DE2244595A1 - METHOD AND DEVICE FOR MANUFACTURING A GLAZING MATERIAL CONSISTING OF A PLASTIC FILM AND A GLASS PANEL - Google Patents

Description

Br '. Michael Hann 11th Septem & r '. 197-125

Patent attorney H / W (477) 5012/5013/5014 63 Giessen
Ludwigstrasse 67 2244595

PPG Industries, Inc., Pittsburgh, Pa., USA

METHOD AND DEVICE FOR MANUFACTURING ONE FROM ONE PLASTIC FILM AND GLAZING MATERIAL COMPOSED TO A GLASS PANEL

^ Priority: USA / September 16, 1971 / Ser.No. 181,137,

181.129 and 181.130

The invention relates to a windshield for the manufacture of automobiles and laminated safety glass suitable for other industrial purposes.

For the production of windshields for automobiles, a three-layer, namely laminated glass consisting of two panes of glass and a thermoplastic intermediate layer.

In contrast to this, the invention relates in more detail to the production of a laminated glazing material which is used in the essentially from a single sheet of transparent glass and a single, consequently uncovered synthetic resin film, for example a film made of a polyurethane resin, exists. and especially for the manufac-

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development of windshields is suitable. The expression "two-layer windshields" used in the following for this purpose the two-layer laminates of the invention are not intended to be specifically used as a Limit windshields but include any laminated glazing material made up of a Glass pane and a smooth plastic layer on its outside produced under pressure in a mold will. The smooth plastic layer of the laminate can be covered with a protective layer. The described "two-layer windshields" can also as windshields also for the glazing of the side and rear windows in automobiles and as glazing material for other vehicles and means of transport and for Glazing of buildings can be used. The term "two-layer windshield" also means laminated ones Bodies intended for use as bulletproof glass or laminated window glass their side not coated with the synthetic resin by a plastic layer with another glass layer to a laminate consisting of at least two layers of glass or in alternating sequence with several layers of plastic and several layers of glass can be connected. As glazing material on motor vehicles, When used, these laminates are always inserted into their frames with their plastic side facing inwards.

In US Pat. No. 2,047,253, it is said that one made of two panes of glass and one that connects them to one another

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adhesive plastic layer underneath existing laminate a shock or impact load is less break-proof than one made of a single glass layer and a plastic layer connected to this existing laminate in which the glass layer and the Plastic layer have the same thickness as the three-layer one consisting of two layers of glass Laminate. Tests using the falling ball method have shown that laminates made with a single layer of glass are at least 50% stronger than the one after the named .ter,.:. made of two layers of glass manufactured Lan. 3Le lan writes the higher resistance ähigk ^ .an? >. xer two-layer windshields the fact that there is no shear effect with only one pane of glass, while with the laminated windshields of the conventional type do not place the plastic between layers of broken glass are subject to a shear effect. Trot a ^ reference in U.S. Patent 2,047,253 has m < .ü .._ ned

Automobile windshields widen a out of two

Glass panes and an intermediate plastic layer. The insistence on the traditional structure of windshields is explained by the lack of it of suitable arfah: on for the production of two-layer Windscl

In US Pat. No. 2,120,628, one of a single pane of glass and a layer of a polyvinyl acetal resin existing two-layer windbreak

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disk described and claimed, wherein, the laminate special properties are given by a special treatment of the resin. However, in the examples this patent only speaks of glass-plastic laminates, which consist of two sheets of glass and a film made of a polyvinyl acetal resin inserted between these exist. Again, it should be noted that an example of the manufacture of a Two-layer laminate could not be presented because there was a suitable method for its production does not know.

According to US Pat. No. 2,184,876, glass is coated with a film made of plasticized polyvinyl acetate and on the outward-facing surface of the polyvinyl acetal film, a protective layer made of unplasticized material Polyvinyl acetal applied. As a separating layer between the printing plate of the press and the polyvinyl acetal film and then between the pressure plate of the press and the protective layer made of non-plasticized polyvinyl acetal a thin, flexible foil plated with chrome is used for lamination. According to this patent you only get ' flat laminates, the shape of which is the chrome-plated, adapts flexible film.

U.S. Patent 3,509,015 describes the manufacture of two-layer, single-layer glass and a polyurethane layer consisting of windshields, with the polyurethane between a pane of glass and a

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Serving as a mold and coated with a release agent plate made of glass or another material will. According to the method described in this patent, the space between the glass pane and its Counterplate and thus the thickness of the cast resin layer is determined by inserting spacers peripherally between the glass plate and its counterplate. The resin polymerizes when heated and forms a layer that is firmly bonded to the glass. It deals This is a discontinuous, slow process.

According to the invention is used for the production of two-layer windshields as a plastic layer prefers prefabricated polyurethane films because these are easier to handle when the elements forming the two-layer windshields are brought together, than the polyurethanes used in liquid form according to US Pat. No. 3,509,015, in the production of a laminate from a prefabricated polyurethane film and glass under increased To work under pressure and at elevated temperature, and the difficulty, the free area of the prefabricated polyurethane film and the mold resting on it during the lamination process at the end of the lamination from each other to separate without damaging the polyurethane film, the relevant industry has been deterred from making two-layer windshields with prefabricated polyurethane films to manufacture.

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Any release agent introduced between the mold and the plastic layer, even if only slightly the plastic layer adheres, causes unevenness on the surface of the film if you take the shape of it the two-layer laminate produced under pressure in the heat lifts off. Laminates made with optical Such deficiencies are not alone a source of anger for the driver and the occupants of a car, they are also at risk of being rejected from the market.

Curved two-layer windshields consist of an outside pane of glass with an im general convex outer surface and, connected to this, made of a surface of the same area as the pane of glass, inside polyurethane film. The polyurethane film has the shape of the glass pane a concave surface facing the interior of the car. One of the difficulties with detaching a Form of the polyurethane film of a two-layer laminated by the application of heat and pressure Connected to the windshield, there is also the fact that the shape is based on the concave film surface the windshield facing side must be convexly curved in a corresponding manner.

Furthermore, the film tends to wrap around the edges of the mold, especially when

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Furthermore, the film tends to get rid of the sand Wrap around foil, especially if the windshield has one or more parts that are sharply opposed the other parts are bent, as described, for example, in US Pat. No. 3,300,351 is. The more complicated the shape of the laminate, the more difficult it becomes to separate the shape from. the two-layer windshield.

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Even if you have the laminate or the two-layer windshield If there is a complicated shape, it can be difficult to detach the glass mold. The finished two-layer, According to what has been said, a transparent windshield free from optical defects consists of at least one a convex curved glass pane and a relatively soft one connected to it and smooth with its concave outer surface of the interior of the vehicle facing plastic film. Two-layer glass-plastic laminates of the type according to the invention with a relatively soft plastic film as the inside layer have a lower impact index and consequently offer there is less of a risk of car occupants getting cuts in an accident than laminates of the conventional type with an inside glass layer.

According to the invention, a two-layer windshield is made by choosing between one that serves as a form and one that becomes part of the windshield Glass pane a plastic layer not by pouring a resin, but in the form of a prefabricated one Brings in plastic film. The form used here is preferably a pane of glass Young's modulus, the hardness and the coefficient of thermal expansion concerning, has the same physical properties as the pane of glass with which the prefabricated Plastic film is to be connected in order to prevent that

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where the application of heat and pressure causes local deformations of the plastic film. Furthermore, the glass pane used as a mold must have a smooth, hard surface, the shape of which is adapted to the surface of the glass pane to be connected to the plastic film. In this way, a uniform pressure is exerted on the plastic film when it is pressed onto the glass pane to be coated, ¹ and has the effect that the uniform thickness of the plastic film is maintained during the lamination carried out under heat under pressure. The mold is made of a material that is harder than the prefabricated plastic film within the temperature range in which the lamination is currently being carried out.

The pane of glass used as the shape has, as already said elsewhere, the same shape and moreover about the same thickness as the glass pane to be coated with the prefabricated plastic film. Through this there are fluctuations in temperature and pressure that occur during the amination through the glass panes are applied through to the film, approximately evenly over the entire surface of the film. A separating agent layer optionally inserted between the mold and the prefabricated plastic film one gives a thickness of about 0.013 mm or less, preferably 0.005 mm or less, to avoid the causes of uneven temperature and pressure effects on the plastic film to a minimum.

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The invention relates to a new way of working in the production of glass-plastic laminates, which are excellent Results and is characterized by the fact that the form used is polished to a smooth finish Surface carries a coating made of a material that is not with that facing the coating Plastic surface glued, but remains firmly attached to the shape. The invention relates to this Coating of the mold with a release material that allows the mold to be removed from the mold after lamination The polyurethane film that has become part of the two-layer windshield can be peeled off without losing its shape Facing smooth, optical surface that is inherent in the film or in the case of the one connected to the lamination Pressure-heat treatment is imparted to damage. The invention also relates to the coating of the mold with certain thermosetting organopolysiloxanes, as described in US Pat. No. 3,451,838 for the manufacture of protective coatings on certain plastics and proposed in U.S. Patent 3,460,890 for the manufacture of protective coatings on metals will. For the purposes of this invention, the separating layer consisting of the substances mentioned is incorporated into the surface baked into the mold., The separating layer produced in this way has the same excellent effect when the plastic layer is used in the manufacture of the two-layer windshield, as in the US patent 3 509 015, is poured onto the pane of glass or if it is in the form of a

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made polyurethane film is placed on the glass pane.

The invention also relates to means which, after the production of a glass-plastic »laminate, facilitate the detachment of the mold from the plastic layer of the two-layer windshield obtained with him opposite the exposed portion of the film ■ a peripherally extending groove forms "This groove is used for inserting and guiding a Trennwerk-. stuff with which one penetrates so deeply into the space between the mold and the film of the laminate ₉ that one can. the opening created here can be easily expanded manually until the two parts are completely separated,

The invention also relates to a form, the ' Lamination under pressure on the surface resting on the resin layer circumferentially surrounds a channel »You put this Form preferably made of glass «If the invention in connection with this form primarily also applies to the Manufacture of two-layer windshields, directed, in which the plastic layer is prefabricated in »; If the film form is laminated with the glass pane, then two-layered ones can also be used with good results

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Laminates prepared when infuses _s example, according to US Patent 3,509,015 di <a plastic layer.

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According to a further embodiment of the invention can You can use a release agent that adheres to the plastic film but not to glass. You can use a separating means of this type with advantage in a windshield coated with polyvinyl butyral as a protective layer use for the plastic layer exposed to the pressure of the mold.

For the production of the inside plastic layer of "two-layer windshields" according to the invention a polyurethane is preferably used as the self-closing transparent resin, as is obtained when one an organic polyisocyanate with a compound containing a large number of active hydrogen atoms, for example a polyether polyol and / or a Reacts polyester polyol or a polyamine.

Suitable polyether polyols are described in U.S. Patent 3,509,015.

Polyurethanes of this type have hitherto been used as an intermediate layer in laminated safety glasses it is produced in such a way that the polyurethane is kept in the liquid state between two spaced apart Poured glass panes and hardened in the heat. The polyurethanes are generally heat curable.

