WO1998017468A1 - Method for producing laminated safety glass windows - Google Patents

Method for producing laminated safety glass windows Download PDF

Info

Publication number
WO1998017468A1
WO1998017468A1 PCT/DE1997/002409 DE9702409W WO9817468A1 WO 1998017468 A1 WO1998017468 A1 WO 1998017468A1 DE 9702409 W DE9702409 W DE 9702409W WO 9817468 A1 WO9817468 A1 WO 9817468A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
silicon
silane
panes
polyvinyl alcohol
Prior art date
Application number
PCT/DE1997/002409
Other languages
German (de)
French (fr)
Inventor
Michael Henkel
Manfred Hoss
Bernhard Koll
Karl-Heinz Spiess
Original Assignee
Ht Troplast Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ht Troplast Ag filed Critical Ht Troplast Ag
Priority to DE19781146T priority Critical patent/DE19781146D2/en
Priority to AU53976/98A priority patent/AU5397698A/en
Publication of WO1998017468A1 publication Critical patent/WO1998017468A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B32B17/10825—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts
    • B32B17/10834—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid
    • B32B17/10844—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid using a membrane between the layered product and the fluid
    • B32B17/10853—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid using a membrane between the layered product and the fluid the membrane being bag-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds

Definitions

  • the invention relates to a method for producing composite security panes, consisting of at least two glass panes and an intermediate layer made of partially acetalized polyvinyl alcohol containing plasticizer, in a one-step, autoclave-free process.
  • Composite safety panes consisting of two glass panes and an adhesive film connecting the glass panes, preferably made of polybutyral (PVB), are used in particular as windscreens in motor vehicles, with a glass pane possibly being replaced by a plastic pane, primarily made of an amorphous polyamide, transparent PMMA, polycarbonate or polyester can be.
  • a glass pane possibly being replaced by a plastic pane, primarily made of an amorphous polyamide, transparent PMMA, polycarbonate or polyester can be.
  • silicate glass / silicate glass or silicate glass / plastic composites are used, where appropriate depending on their use, e. B. as composite armored glass, also multiple composites, ie composites that consist of more than two load-bearing layers, can be used.
  • a two-stage manufacturing process is generally used for the production of composite safety disks.
  • a so-called pre-composite consisting of the two glass panes and the adhesive film arranged between them, usually made of PVB, is produced.
  • This pre-composite is pressed in a second process step in an autoclave at temperatures of approx. 130 - 145 ° C and pressures of at least 11 bar to the actual composite safety disc.
  • This method is described, for example, in the introduction to EP 0 331 648 A2.
  • the water content of the PVB film used significantly influences the bond strength of the composite.
  • a water content of 0.40 to 0.55% by weight of the film is usually maintained - with very small tolerances. Due to the use of an autoclave, this known two-stage process is relatively complex and requires a high investment, so that it is unprofitable for small production quantities.
  • EP 0 331 648 A2 discloses an autoclave-free method of this type for producing composite safety disks.
  • the glass panes are glued together with the intermediate PVB film in an airtight, evacuated sack at elevated temperature by the external air pressure.
  • the PVB film used should have the lowest possible water content in order to avoid bubbles in the composite.
  • the adhesion that can be achieved between the layers of the composite, especially for the construction sector is not always sufficiently high.
  • DE 24 10 153 C3 discloses a method for adjusting the adhesive force of plasticized partially acetalized polyalcohols with silicon-functional and silicon-organofunctional silanes, the silicon-functional silanes reducing the adhesion and the silicon-organofunctional silanes increasing the adhesion.
  • the effect is not very high in normal processes.
  • the object of the present invention is a process for the production of composite safety glass, consisting of at least two glass panes and an intermediate layer of weichma ⁇ cher Reginam partially acetalized polyvinyl alcohol, m a single-stage, autoklavenUF method for jointing to provide that with sufficient process safety bubble-free laminated safety glass high liability, which in particular meet the requirements for the construction sector.
  • the invention achieves this object by using a plasticizer-containing partially acetalized polyvinyl alcohol film with a water content of less than 0.35% by weight, based on the mass of the film, and an effective content of an adhesion-increasing silicon-organofunctional silane in a one-step, autoclave-free process.
  • the partially acetalized polyvinyl alcohols can be prepared in a manner known per se by saponification of polyvinyl acetate and subsequent acetalization with aldehydes, such as, for. B. formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like. the like getting produced. They usually still contain about 0.5 to 5 percent by weight, in particular about 0.5 to 1.2 percent by weight, of acetyl groups, calculated as vinyl acetate residues. Other polyvinyl esters of aliphatic acids with up to 9 carbon atoms can also be saponified and then acetalized. Partialized polyvinyl alcohol (PVB) is preferred. With regard to the polymers that can be used, reference is also made to DE 24 10 153 C3.
  • the film used for the process according to the invention contains plasticizers in amounts of preferably 20 to 40% by weight.
  • plasticizers that can be used are triethylene glycol di (2-ethylbutyrate), di-n-hexyl adipate (DHA) and preferably triethylene glycol bis-n-heptanoate (3G7).
  • the water content of the adhesive film is adjusted to a value of less than 0.35% by weight, preferably equal to or less than 0.30% by weight, in each case based on the mass of the film.
  • the water content to be observed according to the invention serves, on the one hand, to avoid bubbles in the finished composite safety panes, and together with the added silicon-organofunctional silanes, it also synergistically influences the adhesion between the adhesive film and the glass panes.
  • the silicon-organofunctional silanes used to increase the adhesion are known per se, for example from DE 24 10 153 C3, so that reference can be made to this document. While the addition of silicon organofunctional silanes which increase the adhesion in the customary autoclave process only brings about a moderate increase in the adhesion of film / glass, it has surprisingly been found that the same silane compounds have a multiple-fold effect when using an autoclave-free process. This is illustrated below using examples and comparative examples as well as the drawing.
  • Fig. 1 shows the pressure and temperature curve vs. Time according to Examples 1, 2 and Comparative Example 3
  • Fig. 2 shows the pressure and temperature curve vs. Time according to comparative examples 4 to 6
  • Fig. 3 is a schematic representation of an experimental device for a compression shear test.
  • a PVB adhesive film roughened on both sides is produced by a method according to EP 0 185 863 B1, Example 1.
  • Triethylene glycol bis-n-heptanoate (3G7) is used as the plasticizer.
  • a ⁇ -aminopropyltriethoxysilane is added to the plasticizer as silicon-organofunctional silane in an amount of 0.03% by weight, based on the mass of the film.
  • the water content of the PVB adhesive film was set at 0.29% by weight.
  • Two flat silicate glass sheets and the PVB adhesive film are then kuum vide in a single stage, autoklavenpli ⁇ Va, as described in EP 0331648 A2, processed into a laminated safety glass.
  • the process parameters were as follows: Table 1
  • Composite safety panes are produced by the same method as in Example 1, but using di-n-hexyl adipate (DHA) as a plasticizer.
  • DHA di-n-hexyl adipate
  • Composite safety panes are produced using the same procedure as in Example 1, but no silane is used.
  • the laminated safety glass thus produced are subjected to a standard compression shear test that allows a quantita tive ⁇ assessment of the glass / film adhesion.
  • the composite safety washers to be tested are clamped at an angle of 45 ° in a two-part test apparatus.
  • the obe ⁇ re half is exactly vertically subjected to a steadily increasing, downwardly directed force until tion to a Absche ⁇ within the test specimen, that is to be tested laminated safety glazing, comes.
  • the test device used for this is shown schematically in FIG. 3.
  • the test parameters were as follows:
  • the force exerted during shear is averaged from ten identical test specimens.
  • the standard deviation of the individual measurements is also calculated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The present invention relates to a method for producing in one step laminated safety glass windows made of at least two glass panes and a partially acetalised polyvinyl-alcohol interlayer containing a plasticizer. According to the non autoclave method, a foil of partially acetalised polyvinyl alcohol is used which contains a plasticizer and less than 0.35 w-t % of water in relation to the foil mass and an effective quantity of functional organosilicone which increases adhesion.

