxane was varied from 1.5: 1. Attempts at a weight ratio of about 1: 1 resulted to a wear rate of 0.002946 / h (0.0116 mil / h) and a life in the Pilot plant from 15 to 22.5 hours. Try at a weight ratio of Graphite to organopolysiloxane solids of about 1.75: 1 resulted in a degree of wear of about 0.002667 millimeters / hour (0.105 mils / hour) and a life of about 25.25 up to 30.5 hours This shows the surprising improvement using a weight ratio from graphite to organopolysiloxane solid from 1.5: 1.

Example V (I) A curable, thermosetting further curable organopolysiloxane with methyl and phenyl groups as organic radicals in the ratio of methyl to Phenyl of about 3.6: 1 and a molar ratio of the organic radicals, i.e. methyl plus phenyl to silicon atoms (R: Si ratio) of about 1.4 was made from about 2.98 moles of dimethyldiethoxysilane, about 2.31 moles of methyltriethoxysilane, and about 2.27 moles of phenyltriethoxysilane. These starting materials became approximately 19.7 moles of water and then about 20 ppm HO1, based on the silane used, added. The mixture was heated to boiling under reflux and four hours at this temperature held.

Before reaching reflux, the two-phase mixture went into one single phase over. After that the solution was through Remove from some ethanol by-product and water concentrated by distillation and then further heated to pre-cure the resin without gel formation. This procedure is from the US-PS 3 389 121 known. Then xylene was added to obtain a solution that was about Contained 80% organopolysiloxane solids. After adding xylene and using a Dean-Starke trap, the system was refluxed for four hours with the Water was removed by means of the Dean-Starke trap throughout the period. The solution of the thermosetting, further curable organopolysiloxane was then on Cooled to room temperature and diluted with more xylene, so that a 60 percent by weight Solution resulted.

Then the procedure of Example II- (E) was repeated, except that this resin solution was used instead of the resin solution R-630 and only about 90 grams of additional xylene was added; i.e. 150 grams of this resin solution (the contained about 60% further curable organopolysiloxane resin solids and about 40% xylene) were used in place of the 150 grams of R-630 and 90 grams of additional moles instead the 150 grams The material was then sprayed onto the molds and cured. The blank molds showed a wear rate of about 0.00234 millimeters / h (0.092 mil / h). The viscosity of the dispersion that was sprayed on was of the order of magnitude from about 550 to 600 cps. The same spray dispersion was then continued with xylene diluted until the viscosity was about 250 to 270 cps. The shapes were then erliitzt to cure the organopolysiloxane. They showed a degree of wear of about 0.00178 millimeters / hour (0.070 mils / hour). The lifespan fraud about 16 to about 31 hours, or about 19 to about 3-1 Stulicl-n.

(J) The procedure of Example II- (E) was repeated, except that the 60% organopolysiloxane solution, prepared according to Example V-I, instead of the R-630 solution was used and the amount of the solution of the butylated melamine-formaldehyde resin from 15 grams to about 1.5 grams. The blank molds with the hardened Layer of solid lubricant film as a glass-forming, cavity-crossing surface showed a wear rate of about 0.001956 millimeters / hour (0.077 mils / hour) and one Service life in the test facility from approx. 12.5 to approx. 23.75 hours0 (K) in one Another experiment was a 60% organopolysiloxane solution, prepared according to the example V-I used in the formulation according to Example II- (E) (with of course the R-630 solution was replaced by the resin solution according to Example V- (1)). It became a degree of wear of about 0.00149 millimeters / hour (0.059 mils / hour) and a life of about 19 to 46 hours received.

Example VI To study the processability of colloidal graphite was an experiment using colloidal graphite (colloidal graphite No. 154 of Acheson Colloid Comp. as a dispersion of 20% colloidal Graphite in 80 percent by weight isopropyl alcohol), a Coulter Counter particle size distribution of curve A in the attached diagram. The spray dispersion was by intimately mixing about 150 grams of the R-630 solution, 675 grams of the colloidal Graphite (weight ratio of graphite solid to organopolysiloxane solid of 1.5: 1) and made 15 grams of the Koprez 70-10 solution; the solution had one Viscosity of about 560 cps at 25 ° C. The dispersion was made several times in succession sprayed on, b.is d. the thickness of the finished layer t of the cured organopolysiloxane bound graphite was about 0.066 to 0.069 millimeters (2.6 to 2.7 mils). IT had been cured at 343 ° C for about an hour. When using the blank molds an average degree of wear of about 0.00533 milllmeter / h was found (0.210 mil / h) and a life of about 8 to 12 hours. It is to be noted that the degree of wear is significantly higher than the degree of wear during manufacture of glass objects using the system of the invention, that is significantly higher costs when using colloidal graphite because a common one Changing the molds becomes necessary.