Also suitable for the purposes of the invention are polyurethane compounds, those with terminal hydroxyl groups

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containing polyesters of the type described in U.S. Patent 2,871,218. These polyurethane compounds are generally thermoplastic and can be processed into films. Are suitable
also polyurethane resins such as those made by JH Saunders and
KC Frisch in her at Interscience Publishers 1964
published book "Polyurethanes Chemistry and Technology".

The polyurethanes are particularly suitable for the purposes of the invention because they are transparent to a high degree, abrasion-resistant and impermeable to air and moisture. Furthermore, they form a firm and permanent bond with glass. You can use both heat-retaining and
also laminate thermoplastic urethanes with glass to make two-layer windshields.

A polyurethane in which a considerable part of the polyurethane chains is cross-linked is called thermosetting. Crosslinking of the polyurethane chains occurs, for example, when so-called polyurethane pre-adducts, that is to say linear polycarbamate esters containing terminal isocyanate groups, made from a diisocyanate and a diol, with a trifunctional hardener, for example with a
three or more hydroxyl-containing glycol and / or with a three or more amino-containing polyamine cures.

A polyurethane is called thermoplastic, which

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contains essentially only linear polyurethane chains which crosslink only to a very small extent. The thermoplastic Polyurethanes become flowable under the influence of heat and pressure and can therefore become films extruded or calendered. In contrast, the thermosetting polyurethanes because of the between the Crosslinking occurring in individual polymer chains under the influence of heat and pressure is not desirable Dimensions flowable. The films produced from such polyurethanes by extrusion or calendering show significant optical distortion and are therefore for the Making two-layer windshields less suitable.

The reaction products of organic are suitable as thermosetting polyurethanes for the purposes of the invention Polyisocyanates and glycols containing at least three active hydrogen atoms with one organic compound are hardened or crosslinked. Preference is given first to the implementation an organic polyisocyanate with a glycol produces a pre-adduct with a terminal isocyanate group, which forms one part of a two-part system. In this system, the hardener or crosslinking agent forms the other part. Mix the two parts of the system just before using it.

The known organic polyisocyanates can be used organic compounds with two or more

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Isocyanate groups or mixtures of these compounds. The aromatic, aliphatic and cycloaliphatic diisocyanates and triisoeyanates, and of these as examples, 2,4-toluene diisocyanate, meta-phenylene diisocyanate, 4,4 ^f -diphenylene diisocyanate, 3,3 ^s -dimethyl ^, 4'-diphenylene diisocyanate, I ₉ 5-haphthylene diiso =. diisocyanate, 1,4-tetramethylene diisocyanate 1,6-hexamethylene diisocyanate _s, 1,10-decamethylene diisocyanate, 1,4-Cyclor hexyldiisocyanat, 4J4 methylene ⁸ "bis- (cyclohexylis © eyanat), 1,5-Tetrahydronaphtnylsxidiisocyanat, para xylene °" diisocyanate, toluene diisocyanate and 1,2,4-benzene triisocyanate. Preference is given to using arylenediocyanates, that is to say diisocyanates in which each of the two isocyanate groups is attached directly to an aromatic ring. -

Sterically hindered diisocyanates such as 3,5-diethylmethylene bis (4-phenylene ^{isocyanate) and o, o 8} - »diethyl para-benzene diisocyanate, whose isocyanate groups differ in their reactivity, are also suitable do not react with the isocyanate group. In the case of diisocyanates of condensed aromatic sing systems, the isocyanate groups can be bound to one ring or to different rings. Dimers of the monomeric diisocyanates and di "(3-isocyanato» 4 ™ methy! Phenyl) urea can be used

The glycol component is of particular importance, preferred if one uses a polyether from a poly (oxy

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polymethylene) glycol, in its oxypolymethylene groups the linear chain with about 3 to 6 carbon atoms separates two adjacent oxygen atoms. Are suitable for example polyethers of the formula

in the η for a number from 3 to 6 and m, for example, for a number from 2 to 30 or a number higher than 30, however, it is preferably a number from about 6 to about 20. For the purposes of the invention are suitable Poly (oxytetramethylene) glycols, which are used with preference, and the poly (oxytrimethylene) glycols, the poly (oxypentamethylene) glycols and the poly (oxyhexamethylene) glycols.

It is desirable that the polyethers used have a molecular weight between about 400 and 3500, preferably between about 550 and about 1800. With poly (oxypolymethylene) glycols, whose molecular weight is outside of the preferred range designated area is, you can probably polyurethane compounds with good optical transparency and good Produce glass adhesion, but these polyurethanes do not have the same properties as for the two-layer windshields according to the Invention desired optimal physical properties. When the poly (oxypolymethylene) glycol has a molecular weight less than 550, the polyurethane becomes too brittle at low temperatures. On the other hand, if the molecular weight of poly (oxypolymethylene) glycols exceeds 1800, Polyurethanes of insufficient hardness are obtained

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high temperatures and with them laminates that are not im desired dimensions are shock and impact resistant.

When the polyisocyanate is reacted with the polyether, the polyisocyanate is usually used in one such an amount that auf.ein mole of the polyisocyanate Hydroxyl equivalent of the polyether comes. However, this ratio is not essential for the invention, if you also get optimal results with it. You can also use the two components in larger or smaller sizes Use proportions. With a larger amount of the polyisocyanate, the so-called pre-adducts are obtained, while the use of smaller amounts of the polyisocyanate only results in an incomplete conversion of the glycol and plasticizing on the formed polyurethane can act.

The polyisocyanate and the polyether are preferably used in the form of their so-called pre-adduct, that is to say the addition product containing terminal xsocyanate groups obtained by the partial reaction of the polyisocyanate with the polyol and post-condensed , i.e. hardened, after its preparation. Pre-adducts of toluene diisocyanate and poly (oxytetramethylene) glycols are commercially available under the name ADIPRENE.

Any organic compound with at least three active hydrogen atoms can be used as hardening or condensing agent

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use in the molecule, with at least a portion of the active hydrogen preferably in a hydroxyl group is included. According to Zerewitinoff, the term "active hydrogen" denotes certain labile hydrogen atoms, that is, hydrogen atoms whose instability is determined by the organic compound used with a Zerewitinoff reagent ("The Journal of the American Chemical Society", Volume 49, Page 3181 (1927)). Polyols and amines are used as hardening or condensing agents.

If polyols are used for curing, then these must contain three or more labile hydrogen atoms in the molecule and be compatible with the reaction system. Examples of suitable polyols are trimethylolpropane, trimethylolheptane, Trimethylolethane, pentaerythritol, sorbitol and castor oil are called.

If a polyol is used as the only hardener, it is advisable to use it with a pre-adduct of a glycol and a polyisocyanate for the preparation of which the polyisocyanate has been used in an amount is that about the amount in which it is used to prepare a pre-adduct with terminal isocyanate groups with a Must convert glycol, that is, via the ratio of one mole of the polyisocyanate to one hydroxyl equivalent of the glycol. More than two, preferably about four, moles of the polyisocyanate are used in one Moles of glycol, but can also double or one more

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use larger amount * In general, however, are a Lower shelf life, processing difficulties and properties that are below the optimum are the result of a too large excess of polycyanate.

Also, a mixture of a polyol having three or more hydroxyl groups _x and a diol can be used as curing agent. For the preparation of such hardeners, for example, the polyols containing three or more hydroxyl groups of the aforementioned type can be used together with diols of very different types, for example the low molecular weight glycols such as ethylene, propylene, butylene, pentylene and higher or substituted alkylene diols, as well as a Use a range of hydroxyl-substituted aryl compounds. 1,4-Butanediol, 2,2-bis (4-hydroxylcyclohexyl) propane, 1,5-pentanediol, 2-methyl-2-H-PrOPyI-IjS-PrOPaTIdIoI, the bis (hydroxyethyl) ether of resorcinol are particularly suitable and the bis (hydroxyethyl) ether of hydroquinone. In these curing agents, the polyol functions as a crosslinking agent and the diol functions as a chain extender.

You get the best results when you get that out of one Polyol and a diol existing hardener used in such an amount that the entirety of its labile hydrogen atoms is stoichiometrically approximately equivalent to the free isocyanate groups of the pre-adduct. However good results are obtained even if the amount of hardener is in a range of 5% above

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half of the stoichiometric point and 10% below the stoichiometric point. Preferably, the amount of the curing agent composed of a polyol and a diol is within a range of 3% above and 3% below the stoichiometric ratio.

To with the poly (oxypolymethylene) glycols of different Polyurethanes produced at molecular weight to achieve optimal curing, one has to do that combine the components of the hardening agent forming diol and polyol in certain proportions. Preferred if the two components are used, for example, in a ratio of about 3.5 equivalents of the diol to one equivalent of the polyol in the case of poly (oxypolymethylene) glycols having a higher molecular weight, for example a molecular weight of about 1250 to 1800; in a ratio of about 6 equivalents of the diol one equivalent of the polyol in the case of poly (oxypolymethylene) glycols having an average molecular weight of about 650 to about 850 and in a ratio of about 9 Equivalents of the diol to one equivalent of the polyol in the case of poly (oxypolymethylene) glycols with a low Molecular weight from about 500 to about 650. In general, resin formulations in which the ratio of the diol to the polyol is in the range from 1.5: 1 to 10: 1, satisfactory results.

One can see the physical properties of the final product

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furthermore change to a certain degree by, ■ either a diol with a plasticizing effect or a Diol used with a stiffness-imparting effect. A Diol of the former type is, for example, straight-chain poly (butylene oxide) glycol, a diol of the latter type, for example 2,2-bis (4-hydroxycyclohexyl) propane. Diols of this type make the use of glycols with higher levels or lower molecular weights than those mentioned are possible.

A polyamine can also be used as a hardener use with a polyol. If you use a polyamine on its own as a hardener for pre-adducts from poly (oxypolymethyien) glycols can use, the use of a polyol increases the curability of the pre-adducts - but greatly increased. However, one can pre-adducts from glycols with higher molecular weights, for example a molecular weight of 2000 to 3000 with polyamines alone cure in the desired manner and appropriately make durable. One can change the shelf life of the resin preparations, including those with low molecular weight Glycols have been made by regulating the hardening time in such a way that you can improve the polyols added in different amounts.

Polyamines with 2, 3, 4, 5 or 6 reactive are suitable Amino groups. It is preferable to use aromatic diamines, for example 4,4'-methylenebis (2-chloroaniline), Diaminodipheny-Isulfon, 4,4'-Diaminobenzophenon and DialIyI-

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melamine. Other polyamines that can be used are the aminotriazines, for example melamine and alkyl-substituted melamines, benzguanamine, the aliphatic polyamines and other aromatic diamines, for example ortho-, meta- and para-phenylenediamine and para, para ¹ -methylene dianiline.

Virtually any polyol can be used with a polyamine. Examples of polyols that may be mentioned are the low-molecular glycols such as ethylene, propylene, butylene and pentylene glycol, the higher alkylene diols, the low molecular weight poly (alkylene oxide) glycols, for example polypropylene oxide glycol with a molecular weight between 250 and 400 and various hydroxy substituted aryl compounds. Are particularly suitable 1,4-butanediol, 1,5-pentanediol, 2,2-bis (4-hydroxycyclohexyl) propane, Reaction products of polyols with alkylene oxides, trimethylolpropane, trimethylethane, pentaerythritol, Castor oil and trimethylolheptane.

Optimal results are achieved when the hardening agent consisting of a polyamine and a polyol is combined in one used in such an amount that all of its labile hydrogen atoms become the isocyanate groups of the pre-adduct is in a stoichiometrically balanced ratio. However, very good properties will also be obtained with less than the theoretical amount of labile hydrogen atoms. This is likely to sit down many of the urea hydrogen atoms formed with the

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remaining isocyanate groups under further crosslinking. One uses the curing agent in a ¹ at least 80% of its stoichiometric amount corresponding amount. However, an amount slightly exceeding the theoretical limit is also permissible.

The thermosetting polyurethane resin is generally produced in such a way that a pre-adduct is made a glycol and a polyisocyanate heated for about 1 to 2 hours under reduced pressure and then in one mixes a suitable container with the hardener. After preparing the mixture, turn the heating to reduced Pressure to remove gases that may have formed during mixing or trapped in the mixture are. The polyurethane resin prepared in this way can be used to produce a two-layer Windshield can be introduced into a casting cell suitable for this purpose. The one used here The casting process is described in detail in US Pat. No. 3,509,015.

Thermoplastic polyurethanes are manufactured in the way that one reacts an organic polyisocyanate with a long-chain glycol and a compound that is im Molecule contains two reactive hydrogen atoms that react with the isocyanate groups. You keep the implementation in the process until a solid but still thermoplastic mass forms. Then you stop the implementation and put from the plastic mass obtained by extrusion,

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Calendering or pressing foils. Thermoplastic polyurethanes and their manufacture are described in U.S. Patent 2 729 618.

As prganische polyisocyanates and in the context of this invention are all organic compounds with two or more isocyanate groups or mixtures of such compounds, including aromatic and cycloaliphatic diisocyanates and triisocyanates and mixtures thereof are suitable. As examples of the manufacture of thermoplastic polyurethanes Organic polyisocyanates which can be used are those which have already been mentioned elsewhere for the preparation the thermosetting polyurethanes have been mentioned. Dinuclear cycloaliphatic ones are preferably used Diisocyanates, for example 4, A'-isopropylenebis (cyclohexyl isocyanate) and 4,4'-methylene-bis (cyclohexyl isocyanate. The latter is under the name HYLENE W as a 55% by weight trans-isomer and 45% by weight cis-isomer containing mixture available commercially. .

The long-chain glycols used to produce the thermoplastic polyurethanes are polyesters with terminal ends Hydroxy groups and molecular weights between about 500 and 20,000, preferably between about 750 and 5000, optimally between about 1000 and 3300. The molecular weight is determined by a hydroxyl end group analysis according to the following formula:

(Functionality of the polyester with final

',. ,, .I ₁ . standing hydroxyl group) (56.1) (IOOO)

Molecular weight = ⁰ ^ - r * - ** - 1 - ο u

⁶ hydroxyl number

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The hydroxyl-terminated polyester is produced in such a way that you can get a polycarboxylic acid with a esterified polyhydric alcohol. Since the polyesters contain a hydroxyl group at the end, one must in their production Use the polyol in excess of the polyacid. The two components are preferably used in a ratio of more than one mole of the polyol to one mole of the polyacid. The conditions under which the polyesterification is carried out, for example the reaction time and reaction temperature, the molar ratio the reactants and the catalyst to be used are known to the person skilled in the art. You can see the details about this in the work "Unsaturated Polyester Structure and Properties" published by Elsevier in New York in 1964 by Hermann E. Boening and in the work "Polyesters and Their Application" published by Reinhold in 1956 from Bjorksten.

It is preferred to use for the production of the thermoplastic Polyurethanes as polyesters with terminal hydroxyl groups are the esterification products from aliphatic dibasic acids or the anhydrides of these acids

and aliphatic diols. Suitable aliphatic dicarboxylic acids are the. Alkylenedicarboxylic acids with 4 to 14 carbon atoms in which the alkylene group, for example the adipic acid group, the succinic acid group ,. the pimelic acid group, the suberic acid group, the azelaic acid group, or can be the sebacic acid group. In addition to the saturated ones, one can also use unsaturated dicarbon

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acids or optionally the anhydrides of such acids as maleic acid and maleic anhydride, fumaric acid and use the itaconic acid. It is preferred to use saturated aliphatic diols having 2 to 15 carbon atoms. Examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol called. However, you can unsaturated diols, for example 2-butene-1,4-diol and 2-butyn-1,4-diol, can also be used.

Most preferred as the hydroxy terminated polyester is a poly-1,4-butylene adipate with a Molecular weight from about 1000 to about 3000.

Except for the polyesters with terminal hydroxyl groups the organic polyisocyanates react with another compound which, according to Zerewitinoff, determines contains at least two active hydrogen atoms.

It is preferred to use compounds with only two active hydrogen atoms reacting with the isocyanate groups, ... and as such, the aliphatic diols having from about 2 to 15 carbon atoms. Examples are saturated aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol, and unsaturated aliphatic diols, such as 2-butene-1,4-diol and 2-butyn-1,4-diol.

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ζ?

N, the preferred aliphatic diols. are also amines or mixtures of amines and diols, which contain at least two and optimally no more than two active hydrogen atoms in the molecule, than active hydrogen-containing compounds are suitable.

The amines used here can be primary and secondary diamines and those with the nitrogen atoms in them linked groups may be saturated or unsaturated aliphatic or alicyclic groups. Also diamines with aromatic, aromatic substituted aliphatic, aliphatic substituted aromatic or heterocyclic groups and mixed amines with different types, for example aromatic and aliphatic Groups can be used as well as those attached to carbon atoms or nitrogen atoms, other reactive groups, for example carboxyl, hydroxyl, halogen or nitroso groups. As examples suitable aliphatic and alicyclic diamines are 1,2-ethanediamine, 1,2-propanediamine, 1,3-propane diamine, 1,3-butanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexane diamine, 1,8-octane diamine, diaminopropyl tetramethylene diamine and called 1,8-menthandiamine.

Of the aromatic diamines, for example, the phenylene diamines and the toluene diamines can be used will. Examples of these amines are o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-m-tolylenediamine and called p-TColylenediamines. Furthermore, the

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N-alkyl and N-aryl derivatives of the aforementioned amines, for example Ν, Ν'-dimethyl-o-phenylenediamine, Ν, Ν'-di-ptolyl-m-phenylenediamine, N, N ¹ -di-2-naphthyl-m- phenylenediamine, N, N'-dimethyl-p-phenylenedianiine, N, N'-diethyl-pphenylenediamine, N, N ¹ -di (sec-butyl) -p-phenylenediamine, p-aminodiphenylamine, N, N ¹ -diphenyl- p-phenylenediamine and N, N'-di-2-naphthyl-p-phenylenediamine _t be used.

In addition to the aliphatic diols and amines mentioned, the numerous compounds which contain the active hydrogen atom bonded to oxygen, nitrogen or sulfur can also be used as carriers of active hydrogen atoms for the production of the thermoplastic polyurethanes according to the invention. Particularly suitable are the compounds which contain, in any combination, at least two of the substituents -OH, -SH, -NH-, -COOH, -CONH ₂ , SO ₂ OH, -SO NH ₃ and CONHR, where in the latter substituent R is one organic residue. The groups associated with these substituents can be aliphatic, aromatic, cycloaliphatic or mixed groups. Examples of suitable active hydrogen-containing compounds of the type described are the polyoxyalkylene glycols, for example diethylene glycol; the cycloaliphatic diols, for example 1, A-cyclohexanedimethanol, the dihydric aromatic phenols, for example resorcinol and hydroquinone, and the bis (beta-hydroxyethyl) ethers of resorcinol and hydroquinone, and 4,4'-dihydroxydiphenyldi-

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22U595

methyl methane. Also amino alcohols, diamines, sulfonamides and also derivatives containing terminal mercapto groups and mixtures of these compounds can be used. Suitable mixed compounds are, for example, monoethanolamine, 4-aminobenzoic acid, 4-aminobenzamide, sulfanilamide, aminopropionic acid, 4-hydroxybenzoic acid, p-aminophenol, and beta-hydroxypropionic acid. Suitable sulfonamides are 1,3-propanedisulfonamide and 1,4-cyclohexanedisulfonamide and 1,4-butanedisulfonamide.

In addition to the above-described and preferably used aliphatic polyesters, polyesters can also be used. use aromatic groups in the polyester groups, the aromatic character is derived either ¹ of the dicarboxylic acid esters or the "diol groups. As examples of suitable aromatic dicarboxylic acids are terephthalic acid and isophthalic acid, and suitable as examples of aromatic diols, resorcinol, the bis (beta-hydroxyethyl) ether of hydroquinone and 4,4'-dihydr oxydiphenyldime thy lme than called.

One can use the thermoplastic polyurethanes for the lami- '. Produce nated windshield according to the invention by various methods. The polymerization can be controlled selectively according to the so-called two-stage prepolymer process. According to this, the polyester is first mixed with a diisocyanate used in excess to form an adduct or prepolymer of medium

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implemented leren molecular weight. The prepolymer or pre-adduct is then used for chain extension with a Diol, a diamine or other active hydrogen-containing compound polymerized. One can bring about a certain crosslinking by adding a small amount of a Triols or another trifunctional substance added. When you get through the thermoplastic polyurethane If you want to process extrusion into films, it must only have a very low degree of crosslinking, otherwise it is involved the heat of extrusion and not under the extrusion pressure comes to flow. Made from a strongly cross-linked polyurethane one obtains, as a result of his poor footing, optically distorted films.

In contrast to the prepolymer process, in which the Reaction of the isocyanate with the polyester is terminated before the active hydrogen-containing compound, alternatively also called hardening agents are added in the one-step so-called "one-shot" process all components mixed at the same time. In general, satisfactory results are then obtained with this process Results when all active hydrogen atoms with about react at the same speed, that is, if the hardeners only have hydroxyl groups as reactive Groups included. If a diamine is used as a hardening agent containing the active hydrogen, You can usually only achieve a satisfactory result if you add a catalyst

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the U _mse estimation with the hydroxyl groups, catalyzed selectively in such a way that their reactivity is equal to that of amino groups. Otherwise, the diamine converts to a polyurea, which separates out of the reaction mixture. Particularly suitable catalysts here are the tin catalysts, such as dibutyltin dilaurate and tin (II) octoate.

Since the isocyanate group is sensitive to moisture, the hydroxyl-terminated reactants should contain as little water as possible.

The reaction of the isocyanate should be done with dry reactants generally in an anhydrous environment, for example under nitrogen, under atmospheric pressure at a Temperature between about 70 and about 200 ° C can be carried out. Keep the reaction going until essentially no more free isocyanate or hydroxyl groups are present, that is, until the reaction mixture is less than about 0.6, preferably less than 0.3% by weight of NCO.

The use of catalysts, although not required in all reactions, is generally convenient. The Zinri catalysts already mentioned are suitable, for example Dibutyltin dilaurate and tin (II) octoate. It is also useful in the case of aromatic diisocyanates an ultraviolet light absorbing agent, for example 2,4-hydroxybenzophenone or one under the designation TINUVIN commercially available substituted benzotriazole

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to use. Among the more stable aliphatic diisocyanates, an absorbent of this type is generally of this type not mandatory. The addition of a heat stabilizer may also be necessary for some preparations / be. Suitable for this purpose are dilauryl thiodipropionate and the hindered phenolic resins.