Example VII The procedure of Example II- (E) was repeated, but instead of graphite: A-98 a mixture of 20 percent by weight graphite 007-S (used in example III), and about 80% graphite A-98 (used in example II- (D)) is used.

The molds in this test showed a degree of wear of about 0.00259 millimeters / h (0.102 mil / h) and a life of about 17.5 5 to 26 hours.

Example VIII (L) As described above, a available further curable thermosetting organopolysiloxane (Dow 805 from Dow Corning Comp.) Used. This material was a 50 weight percent solution of a further curable, thermosetting organopolysiloxane in toluene. About 360 grams of this solution, 270 grams of graphite A-98, 220 grams of xylene, 36 grams of Koprez 70-10 (solution of the butylated melamine-formaldehyde resin) and 1.6 grams of Thixin R became intimate mixed to obtain a sprayable dispersion. This dispersion was then applied to the cavity delimiting surface of blank molds and about a Hardened hour at 343 ° C to mold the blank with a glass-forming, cavity-delimiting. Layer of graphite bound in a thermosetting hardened organopolysiloxane resin, to obtain. The evaluation indicated a degree of wear of approximately 0.00223 millimeters / h (0.088 mil / h) and a life on the order of about 24 to 31 hours obtain.

(M) Iie in Example VIII- (L) became a commercially available one curable, thermosetting organopolysiloxane (SR-240 from General Electric Comp.) used. This material is also a 50 percent by weight solution of a further curable organopolysiloxane in toluene. The materials were in same Ratios as in Example VIII- (L) put together, except, of course, that the SR-240 was replaced by the Dow 805. The resulting dispersion had a Viscosity of about 1260 cps at about 25 ° C. The forms with the solid lubricant film, obtained from this system showed a degree of wear of about 0.00309 millimeters / h (0.122 mil / h) and a life on the order of about 16.75 to about 22 hours.

(N) A solvent-soluble, further curable, thermosetting, pre-cured Organopolysiloxane was made according to the teachings of US Pat. No. 3,389,121, below Use of a condensed monomeric mixture of phenyltriethoxysilane and Methyltriethoxysilane in a molar ratio of about 4: 1. So this material has one R: Si ratio of about 1: 1 and a ratio of methyl to phenyl groups in of the order of about 0.25: 1. 90 grams of this resin were in 60 grams of xylene solved. The solution was used as in Example II- (E) to make a lubricant film to get on the forms.

The molds showed an average degree of wear of about 0.00259 millimeters / hour (0.102 mils / hour) and a life of about 15 to about 18.75 hours (O) Similarly, a resin was made according to the teachings of U.S. Patent 3,389,121 prepared to provide a thermosetting, curable, further curable to obtain precured organopolysiloxane; it became a monomer condensation mixture of about 4 moles of phenyltriethoxysilane and about 0.5 moles of dimethyldiethoxysilane are used. This composition had an R: Si ratio of 1.09: 1 and a ratio of Methyl to phenyl on the order of about 0.5: 1. 90 grams of this material were dissolved in 60 grams of xylene. This solution was incorporated into the composition according to Example II- (E) instead of the R-630 solution and a layer of the in the hardened, thermosetting organopolysiloxane bound or dispersed graphite educated. The molds provided with this layer showed a degree of wear of about 0.00210 millimeters / hour (0.083 mils / hour) and a life of about 16.5 to 19.5 hours.