Decisive for the selection of the hardening agent are the properties which are to be imparted to the polymer and the conditions under which it is processed in practice shall be. When working according to the prepolymer process, the prepolymer or pre-adduct is expediently applied heated to a temperature above the melting point of the hardener. This increases the viscosity of the prepolymer reduced to a few hundred or at most a few thousand centipoise. This makes it easier to mix and match prevents the hardening agent from solidifying. The hardener is also usually at a temperature above his Heated melting point. Mixing the prepolymer with the curing agent is a critical process that is a brisk one and even stirring is necessary.

The same or even better results are obtained with the "one-shot" method, if one is for a proper rebuff the heat of reaction and regulates the reaction rates of the components so that they approximate each other are the same. Otherwise a catalyst must be used.

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. _M.

The ratio of the reactants to one another can be a function vary depending on the materials used and the use to which the urethane is to be put. Preferred however, is the total number of labile or active hydrogen atoms approximately equivalent to the number of isocyanate groups. In general, the ratio of the isocyanate groups lies to the labile or active hydrogen atoms between about 0.9 and 1.1. Also, the ratio of the hydroxyl terminated polyester to the active one Hydrogen-containing compound can depending on, for example, the molecular weight and the chemical Identity of the hydroxyl-terminated polyester and, for example, the type and molecular weight of the active hydrogen-containing compound vary within wide limits. When you think of polyester with a terminal hydroxyl group, for example poly (1,4-butylene adipate) having a molecular weight of about 1000 to 3000 and as the active hydrogen containing compound 1,4-Bu tandio L is the ratio of the polyester to the active hydrogen containing compound at about 1: 1 to 1: 6.

When the reaction has essentially ended, the resulting polymer is used to produce films directly to an extruder, a calender or similar devices. You can use calenders or similar Use devices of the type described in U.S. Patent 2,186. You can do that incompletely

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polymerize the polymerized material to the end in the device used to produce the films. If it is not possible to transfer the polymer from the reaction vessel directly into one of the devices mentioned, it can be poured into pans or similar containers and allowed to solidify into blocks. It is useful to cover the inner surface of the pan with a coating made of the polymer to be filled in order to to prevent the polymer from sticking to the pan and making it difficult to remove it. as TEFLON, which consists of halogenated hydrocarbons, is also suitable for the coating material. One can then process the polymer further as required and, if it has to be available in comminuted form for this purpose, in ' cut into pieces by the heat, as it is easier to cool and granulate in this form.

To protect against dust, the foils are placed between a non-sticky material, for example between polyethylene foils and then seal it in a container to protect against moisture. You can use the individual slides also sprinkle with a powder, for example sodium bicarbonate powder, to prevent them from lying on top of each other Glue the foils. Before using the foils for the production of laminates, it is advisable to regulate their moisture content and use them for this purpose a few hours or up to about three To dry days and longer at room temperature or at a temperature of up to 48.90 C in an oven.

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Before the amination can be applied an optionally applied Rinse off the powder layer in a water bath and then dry the foils. You can with the polyurethane foils then, to produce the laminates according to the invention, coat substrates made of other materials.

Instead of the polyurethanes according to the invention, one can use a transparent plastic mass for the plastic layer a two-layer windshield also a polyvinyl acetal resin, use, for example, a plasticized polyvinyl butyral resin coated with a thin protective layer, for example, is coated from the non-plasticizing resin. Plasticized polyvinyl acetal resins have the same transparency, tear resistance and flexibility as polyurethane resins. Make polyvinyl butyral U.S. Patent No. 2,400,957. It is used in the manufacture of laminated windshields as an intermediate layer because at a suitable temperature and pressure with glass there is a strong Adhesive bond enters into, because it, placed between two panes of glass as an intermediate layer, is transparent and because it does not deform, that is, it does not bulge, when an object is placed on top of it as an intermediate layer produced laminated, i.e. multilayered safety glass.

You can choose the polyvinyl acetal resins from unsubstituted Aldehydes and mixtures of such aldehydes or from unsubstituted ketones that have an active carboxyl group

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or from mixtures of unsubstituted aldehydes and ketones. Formaldehyde are suitable, Acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexaldehyde, benzaldehyde, crotonaldehyde and cyclohexanone and mixtures of these compounds. The polyvinyl acetal resins produced from butyraldehyde are used with preference, the so-called polyvinyl butyral with a molecular weight in the range of 150,000 and 250,000. One can the 'polyvinyl acetal resins as from 5 to 25% by weight as poly ~ hydroxyl groups calculated from vinyl alcohol, acetate groups calculated from 0 to 40% by weight as polyvinyl acetal and consider consisting essentially of acetal as the remainder. If the acetal used is butyraldehyde acetal, the polyvinyl acetal resin contains 16 to 25% by weight as polyvinyl alcohol calculated hydroxyl groups, 0 to 10% by weight as polyvinyl acetate calculated acetate groups and im essential butyraldehyde acetal as the remainder. in particular polyvinyl butyral are used as high-performance interlayers of multilayered Safety glass windshields known. As polyvinyl acetal resins and their production are well known to those skilled in the art, there are others at this point Information on this is not required. More information on the manufacture of polyvinyl acetal resins can be found U.S. Patents Re 20,430 and 2,496,480.

Usually, polyvinyl acetals, in particular polyvinyl butyral, are used when they are used for production

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of glass laminates · a plasticizer too. In general· ·· · the water-insoluble ester is used as a plasticizer from a polybasic acid and a polyhydric alcohol. Triethylene glycol, di- (2-ethylbutyrate), Dibutyl sebacate, di (beta-butoxyethyl) sebacate and dioctyl phthalate are particularly suitable as plasticizers.

It should be noted that the polyvinyl acetal resins are well usable in the context of this invention that their Use but makes certain measures necessary. So the resins are very sensitive to moisture. As a result, moisture can penetrate the polyvinyl acetate layer and weaken the bond between the resin layer and the glass layer. To prevent this from happening, one overlooks the free surface of the polyvinyl acetal film with a thin - · layer of a moisture-resistant material.

According to the aforementioned US Pat. No. 2,184,876, the coating material used for this purpose is, for example, unplasticized Polyvinyl acetal suitable. The protective layer can be sprayed on or painted on in a known manner.

The free surface of the polyvinyl acetal layer can also be protected by a coating of SiO ₉ applied in vapor form. This process is described in British patent specification 1,144,099. · - · ■

To protect the free area of the polyvinyl acetal layer a thin coating of a polyurethane according to the invention is also suitable.

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22U595

For the outside glass layer of a two-layer windshield according to the invention, any one can be used known and commercially available mirror, float or pane glass, as well as any other transparent Use window glass. Glasses of the type of soda-lime-silicate glass, which in a Amount of about 0.5% a coloring substance, for example an iron oxide, can be added. The pane of glass preferably has a thickness of 0.254 to 3.3 mm.

In a preferred embodiment, the invention relates the production of two-layer windshields, as the outer layer of which is a commercially available one Soda-lime-silicate glass of the following composition is used:

Na ₂ O 10 until 15th Gew7o K ₂ O 0 until 5 Weight% CaO 5 until 15th Weight% SiO ₂ 65 until 75 Weight% MgO 0 until 10 Weight% B ₂ O ₃ 0 until 5 Weight%

A soda-lime-silicate glass particularly suitable for the purposes of the invention has the following composition:

71.38 Gew7o (fluctuation range 71 to 74 Gew7 »)

₂ 12.76 Gew7o (fluctuation range 12 to 14 Gew7 »)

Κ "0 Gew7o 0.03 (range 0 _o to 1 Gew7)

3 0 9 8 2 9 / Q 7 o 3

CaO 9.67 wt. To (fluctuation range 8 to 12 wt.%)

Mg'o "4.33% by weight (range of variation 2 to 5% by weight)

Na »S0 0.75 wt% (fluctuation range 0.1 to 1.0 wt%)

Fe ₂ O ₃ 0.15 wt% (fluctuation range 0.1 to 1.0 wt%)

Al 0 0.81 Gextf% (fluctuation range 0.1 to 1.0% by weight)

One can have the same pane of glass as that used as part of the windshield glass pane used during lamination in contact with the free surface of the polyurethane film use as a shape. However, the sheet of glass used as a mold differs from that used as part of the Laminate used glass pane that this either directly or by means of a applied to their contact surface Layer made of an adhesion promoter with the polyurethane .thane film is connected, while the serving as a mold Glass pane is coated on its side facing the film with a release agent, by means of which it is after completed lamination can be more easily removed from the two-layer laminate. For this purpose are Release agents as described and claimed in U.S. Patent Application No. 181,129. The as Fgrm The glass pane serving can also be provided with a peripheral bevel on its side facing the film and the ground surface can be covered with a tape that adheres to glass but does not adhere to polyurethanes. You can use a tape made of polytetrafluoroethylene for this.

You can change the sheet of glass used as a shape according to their

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Faceting, but before they are coated with a release agent, if appropriate according to that in the US patent 3,477,834 by ion exchange at an increased voltage below its voltage limit Chemically temper temperature. A typical chemical tempering process consists of removing the pane of glass Immersed in a potassium nitrate bath at 480 ° C for 6 hours. You can use this to strengthen the glass without it deformed. The tempered glass can be used in many forms in the manufacture of two-layer windshields Times to be reused.

In some cases it has been found necessary to use an adhesion promoter to bond the glass pane to the polyurethane film. Various alkoxysilanes are suitable as adhesion promoters, for example ^{gamma-aminopropyltriethoxysilane, which is commercially available under the name A-1100 R} and Z-6020 ^R, and N- (beta-amirioethyl) gamma-aminopropyltrimethoxysilane, which is commercially available under the name A-1120 ^R. The adhesion promoter can be added to the urethane reactants or applied to the film or, preferably, to the glass surface. Furthermore, in some cases it may also be necessary to use an agent which regulates or inhibits the adhesion of the polyurethane films. Suitable for this purpose are those described in Canadian Patent No. 861 469 described acidic alkyl phosphates, in particular the acidic methyl phosphate and the acidic stearyl phosphate, both of which, as has been found, affect the adhesion of the film in such a way that they have an excellent

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excellent diaphragm effect and to hold the pieces of glass in place when a laminate breaks able. The addition of an adhesion inhibitor is generally necessary when laminates are poured on 'ren manufactures because here the urethane is very strong. connects with the glass. If you look at that, for example Polyurethane produced using the single-stage block polymerization process, extruded into films and / or calendered, it depends on the type of polyurethane whether. an adhesion promoter must be used or not. The inhibitors are generally added to the urethane reactants, but in some cases they can be added apply as a coating on the foils. The adhesive regulating agent is used in a very small amount, for example in an amount from about 0.00001 to about 0.1%.

One can, for the separating layer between the form and the prefabricated plastic film use any suitable material with which coatings of such a small size Can be made starch that they aus'der glass pane, with this plastic film to be glued, the Separation layer and the detachable glass form composite unit in their strength is not significantly asymmetrical. metry shows. The separating layer must be thinner than 0.127 mm. This is intended to prevent one from acting on the two surfaces of the plastic film uneven force unevenness iii

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"22U595

the thickness of the film, which would result in optical distortion of the laminate.

The separating material must be smooth. It is generally used in the form of one made of a polyvinylidene fluoride or a film made of a polyvinylidene fluoride mixture. These are commercially available fabrics in U.S. Patent 3,451,978. Films made of polyethylene glycol terephthalate are also suitable as a separating material and thin metal and metal oxide layers firmly bonded to the mold on its pressure-loaded side, for example as described in U.S. Patent 3,506,556 by cathodic sputtering at temperatures below the voltage limit of the glass. if the pane of glass used as a mold when applying the coating serving as a separating material at a temperature temperature, which is well below the deformation temperature of the glass, it prevents it warps and no longer corresponds in shape to the shape of the glass pane to be laminated with the plastic film.

Particularly suitable release agents are those described in the US Patent application no. 181 130 of September 16, 1971 described coating compositions made of organosiloxanes, which one obtained when at least one compound of the formula T SiZ /, ν is hydrolyzed and condensed. In the formula T stands for an alkyl radical, an alkenyl radical or

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an aryl radical, for example for methyl, ethyl and propyl, butyl, pentyl and hexyl, these in their normal and isomeric form, cyclopentyl, cyclohexyl and vinyl as well as propenyl, butenyl, pentenyl and hexenyl, too these in their normal and siomeric form; Z for a hydrolyzable group, for example for chlorine, bromine, Fluorine or iodine, for an alkoxy group, for example the methoxy, ethoxy, propyloxy, butyloxy, pentyloxy or the hexyloxy group or for an acyloxy group, for example the acetoxy, propionoxy, butyroxy, pentanoxy and hexanoxy groups and for an aryloxy group, for example the phenoxy group and η for a positive integer of less than 4, preferably for 1. For the For the purposes of the invention, the organosiloxane used is preferably a solution of a methyltrialkoxysilane or a Solution of a mixture of a methyltrialkoxysilane and a phenyltrialkoxysilane in which the alkoxy group contains less than 5 carbon atoms. Among the hardenable Organopolysiloxanes and their preparation are referred to the US patents 3 451 838 and 3 460 980 pointed out. In the former, their use for the manufacture of hard, Acetone-resistant and heat-resistant coatings on substrates made of polycarbonates and acrylic acid esters !!, in the latter their use for making hard, abrasion-resistant, weather-resistant, chemically-resistant and easy to use cleaning coatings on metal substrates.

A separating layer with excellent properties is obtained if a coating is applied to the surface of the glass mold

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from what is known as Owens-Illinois Glass Resin

R.
T 650 bakes in commercially available organopolysiloxane in situ. This glass resin contains about 89 silica. Separating layers which are produced in this way from a material with a high, that is to say over 75% by weight, silicon content have a better separation effect than those which are produced in the same way from a material with a lower silicon dioxide. The release agent adheres better to the mold if an adhesion promoter is applied to it beforehand, as is used in the production of the windshields according to the invention for bonding the polyurethane film to the glass pane.

Because windshields are curved in shape today and a higher temperature is required for deforming glass than in the production of glass-plastic laminates, one deforms in the manufacture of two-layer windshields according to the invention Glass panes to be used on the outside in layers of two or more such panes and then used one of the curved panes as a reusable shape for the windshield. In the US patent 3 453 161 describes a process by which a large number of panes of glass are stacked on top of one another Can bend in the vicinity of its softening point according to the "gravity sagging" method. You can search for the "gravity sagging "method, of course, you can also bend a single pair of discs or even a single disc.

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Except for the "gravity sagging" method one can Glass panes for the production of laminated windshield "panes according to the invention, also individually under pressure deform (British Patent 1 202 187). One of the glass panes deformed in this way is then used, chemically tempered, as a reusable mold for coating the other uniform panes with the plastic film. The pane is tempered by ion exchange at a temperature below the stress limit of the glass. Here the curved shape of the disc remains unchanged. The term "compression deformation" includes both Working with a vertical arrangement of the glass pane according to US Pat. No. 3,367,764 as well as working with a horizontal one Arrangement of the glass pane according to US Pat. No. 3,374,077 and also working in a vacuum according to US Pat 3,468,645 a.

To produce the two-layer windshield according to the invention, the glass pane and the plastic film are placed together, after having previously either one of the contact surfaces or both contact surfaces with an adhesion promoter has coated. Furthermore, a second glass pane serving as a shape is coated on its convex one Side with a thin film. Then you put the two units one inside the other in such a way that the coated surface the shape and the free surface of the plastic film are opposite one another. Air pockets between the The pane of glass and the plastic film can be removed in the same way that you can remove them from the glass-plastic laminate

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and place the existing unit in a thin, flexible bag and apply a partial vacuum. The bag is then closed and the glass is laminated to the film under pressure, the unit being heated to the softening temperature of the polyurethane. In order to bring about the lamination, one works for about 5 to 10 minutes under a pressure of 0.7 to 1.75 kg / cm.sup.3 at a temperature of 148.9 ° C. The unit can then be used to complete the lamination for about Place for 45 minutes to 2 hours under a pressure of 3.5 to 17.5 kg / cm ^ in an oil or air autoclave heated to about 93 to 177 ° C. However, the conditions prevailing in the autoclave are determined by the type of polymer used.

You cool down, relax and lift the shape off the laminate.

According to a preferred embodiment of the invention If you bend two panes of equal surface glass together in a bending form of the one, for example, in the US patents 2,933,856 and 2,794,300 with heating to their deformation temperature. To prevent the panes from sticking together, a layer of a suitable one is put in place Separation material, for example a layer of an aqueous dispersion of a diatomaceous earth such as this in U.S. Patent 2,725,320, between she an.

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When the panes of glass took the shape of the mold you lift them off from each other and wash them thoroughly free of the release agent. You use one of the 3.175 mm thick float glass panes as a form and the other as the outer glass layer 'a two-layer Windshield ..

• Example A

As described below, a curved outside glass layer and an inside layer made of plasticized polyvinyl butyral one Number of two-layer windshields.

One puts on the concave surface of a curved according to the shape of the desired windshield, for example 3.175 mm thick float glass pane made of a commercially available plasticized polyvinyl butyral resin Foil with a thickness of 0.762, 1.143 or 1.524 mm. On the outward facing surface of the polyvinyl butyral film a layer of polyvinylidene fluoride about 0.0254 to 0.0508 mm thick is applied and smoothed she. Thereafter, a second float glass pane is placed which has the same shape as this first float glass pane of the same thickness on the first pane so that its polyvinylidene fluoride layer and the convex Surface of the second disc are opposite to each other, closes the two parts at their edges with a ribbon, wraps it in a plastic wrap,

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22U595

to prevent the individual layers from clashing against each other slide and place the composite in a laminated sack of the type disclosed in U.S. Patent 3,311 described type. The sack consists of an outer layer made of polyethylene glycol terephthalate .und a layer of polyethylene glued to this layer. It does not exceed 0.127 mm Overall strength. It is evacuated after the laminate has been inserted to a vacuum of 0.176 kg / cm ^, closed it, places it in an oil autoclave and subjects it to a pressure of 14 kg / cm at 135 ° C. for 45 minutes It is cooled in the autoclave under the pressure mentioned to about 65 ° C., relaxed and the sack is removed from the Autoclave out.

The laminated body unit wrapped in plastic film is removed from the sack, the plastic cover is removed and lifted the second pane of glass serving as a mold, the polyvinylidene fluoride film with the polyvinyl butyral layer remains connected. The laminate obtained consists of that coated with a smooth thin film of polyvinylidene fluoride Polyvinyl butyral foil on its concave side - and a sheet of glass on its convex side.

■ A method has been developed to test windshields for their dielectric strength after which a so-called Alderson doll on a sliding device, as published on page 143 of the Society of Automotive Engineers, New York, 1967

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22U595

Reports on the 11th STAPP conference (Eleventh STAPP Car Crash Conference) is thrown at a certain speed against a test disc. In order to determine the degree of soft tissue injuries, especially lesser degrees of soft tissue damage to be able to, one covers the head of the Alderson doll to imitate the human skin with a double layer of damp chamois leather. Injuries in the form of slight scratches on the surface of the external Lexler cover are considered "minor" and with the injury degree 1, whereas injuries caused by cuts and broken tissue (tears), which go through the two layers of leather are described as "heavy" and with a degree of injury of 5. Between these two grades are grades 2, 3 and 4, distinguished by their severity. those with an undamaged inner layer only a few light ones on the outer layer of the leather cover Sections show the degree of injury 2, dolls that, also only on the outer leather layer, have a larger one Number of cuts and tissue fragments show that Injury degree 3 and dolls with a large number of Cuts and fragments of tissue, some of which go through the two layers of the leather cover, degree of injury 4.

Further two-layer windshields are made with prefabricated foils made of polyurethanes of the polyester type

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22U595 SO

as an intermediate layer · between panes of glass of the same size, whereby here, too, between the as a form Serving disc and the polyurethane film inserts a layer of a release agent, and compares the with These laminates noted degrees of injury with those who deal with the conventional, made of two panes of glass and a plastic inner layer result in three-layer laminates.

Examples 1 to 20 describe the production of films from a range of polyurethanes of the polyester type and the production of two-layer windshields, in which a film of approximately more uniformity Thickness glued on the inside with a curved glass pane and a second glass pane of the same Curvature used as a shape.

POLYURETHANE 1

After drying 785.6 g (0.4 moles) of a poly (I, 4-butylcn- * adipate) polyester with a molecular weight of 1965. The hydroxyl 57, an acid number of 0.5 and a dripping point of 51 ⁰ C and 707 4 g (0.698 mol) of a poly (1,4-butylene adipate) polyester with a molecular weight of 1014, the hydroxyl number 111 and the ¹ acid number 0.5 at 100 to 105 C with stirring for three hours under a pressure of 3 mm Hg in a reaction vessel

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Si 22U59-5

Glass to remove · traces of water. Normal pressure is then restored by introducing pre-cleaned nitrogen, and 260.6 g of ^K (12.892 mol) of a 1,4-butane containing 0.03% water are added to the dry polyester mixture at 93 G with stirring over the course of 1 minute. ; diols and increases the temperature to 95 ° C in 15 minutes . 1046.8 g (-3.989 mol) of 4,4'-methylene-bis (cyclohexyl isocyanate) containing between 0.27 and 0.40% monoisocyanate and having a stereoisomer content of 19 to 21% are added to the homogeneous mixture obtained over a period of 1 minute. trans-trans, 17 to 18% cis-cis and 62 to 64% cis-trans (urethanes in the following Pol}>, having a d _v ti isocyanate the same isomer unless expressly stated otherwise) · ■. together with 0.280 g (0.01% of the total reactants) of dibutycin dilaurate as a catalyst. A nitrogen atmosphere prevails in the reactor both when adding the butanediol and when adding the diisocyanate, both of which have a temperature of 22 ° C. The mixture is stirred vigorously for one minute, the temperature rising from 80 ° C. to 95 ° C. Then it is poured into a layer of polytetrafluoroethylene

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224-595

Pull out the dry reaction vessel, close it and place it with the polymer, which has a temperature of about 143 C, in an oven heated to 130 C, which is flushed with a continuous stream of nitrogen. After about 2 hours, the reaction is practically complete with the formation of the polyurethane. Determined by infrared spectroscopy, the polymer contains 0.07% by weight of NCO. The semi-solid polymer is allowed to cool to room temperature, taken out of the reaction vessel, cut into pieces, ground at a front roll temperature of 82 ° C and a rear roll temperature of 57 ° C and calendered on a three-roll calender, the upper roll of which has a temperature of 121 ° C , the middle roller of which has a temperature of 107 C and the lower roller of which has a temperature of 101.6 C, to films with a width of 35.5 cm and a thickness of 0.839 mm. The polymer has in 0.5% concentration in N-methyl-2-pyrrolidone e5.ne inherent viscosity of about 1.40 prior to milling and an NCO content of 0.077 _o. After calendering, the polymer has an almost unchanged inherent viscosity of 1.41.