(P) According to the teachings of US Pat. No. 3,389,114, a further hardenable, heat-curable, pre-cured organopolysiloxane made from methyltriethoxysilane is the only one condensable monomers produced. About 90 grams of this thermosetting, further curable, solvent-soluble organopolysiloxane were mixed with about 210g xylene and about 32 grams of isopropyl alcohol along with about 135 grams of graphite A-98, about 15 grams of Koprez 70-10 and about 0.8 grams of Thixin R0 mixed in this way Organopolysiloxane produced has an RsSi ratio of about 1: 1. The dispersion possessed a viscosity of about 140 cps and was set to the void limiting surface of the blank molds to obtain a layer of solid lubricant film. It was cured for about an hour at about 343 ° C. The average degree of wear these shapes were on the order of about 0.00211 millimeters / h (0.085 mil / h) and had a life of about 9 to 18.5 hours0 Example IX This one Example were blank molds with a glass-forming, cavity-delimiting A layer of solid lubricant film as prepared in Example II- (E). In addition, a blow mold was made in substantially the same manner as in FIG Exception that instead of graphite A-98 a graphite (200-42 from Joe Dixon Comp.) Was used, which has a Coulter Counter particle size distribution of about curve B had. So the only difference between the layer and the shape of the glass is there in graphite, the particles of which are not larger, preferably smaller than those of Graphite of the layer on the blank mold.

Excellent results were obtained on the I.S. machine, low Degrees of wear with the blank shape and high quality glass objects with a smooth surface with the blow mold, The e above examples show the surprising technical progress to which the invention leads. Opposite to.

colloidal graphite will have significantly lower degrees of wear Obtain ingot shapes, e.g., of about 0.00317 millimeters / h (0.125 mi / i-) and below.

In view of the foregoing, it should be noted in general that dic Thickness of the final layer of solid lubricant film in the range of about 0.056 to about 0.071 millimeters / hour (2.2 to 2.8 mils / hour). The film is made of graphite, bound in a thermosetting, hardened organopolysiloxane binder and can, As already said before, also an @ hardening proometer, like the butylated one Include melamine formaldehyde resin and suitable adjuvants such as a thixotrope. Regarding the spraying of the dispersion onto the mold for subsequent hardening it has been found that best results are obtained when spraying under Certain conditions are made: The dispersion spray should be used when on the surface of the mold delimiting the cavity is applied, so adjusted be that the solvent evaporation before the dispersion with the mold surface comes in contact, is not so large that only the sprayed solids on the Surface, and the spray should not be so wet that the dispersion, when it hits the surface of the form, it runs away because of too much solvent is present.

If in the description, examples and claims of the Particle size of graphite we are talking about, so is Of course the dry divided graphite is meant as it is first used, i.e. the Graphite as used to make the dispersion, which is then applied to the cavity delimiting Surface of the form is applied, is used.

It should also be noted that the accompanying graph in to include the claims in connection with the 90% and 10% larger particles is.

L e r s e i t e

Claims (15)