309829/0723

S3

Cut the foils with an addition after both. Sides at right angles to the big one, the windshield of the Volkswagen and stores them for appropriate use.

Dissolve 200 g of the Owens Illinois Glass Resin .T-650 ^R commercially available organopolysiloxane in powdered form in 575 cm ^ dry butanol, stir the mixture at room temperature for about one and a half hours at 200 revolutions per minute to completely remove the organopolysiloxane Bring butanol to the solution and filter the solution under reduced pressure through a Buchner funnel lined with a No. 3 filter paper. The solution contains 30% solids by weight. They are kept in a polyethylene bottle.

You take from a supply of prefabricated glass panes of the size and shape of the Volkswagen windshield two disks and provide one of them around its edge with a convex side sloping ground. This glass pane serves as a mold in the manufacture of the windshield ^.

One is sold under the designation A-1100 in stores available adhesion promoter consisting essentially of gamma-aminopropyltriethoxysilane in 0.3 percent by volume Concentration in butanol up, the solution filtered under reduced. Print by one with filter paper No laid out Buchner funnel, it thins and

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5V

pour it onto the convex surface of the one used as a mold Glass pane open.

The 30% organopolysiloxane solution stored in the polyethylene bottle is then diluted with butanol a concentration of 15 wt% solids, filtered under reduced pressure through No. 3 filter paper, degassed until no more bubbles form, also pour this solution on the convex side of the glass pane used as a mold, the pane dries for 30 minutes at room temperature and then cure for 24 hours at 121 ° C in a clean oven. After cooling, you cover it the edge and the ground surface of the disc with a tape of polytetrafluoroethylene of such width that it, beyond the reed area onto the pane of glass placed, forms on this one of the other glass pane facing frame of 4.762 mm width.

Another solution, commercially available under the name A-1120, essentially consists of n- (beta-aminoethyl) gamma-aminopropyltrimethoxysilane existing adhesion promoter in a 50% strength by weight isopropanol-in-water solution at a concentration containing 1 wt% solids, the solution wears on the concave side of the Part of the two-layer windshield will be on and the layer dries. 10 mins at room temperature.

The one provided with the beveled cut is then layered

309829/0723

Glass pane, the prefabricated polyurethane film and the second glass pane to be connected to this in this way on each other that the foil with one of its surfaces, the concave surface of one glass pane coated with the adhesion promoter and with its other · '■ Face of the convex face of the other pane of glass, the one under the designation Owens-Illinois Glass Resin T-650 is coated with commercially available glass resin.

The three-layer body assembled in the manner described is wrapped in a plastic film and then puts it in a so-called "Polymar" bag from of the type described in US Pat. No. 3,311,517. The sack consists of an outer layer of polyethylene glycol terephthalate and an inner layer of polyethylene firmly connected to this. One puts the Sack into a second sack made of the same material, evacuate it and seal it. One lays put it in an oil autoclave and pressurized it for 45 minutes at a temperature of 135 ° C 14 kg / cm ^, cools to room temperature under increased pressure and relaxed.

The sack is taken out of the autoclave and freed the three-layer body from its shells. Then you put it with its concave side up on a support carriage and press to deepen the groove created by the bevel cut along the edge of the mold,

309829/0723

22U59S

one. Razor blade in the space between which the edge zone the tape covering the mold and the polyurethane sheet into it. Place in the opening created in this way you insert a rotating cutting disk similar to a pizza dough cutter and guide it in the groove and in this between the tape and the film around the three-layer body, around the separation between the To deepen the shape and the film in the overall periphery. When the separation reaches a depth of about 2.5 cm you pull the form from the two-layer laminate by hand, with one on the outside Glass layer of the two-layer windshield attaches a suction holder.

The polyurethane layer forming the inside of the two-layer windshield has, within the line, which the pizza cutter reaches when separating the glass pane serving as a mold from the polyurethane layer, a smooth surface, that is, free of any unevenness.

Examples 2 to 20 contain further formulations for the production of polyurethane films for two-layered films Windshields.

309829/0723

POLYURETHANE 2

In the manner described for polyurethane 1 and under the conditions specified there, 2.274 mol of a poly (1,4-butylene adipate), a molecular weight of 1010 and a hydroxyl number of 111.1, are mixed with 1.295 mol of a poly (1,4-butyl) with stirring butylene adipate) with a molecular weight of 1965 and a hydroxyl number of 57.1, first adds 7.23 mol of 1,4-butanediol and then 9.99 mol of 4.4 ^l methylene bis (cyclohexyl isocyanate) to the dried polyester mixture and heats it up 80 C. It is carried out in the absence of a catalyst. The homogeneous mass is then heated in an oven to about 122 ° C. to 129 ° C. and kept at this temperature for 19 hours. The polymer obtained has a 0.5% concentration in N-methyl-2-pyrrolidone at 30 ° C. inherent viscosity of about 0.79 and contains 0.1 wt.% NCO. The inherent viscosity does not change with calendering. When grinding the polymer, the front roller has a temperature of .82 C and the rear roller a temperature of 57 C. In the calender, the upper roller has a temperature of 65.5 C, the middle roller a temperature of 57 C and the lower roller a temperature of 51.6 C.

The polyurethanes 3 to 18 are produced from the compounds mentioned in each case in the manner described for polyurethane 1 and under the conditions mentioned there. The inherent viscosity of the polyurethanes is measured at 30 ^° C. on a 0.5% concentrate in N-methyl-2-pyrrolidone, and the NCO content is determined by infrared spectroscopy.

3098 * 2 9/0723

POLYURETHANE 3

1 mole of poly (1,4-butylene adipate) with a molecular weight from 1014 ,. the hydroxyl number 110.7 and the acid number 0.5, 0.905 mol of 1,4-butanediol and 1.905 moles of 4,4'-methylene-bis (cyclohexyl isocyanate).

Reaction time: 19 hours at an oven temperature

Cx

from 130 C,

^ inherent viscosity 1.21, NCO content 0.1%.

POLYURETHANE 4

1 mol of poly (1,4-butylene adipate) with a molecular weight of 1965, hydroxyl number 57.1 and acid number 0.5,
3.26 moles of 1,4-butanediol and 4.26 moles of 4,4'-methylene-bis (cyclohexyl isocyanate).

Reaction time: 24 hours at an oven temperature

of 13O ⁰ C,

inherent viscosity 0.78, NCO content 0.03%.

309829/0723

POLYURETHANE 5

1 mol of poly (1,4-butylene adipate) with a molecular weight of 1965, hydroxyl number 57.1 and acid number 0.5,
2.34 moles of 1,4-butanediol and 3.34 moles of 4,4'-methylene-bis (cyclohexyl isocyanate).

Reaction time: 19 hours at an oven temperature

from 130 - 131 ° C, inherent viscosity 1.03, NCO content 0.07%.

POLYURETHANE 6

1 mole of poly (1,4-butylene adipate) with a molecular weight of 1965, the hydroxyl number 57.1 and the acid number 0.5,
3.40 moles of 1,4-butanediol and 4.40 moles of 4,4'-methylene-bis (cyclohexyl isocyanate)

Reaction time: 23 3/4 hours at an oven temperature

from 129 - 130 ⁰ C,

inherent viscosity 1.06, NCO content 0.1%.

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- «β - '22U595

POLYURETHANE 7

1 mole of poly (1,4-butylcnadipate) has a molecular weight from 1965, the hydroxyl number 57.1 and the acid number 0.5, 3, -11 moles of 1,4-butanediol and 4.11 moles of 4,4'-methylene-bis (cyclohexyl isocyanate).

Reaction time: 19.5 hours at an oven temperature

temperature from 128 - 130 ° C, inherent viscosity 0.84,

POLYURETHANE 8

1 mole of poly (1,4-butylene adipate) with a molecular weight from 1965, the hydroxyl number 57.1 and the acid number 0.5, 2.71 mol of 1,4-butanediol and 3.71 moles of 4,4'-methylene-bis-icyclohexyl isocyanate).

Reaction time: 19 hours at an oven temperature of 130 - 131 ° C, inherent viscosity 0.88.

POLYURETHANE 9

1 mole of poly (1,4-butylene adipate) with a molecular weight from 1965, the hydroxyl number 57.1 and the acid number 0.5, 3.26 mol of 1,4-butanediol and 4.26 moles of 4,4'-methylene-bis (cyclohexyl isocyanate).

Reaction time: 20 hours at an oven temperature of 130 C,

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inherent viscosity 1.02,
NCO content 0.1%.

POLYURETHANE 10 .

1 mole of poly (1,4-butylene adipate) with a molecular weight of 1965, hydroxyl number 57.1 and acid number 0.4,
3.61 moles of 1,4-butanediol and
4.61 Mo1 4,4 * -Methylene-bis- (eye1ohexy1 isocyanate).

• Reaction time: 18 hours at an oven temperature of 130 C-, inherent viscosity 0.72,
NCO content 0.07%.

POLYURETHANE 11

1 mole of poly (ethylene adipate) with a molecular weight of 1902, hydroxyl number 590 and acid number 0.3,
3.51 moles of 1,4-butanediol,

.4.51 moles of 4,4'-methylenebis (cyclohexylisoeyanate), 0.01% dibutyltin dilaurate and 0.6 pph of the under the trademark "Irganox 1093" (Geigy Chemical Corp.) covered multifunctional parts hindered phenols,

Reaction time: 43 hours at an oven temperature of 128 ° C, inherent viscosity 0.84,
NCO content 0.2%.

POLYURETHANE 12

1.76 moles of single molecular poly (1,4-butylene adipate)

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weight of 1010, the hydroxyl number 111.1 and the Acid number 0.5, 1 mol of poly (1,4-butylenedipate) with a molecular weight from 1965, the hydroxyl number 57.1 and the acid number 0.5, 7.36 moles of 1,3-butanediol and

10.11 mol of 4,4'-methylene-bis (cyclohexyl isocyanate) with a stereoisomer content of 70% trans and 30% ice ("Nacconate H-12").

Reaction time: 17 1/2 hours at an oven temperature of 130 ° C., inherent viscosity 0.62, NCO content 0.03 %.

- \ POLYURETHANE 13

1 mol of poly (diethylene glycol) adipate) with a molecular weight of 1007, a hydroxyl number of 111.4 and an acid number of 1.8, 2.53 mol of 1,4 ^ butanediol, 3.53 mol of toluene diisocyanate (80/20 mixture of 2.4 - 2, 6 isomers) and 0.01 % dibutyltin dilaurate.

Reaction time: 19 hours at an oven temperature of 130 C; Temperature of the reaction vessel 138-142 ° C; catalyst

dissolved in the diisocyanate; Addition at 40 C; no degassing.

Inherent viscosity 0.85, NCO content 0.01 %.

POLYURETHANE 14

1 mole of poly (ethylene / propylene adipate) with a MoIe-

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Weight from 1886, the hydroxyl number 59.5 and the acid number 0.6,
3.49 moles of 1,4-butanediol,

.4.49 moles of 4.4 ^f -ethylene bis (cyclohexyl isocyanate) 0.01% dibutyltin dilaurate and

0.6 pph of the multifunctional under the trademark "Irganox 1093" (Geigy Chemical Corp.) hindered phenols.

Reaction time: 21 hours at an oven temperature of 130 C; Catalyst dissolved in the diisocyanate. Inherent viscosity 0.87,
NCO content Ό, Ι%.

POLYURETHANE 15

1 mole of poly (1,6-hexylene adipate) with a molecular weight of 1032, the hydroxyl number 108.7 and the acid number 0.2,

2.61 moles of 1,4-butanediol and

3.61 mol of a toluene diisocyanate consisting of 80 "L 2,4-isomers and 20% 2,6-isomers.

Reaction time: 19 hours at an oven temperature of 130 C; no degassing; Addition of the diisocyanate a temperature of the mixture of 60 C; inherent viscosity 0.25. . ''

POLYURETHANE 16

1 mol poly (1,4-butylene azelate) with a molecular weight of 1925, hydroxyl number 58.3 and acid number 0.5,
4.55 moles of 1,4-butanediol and

3098 2 9/0723

5.55 moles of a toluene diisocyanate consisting of 80% 2,4-isomers and 20% 2,6-isomers.

Reaction time: 20 1/2 hours at an oven temperature of 126-130 C; no degassing; Polymer caused by the yellow polyester is slightly yellow in color; Polymer contains some vesicles; Beginning of the addition of diisocyanate at a temperature of the mixture of 50 ⁰ C; inherent viscosity 0.56; NCO content 0.8%.

POLYURETHANE 17

1 mole of poly (caprolactone) with a molecular weight of 1233, hydroxyl number 91 and acid number 0.02, 3.05 moles of 1,4-butanediol and

4.05 moles of 80% 2,4-isomer and 20% 2,6-isomer existing toluene diisocyanate.

Reaction time: 17 3/4 hours at an oven temperature of 97 C; no degassing and no continuous Purging with nitrogen; Beginning of the addition of diisocyanate at a temperature of the mixture of 36 C; inherent viscosity 1.73i

POLYURETHANE 18

1 mole of poly (caprolactone) with a molecular weight of 850; the hydroxyl number 132 and the acid number 0, 2.58 moles of 1,4-butanediol and

3.58 moles of toluene diisocyanate consisting of 80% 2,4-isomers and 20% 2,6-isomers.

Reaction time: 26.5 hours at an oven temperature from 92 to 100 ⁰ C; no continuous purging of the furnace with nitrogen; Beginning of the addition of diisocyanate at a Tpmnprahtr Hp, s mixture of 38 C,

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224459b

clear polymer, but containing gas bubbles; inherent viscosity 0.61, measured on a 0.5% concentrate in dimethylformamide at 30 C.

The polyurethanes 19 to 27 x ^ ground in a circulating air oven 20th

threw.

oven for 20 hours of heat treatment at 143 ° C.

309629/072 3

- -s * - '224-595

POLYURETHANE 19

Following the procedure and conditions of Example 1, 1 mole of one of 1,4-butanediol and adipic acid is mixed produced polyester with a molecular weight of 3271, the hydroxyl number 34.3 and the acid number 0.1 with 5.737 moles of anhydrous 1,4-3utanediol under nitrogen at a temperature of about 104 ° C and continues the mixture with vigorous stirring 6.737 mol of 4,4'-methylene-bis (cyclohexyl isocyanate) increases rapidly at a temperature of about 95 ° C. During the addition of the 4,4'-methylene-bis (cyclohexyl isocyanate) the temperature goes back to 77 ° C. The mixture is degassed by reducing the pressure within a few Minutes gradually reduced to 6.5 mm Hg, it is in the reaction vessel and puts this under nitrogen in a fresh air oven where it is kept at a temperature of 130 ° C for 23 hours. One takes then the cloudy urethane out of the reaction vessel and extruded, crushed and calendered it.

POLYURETHANE 20

Example 19 is repeated with the difference that one the reaction mixture is added 0.017 pounds of dibutyltin dilaurate over the course of two minutes while stirring vigorously. While During this time the temperature rises from 69 ° to 95 ° C. The mixture is then placed in a polytetrafluoroethylene

¹ I,

len coated reaction vessel, place it in a

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224A595 ti

Fan oven and keeps it there for 3 hours 143 ° C. A clear urethane with an NCO content is obtained of 0.03%.

The urethanes obtained according to the examples (with the exception of example 19) correspond in their light transmittance and in their degree of cloudiness the minimum requirements applicable to automobiles (ANSI Code Z-26.11966, attempt 18). .

Exam Results -. .

In the event of a collision at a speed of 40.2 km / h, conventional, - from two 3.175 mm strong float glass panes and a 0.762 mm thick plasticized polyvinyl butyral intermediate layer. found three-layer windshields to have an average cut grade of 3.2. In comparison this can be seen from the following table that those produced with the urethanes according to the examples double-layer windshields except for one cut at an impact speed of 51.2 km / h 1 show. In the table, F denotes a float glass with a thickness of 3.175 mm; V. p.lastified Polyvinyl butyral and P a polyester type polyurethane. . ■. · '

309829/07 2 3,

(i

22-595

TABEL

Composition- degree of cut injury the wind impact strength of the windshield speed plastic <(km / h) shift (mm)

FVF
PF

V-F

V-F

V-F

40.2 (avg.)

49.2

49.4

42.5

38.8

48.7

38.3

23.9

42

50.4

40.7

45.9

48.7

51.2

39.2

39.7

40.9

35.7

39.9

0.762 0.762 0.762 0.762 0.762 1.524 1.524 1.524 1.143 1.143 1.143 0.762 0.762 0.762 0.762 0.762 0.762 0.762 0.762 0.762 0.762

3.2 (avg.)

309829/0723

■ 22U595 69

In the drawing shows:

Figure 1

in section the assembly of a glass pane used as a mold, a prefabricated one, the inside Layer of a two-layer windshield forming plastic film and the outer layer a two-layer windshield forming glass pane and in particular the arrangement of the Separation material existing layer;

Figure 2. ·

also in section, with separated glass pane shape, an embodiment which is particularly typical for the use of a prefabricated polyvinyl butyral film a two-layer windshield according to the invention;

Figure 3

also in section a modified embodiment of the windshield according to FIG. 2; "

Figure 4

also in section a multilayer windshield which can be produced according to the invention;

309829/0723

Figure 5. '

in perspective the assembly of a sheet of glass used as a mold, one for use as the inner layer of a two-layer windshield cut to size polyurethane film and one as the outside layer of a two-layer windshield used another pane of glass;

Figure 6

on the embodiment shown in section on the line VI-VI according to Figure 5, the insertion of a cutting tool in the circumferential groove surrounding the pane of glass used as the mold;

Figure 7

in perspective view the insertion of a razor blade in the peripheral groove for the purpose indicated by the To deepen groove given separation between the mold and the two-layer windshield;

Figure 8

a representation similar to that of Figure 7, in which a pizza cutter is used as a cutting tool and

Figure 9

the lifting of the glass pane used as a shape from the manufacture two-layer windshield after the two elements have been applied to those shown in Figure 7 and in Figure 8 Way have been pre-separated.

309829/0723

In the illustration according to FIG. 1, a glass pane 10 with a convexly curved outer surface 11 lies with its concave surface inner surface of a prefabricated plastic film 12, while one preferably made of chemically annealed Glass existing form 14, which has the same curvature as the glass pane 10, the film on the other Side covers. Between the mold 14 and the prefabricated film 12 is a layer 16 made of a suitable one Release agent inserted.

Figures 2 and 3 show two forms of application of the after Invention usable release material. In Figure 2, the release material 16 is made of a film about 0.0254 mm thick Polyvinylidene fluoride. According to FIG. 2, the separating agent layer 16 remains with the inside when the mold 14 is lifted off Plastic layer 12 of the two-layer windshield connected. If you have 12 polyvinyl butyral for the plastic layer used, it must be protected against direct contact with moisture. In this case it serves The release agent layer serves a dual purpose, i.e. it acts as a release agent during lamination and as a Protective layer after lamination.

Around the layer 16, if it is to be used as a protective coating on the plastic film 12, one of wrinkles To give a free, smooth surface, they are pressed before they are placed between the mold and the two elements of the two-layer windshield inlay, under one Pressure of at least 7 kg / cm2 at a temperature · the

309829/0723

comes close to its softening point and, depending on the material of which it is made, between 37.8 ° and 93.3 ° C. The prefabricated plastic film 12 has the required smooth surface, if it is inserted between the two panes of glass during lamination. Moreover, that of the shape 14 ranges from the one side and the pressure exerted on it by the pane of glass 12 from the other side, both of them To keep surfaces smooth.

According to FIG. 3, the separating layer 16 is firmly connected to the glass fiber 14 in the form of a thin film, for example a coating of a metal oxide such as tin oxide, indium oxide or titanium oxide, or a coating of a glass resin mentioned elsewhere. If the films are produced, as is the case with thin films made of metals, metal alloys or metal oxides, by cathodic sputtering or by spraying or flooding with subsequent baking, a temperature is required in order to bond the film to the glass, which is well below the softening point of the Substrate lies. There is thus no change in shape of the pane 14, which consequently continues to correspond in its shape to the pane 10 which becomes the part of the curved two-layer windshield and which is produced with a separating layer of the type mentioned.

In the embodiment according to FIG. 3, the separating layer 16 remains connected to the mold 14 when it is removed from the laminate

309829/07 2 3

detached windshield. The two-layer windshield consists essentially of an outer glass layer 10 with the convex Surface 11 and an inside, that is, the inside of a car facing plastic film 12 with the concave surface 17. Although the shape 14 The glass sheet that forms it is so hard that its shape does not change when it is placed on the sheet 12 is pressed on, on the other hand it is at the same time so flexible that it can be opened after! .lamination of Can be detached from the two-layer laminate by hand with a separator. Is critically important therefore that the separating layer applied to the mold 14 is so thin that the mold does not lose its flexibility, that is, it can easily be detached from the curved two-layer windshield.

If a prefabricated plastic film is combined with a pane of glass to produce a two-layer windshield ^{, the surface of the film facing der.Form 1} is reproduced after the amination of its surface texture. If there is a separating layer between the mold and the plastic layer that closes off a laminate on the inside, it is necessary for the separation to take place because of the intimate contact between the separating layer connected to the mold and the plastic film. begin at the periphery and proceed inward from here. Decisive for an appropriate one, that is, for one without. Damage to the optical properties

stick to the windshield in your field of vision separation carried out, is the way how to start it. When starting the separation from the edge the surface of the film in the edge zone can be damaged. However, if you take care that damage of the film remain limited to its edge zone, and not to the field of vision of the windshield overlapping, they are without disadvantages and tolerable, especially since the windshield during assembly with their Edge zone is let into the window frame of a vehicle, so the edge zone is hidden in the frame.