Verify z @@ m Fermen a glass object P A T E N T A N S P R Ü C H E 1. A method of forming a glass object in which a malleable Hot glass by contact with a glass-forming surface that limits an Eohlravm ciner hot metal blank mold is formed into a blank and the rchlfmg through Contact mft a glass-forming, cavity-delimiting surface of a blown ferrule is transferred into the object, the blank and the object molding A rotation between the glass and the form is relatively spaced apart, and the weave is at its best one of the glass-forming surfaces delimiting the cavity is made of a solid layer Formed from a solid lubricant dispersed in an ergenopolysilok @ n binder is identified by the fact that the glasfor @ nden hehla @ u @@@ limiting @ surface of the Rehlirgsferm a Dienem @ i @@, the aue in the vesantlich nichtholleidalew Grrphit in a @@ r Mange, the @mereicht, the shift gla @@ buei @@@ de Eige @@@@@ ft su varleiben, eicom erganopelysiloxem us to m @ etu @ is Ge .. Important, refer to da @ Orgaulopelysiloxan, a Siloran-Härtu @ gspremetrs consists, applied and hardened to a feat @@ Filu. 2. The method according spoke l, thereby gelen @ drawing @ et that a graphite A particle size distribution is used, which is shown in the attached diagram in the part between the connecting lines of about 90 percent by weight and about 10 weight percent larger particles than the specified diameter in the area which is limited by curves B and F and which is 90 percent by weight and the 10 weight moment connecting line, / lies; and that the binder is essentially by curing the organopolysiloxane in the presence of a curing-promoting henge a siloxane cure promoter. 3. The method according to claim 1 or 2, characterized in that also the glass forming cavity delimiting surface of the blow mold with the feston layer stranded and that a graphite is used for this layer, its particle size distribution is smaller than that of the graphite in the layer of the blank shape. 4. The method according to claim or 2, characterized in that a Graphite is used, its particle size distribution in the range of approximately bounded by curves C and E. The method according to one of the preceding Au @@ prüche, characterized in, that a graphite is used whose particle size distribution is in the area which is bounded approximately by the curves B and F, and the solid layer Has a wear rate of less than about 0.00317 mm / h (0.125 mil / h). 6. The method according to any one of the preceding claims, characterized in, that a graphite is used whose particle size distribution curve in the area which lies approximately by curves C and E and the 90 weight percent and 10 weight percent connecting lines is limited. 7. The method Rach one of the preceding claims, characterized in that that the graphite and the organopolysiloxane n a weight ratio of about 0.8: 1 h'T s about 2: 1 are used, 8. The method according to claim 7, characterized in that that the graphite and the organopolysiloxane in a weight ratio of about 1: 1 up to about 1.75: 1 can be used. 9. Process for making a glass-forming, cavity-delimiting Surface on a hot glass forming metal mold, in which a further hardenable thermosetting organopolysiloxane on a void defining surface of a glass forming Form applied and the organopolysiloxane to a thermoset, cured glass-forming layer hardened on it is identified by that the organepelysiloxane is applied in a system that essentially from the Organepelysi @ oran, an organic solvent, one as a lubricant We end the graphite bucket particle size advantage curve shown in the attached diagram in the part between the ordinate axis connecting lines of about 90 percent by weight and the particles about 10 percent by weight larger than the given particle diameter in the dom range represented by curves B and F and the 90 percent by weight and the 10 weight percent connecting line is limited, lies, and a cure promoter for the organopolysiloxane in an amount sufficient to increase the curing speed to increase the organopolyeiloxane, the weight ratio of the graphite to the organopolysiloxane in the Ehra division. 0.8: 1 to about 2: 1. 10. The method according to any one of the preceding claims, characterized in, that a melamine-fermaldehyde precondensate is used as the hardening promoter. 11. The method according to claim 10, characterized in that an alkylated Melamine-formaldehyde resin and the graphite and the organopolysiloxane in a ratio from about 1: 1 to 1.75: t can be used. 12. Glass-forming mold, characterized in that it is after. the procedure according to claim 9 has been obtained. 13. A method for producing a glass object according to one of the previous claims, geken @ is characterized by a) Forming a malleable glass to a parison in a blank form ehno rotation of the glass and the form relative to each other, wherein the blank shape with a hollow space limiting glass separating and Contact layer of a thickness of about 0.0508 to 0. e762 @ ßn (2 to 3 mil) made of graphite, dispersed in a thermosetting organopoïysiloxane binder is provided by 1) applying to the void-defining surface of a blank ferm a composition, consists essentially of graphite dispersed in an organic solution of a solvent-soluble thermosetting further curable organopolysiloxane and less than about 15 percent by weight, based on the organopolysiloxane of a siloxane curing promoter, wherein the graphite has a particle size distribution in the range roughly represented by the curves B and E is limited, and the weight ratio of the graphite to the organopolysiloxane is between about 1: 1 and about 1.75: 1, the organopolysiloxane has an R: Si ratio from 1s1 or above to less than 2: 1, where R is the one bonded to the Si atom means organic radical, and 2) heating the organopolysiloxane to thermosetting condition, to coat the mold; and b) shaping the parison into a glass object in a blow mold without rotating the parison and the mold relative to each other. 14. The method according to Ansprucb 13, characterized gaken @ neichnet that the Organopoly @ iloxane a methylphonylsiloxane having an R @ Si ratio of about 1.6: 1 or less. 15. A method for producing a glass object, characterized in that that a malleable hot glass by contact with a Glasformonden, cavity delimiting surface of a hot metal mold or rotation of the glass relative to the surface each other to form a blank, wherein the mold according to the method of one of the claims 1 to 14 is produced, and thereafter the blank into a object in a blow mold forms without rotating the blank and blow mold relative to each other.