For the embodiment according to FIG. 3, flexible, preferably about 1.27 to 6.35 mm thick and chemically tempered to increase their breaking strength.

Obtained by the chemical tempering, the mold 14 forming the glass sheet increased flexibility and greater breaking strength _t so that it can be reused many sharks.

When making transparent laminates with a Inside polyurethane layer, the form can of course also consist of a material other than glass, especially if the polyurethane is in the form a prefabricated foil is used. However, one must such a form not made of glass one to the glass

309829/0723

have suitable thermal expansion coefficients, so they do not expand or contract in some places to a very different degree from the glass can. If you disregard that, the manufactured plastic film pressed on differently in different places with the result that Adjust optical distortions.

If the method described above is also used for the production of two-layer windshields is particularly suitable for automobiles, you can of course then with the same good result. ■ Also make laminates with more than one layer of transparent material by, from a two-layer Starting from the laminate, on the side of the prefabricated film, additional layers of glass and alternating sequence other foils laminated on. Take a car windshield as an example of conventional design, made of two glued together by a plastic layer Glass panes and a further, inside plastic squint consists. In the drawing, this embodiment is through Figure 4 is shown. FIG. 4 shows a multi-layer, transparent laminate made from an inside exposed plastic layer 12 with the concave inner surface 17, a glass layer 10 with the convex outer surface 11 and between them an additional Glass layer 18 and an additional layer of plastic 19.

3098 2 9 / Ö723

Both the two-layer and the multi-layer windshields can be used on the contact surfaces Apply an adhesive to the glass and plastic layers.

In FIGS. 5 to 9 of the drawing there is a glass pane 10 with a convex outer surface 11 and one of the concave ones inner side opposite prefabricated polyurethane film 12 shown. Further, one therein is preferable Form 14 made of chemically tempered glass and corresponding in its curvature to the glass pane 10 shown, the on its convex surface 16 a coating of a suitable release agent, for example an in situ baked overcoat of the commercially available Owens-Illinois Glass Resin T-650 available glass resin.

At its edge 20, the mold 14 is along its circumference provided with an inclined bevel 22 running towards its convex side, the surface of which together forms a groove with the opposite part of the polyurethane film. In the drawing is the bevel shown with a flat ground surface. In the same way as a flat cut, however, a hollow cut also fulfills the purpose associated with the groove, which is that, as shown in Figures 6 and 7, one enters the groove Separating tool, for example a razor blade 24, is used and with this the through the approximately 1.587 mm deep and a groove about 3.175 mm wide.

309829/0723

Before the form 14 and the laminate consisting of the polyurethane film 12 and the glass pane 10 'finally'. · ' separates from each other, one loosens the two elements, as shown in Figure 8, with a pizza cutter 26, the consists of a rot'baren separating disk 28 and a handle 30, further from each other.

When the opening made with the pizza cutter 26 is wide enough for a finger to be inserted, is placed on the surface 11 of the glass pane 10 of the two-layer Laminate to a suction plunger 32 and insert one or more fingers into the opening into it. Thanks to its flexibility, the glass pane forming the form 14 can easily be removed from the polyurethane film by hand lift off the laminate.

If desired, the surface 22 and the edge surface can be leashed 20 cover the mold 14 with a separating material, for example with a tape made of commercially available polytetrafluoroethylene under the name TEFLON. This protects before that the polyurethane film sticks at the edge to the mold 14 if the separating layer does not reach the mold 14 covered the edge. The tape also protects the edge of the. Form against damage by the cutting tool.

If in the preceding description the invention, also on essentially consisting of a glass layer on the outside and a polyurethane layer on the inside

309829/0723

- vs- 22U595

layered laminates has been shown, so can other rigid, transparent bodies, for example those made up of multiple sheets of glass and multiple layers of transparent plastic, for example a polycarbonate or an acrylic ester, which form the outer layer of a laminate and which the layer of the laminate facing the mold be a stretchable plastic, preferably a thermoplastic plastic, that would stick to the mold, no separating layer would be inserted between it and the mold.

For the purposes of the invention, the plastic films are expediently used in a uniform thickness of, for example no more than 0.127 mm with a difference of preferably less than 0.0254 mm between locations greatest and smallest thickness. "Too great a difference in strength causes optical distortion.

The flexibility of the shape depends on its strength. One Glass used as a mold should have a thickness of 1.27 to 6.35 mm. While thicker slices because of Due to their lack of flexibility, they cannot be removed from a plastic layer easily enough thinner slices difficult to handle because of their fragility.

The excellent properties of the laminates according to the invention are the result of several factors. First allows the uniform thickness of the prefabricated

309829/0723

Plastic film that the glass pane to be connected to the film and the shape are the same from the start Distance can be brought to each other. Then reduce the. Use a shape that is in their. . Curvature and, in the case of the!, Amination normally applied temperature range, in their physical properties, for example in their thermal expansion coefficient, their Young's modulus and their hardness coincide with the glass pane of the laminate, the risk of a Deformation which occurs during the amination on the finished plastic film could transfer. It is preferable to use a mold made of a material that is compatible with the Material of the curved disc of the laminate matches as closely as possible.

Even if glass is the preferred material for the shape the mold can be made of any other material that is at the lamination temperature harder than the plastic, has a smooth surface, can be bent at room temperature, like Metals, alloys and other substances have physical properties that are reflected in the lamination process applied temperature range with those of the glass can be tolerated and brought into a rigid form that corresponds to the shape that the smooth surface of the plastic film of the "two-layer windshield" should assume.

A two-layer wind turbine produced according to the invention

30982970723

The characteristic shape of a protective window for automobiles consists of a pane of glass on the outside from a thickness of 1.27 to 6.35 mm, preferably from a thickness of about 1.651 to 3.175 mm and an inside Polyurethane layer of a thickness of 0.0254 to 2.54 mm, preferably of a thickness of about 0.762 to 1.524 now. The surface of the polyurethane film turned into the interior of the car is within the field of vision The windshield is smooth and closes by itself if it is scratched.

309829/0723

Claims (2)

Patent claims: 1. Method of making a laminated trans-. parent and curved glazing material a smooth plastic film and, connected to this to form a laminate, made of a curved one A sheet of glass using a prefabricated sheet made of a thermoplastic resin of approximately uniform thickness and a curved sheet of glass placed on top of each other and this laminate is combined under pressure to form a laminate at elevated temperature, characterized in that that the prefabricated plastic film is brought into contact with a shape, face against face, those within the temperature range used for lamination are harder than the prefabricated ones Foil has a shaping surface that resembles the shape of the curved glass pane of the laminate - Corresponds, and their physical properties in the during the manufacture of the glass-plastic laminate Applied temperature range compatible with those of the curved glass pane of the laminate are; between the mold and the prefabricated film used to make the laminate "a layer of a release material-inserts and that the mold is detached from the plastic film after the lamination is complete. 309829/0723 .2. Process according to Claim 1, characterized in that the lamination is carried out under a pressure of more than 3.5 kg / cm ² at a temperature of 93.3 to 204.4 ° C and the pressure used and the temperature used before removal the form diminishes. 3. The method according to claim 1 or 2, characterized in that the release agent layer under the at the temperature and pressure conditions prevailing during the lamination process with the prefabricated plastic film connects and separates from the shape together with the prefabricated film and the curved glass pane. 4. The method according to claim 1 or 2, characterized in that the release agent layer is made of a material consists that during lamination on the surface of the mold, but not on the plastic film, adheres. 5. The method according to claim 3, characterized in that that a thermosetting organopolysiloxane is used as a release agent used. 6. The method according to claim 5, characterized in that that the organopolysiloxane is a methyltrialkoxysilane or a mixture of a methyltrialkoxysilane and is a phenyltrialkoxysilane, wherein the alkoxy group contains less than five carbon atoms. 309829/0723 .-a * - 224A595 7. The method according to claim 4, characterized in that that you act as a separating layer on the surface metal oxide coating applied to the mold. 8. Method according to claims 1 to 4, characterized in that that the plastic film consists of a pole} '' -. vinyl butyral resin. 9. The method according to claim 1 to 4, characterized in that the plastic film consists of a polyurethane resin. 10. The method according to claim 1 to. 9, characterized in that the shape is a prefabricated sheet of glass. 11. The method according to claim 10, characterized in that that the glass pane used as a shape before it comes into contact with the plastic film without loss of shape * Chemically tempered to increase its breaking strength will. 12. The method according to claim 11, characterized in _t that the glass plate used as a mold as the 'same thickness as that of the curved glass plate, which is combined with the pre-made plastic film to form a laminate. ■ 309 829/0723 -> * - 22U595 91 13. The method according to claim 1 to 12, characterized in that that one for the. !. lamination with the plastic film accordingly the shape that the window to be made with the glazing material should have, bends and that the prefabricated plastic film is laminated to the glass pane on its concave side. 14. The method according to claim 1 to 13, characterized in that one before the merging of the prefabricated Glass pane and the prefabricated plastic film at least one of the opposite Coated surfaces with an adhesive. 15. The method according to claim 1 to 14, characterized in that the glass pane to be combined with the prefabricated plastic film to form a laminate is connected with its opposite side to a further trans - - .parent plastic film is laminated on. 16. The method according to claim 1 to 15, characterized in that the glass pane intended for the laminate has a uniform thickness of about 1.27 to 6.35 mm and the prefabricated plastic film has a uniform thickness of about 0.0254 to. 2.54 mm. 309829/0723 "17. The method according to claim 1 to 16, characterized in that that the shape is given a bevel along its edge to match that of him opposite part of the film forms a groove, and that one in this groove is to be removed the shape of the plastic film serving separating tool is used. 18. The method according to claim 17, characterized in that that the width and depth of the groove are dimensioned so that their baseline does not enter the field of vision the windshield consisting of the film and the curved glass pane protrudes. 19. A mold for use in making a laminated transparent windshield according to claim 1 to 18, which are included in the lamination process below Pressure on a plastic film of the windshield., Characterized by a flexible part, the temperature range used for amination harder than the foil with which it touches and in the shape of its surface coincides with the shape of the two-layer windshield to be produced, and by one on its side facing the film applied coating of one in the alkoxy groups less than five carbon atom-containing methyltrialkoxysilane or methyltrialkoxysilane-phenyltrialkoxysilane. Mixture introduced into the surface of the mold. 3098 29/07 2 3 22-595 20. A mold for use in the manufacture of a laminated transparent windshield according to claim 1 to 18, which are placed under pressure on a plastic film of the windshield during the lamination process. 'is characterized by a flexible part, which is in the temperature range used in the lamination is harder than the foil with which it touches and in the shape of its surface with the . Shape of the two-layer windshield to be produced matches, and by one along their pe: q> higher edge running bevel, which forms a groove with the part of the film opposite it and when the mold is detached from the Plastic film is used to insert a cutting tool. 309829/0723