Description

Verfahren zur Herstellung von VerbundsicherheitsScheiben Technisches GebietProcess for the production of composite safety disks Technical field
Die Erfindung betrifft ein Verfahren zur Herstellung von Ver- bundsicherheitsscheiben, bestehend aus zumindest zwei Glas- Scheiben und einer Zwischenschicht aus weichmacherhaltigem teilacetalisiertem Polyvinylalkohol, m einem einstufigen, autoklavenfreien Verfahren.The invention relates to a method for producing composite security panes, consisting of at least two glass panes and an intermediate layer made of partially acetalized polyvinyl alcohol containing plasticizer, in a one-step, autoclave-free process.
Verbundsicherheitsscheiben, bestehend aus zwei Glasscheiben und einer die Glasscheiben verbindenden Klebefolie, vorzugsweise aus Polyvmylbutyral (PVB) , werden insbesondere als Windschutzscheiben m Kraftfahrzeugen eingesetzt, wobei gegebenenfalls eine Glasscheibe durch eine KunststoffScheibe, vornehmlich aus einem amorphen Polyamid, transparentem PMMA, Polycarbonat oder Polyester, ersetzt sein kann. Auch auf dem Bausektor, z. B. als Fensterscheiben oder als Zwischenwände, werden solche Silikat- glas/Silikatglas- bzw. Silikatglas/Kunststoff-Verbunde eingesetzt, wobei gegebenenfalls j e nach ihrer Verwendung, z. B. als Verbundpanzerglaser, auch Mehrfachverbunde, also Verbünde, die aus mehr als zwei tragenden Schichten bestehen, eingesetzt wer- den.Composite safety panes, consisting of two glass panes and an adhesive film connecting the glass panes, preferably made of polybutyral (PVB), are used in particular as windscreens in motor vehicles, with a glass pane possibly being replaced by a plastic pane, primarily made of an amorphous polyamide, transparent PMMA, polycarbonate or polyester can be. Also in the construction sector, e.g. B. as window panes or as partitions, such silicate glass / silicate glass or silicate glass / plastic composites are used, where appropriate depending on their use, e. B. as composite armored glass, also multiple composites, ie composites that consist of more than two load-bearing layers, can be used.
Wahrend Verbundsicherheitsscheiben für den Baubereich l.a. eine möglichst hohe Haftung zwischen Glas und Klebefolie aufweisen sollen, wird für Verbundsicherheitsscheiben für Kraftfahrzeuge eine definierte, nicht zu hohe Haftung angestrebt.While composite safety washers for the construction area l.a. In the case of composite safety panes for motor vehicles, a defined, not too high liability is sought for the highest possible adhesion between glass and adhesive film.
Stand der TechnikState of the art
Für die Herstellung von Verbundsicherheitsscheiben wird allgemein em zweistufiger Herstellungsprozeß eingesetzt. In einem ersten Schritt wird ein sogenannter Vorverbund, bestehend aus den beiden Glasscheiben und der dazwischen angeordneten Klebe- folie, üblicherweise aus PVB, angefertigt. Dieser Vorverbund wird m einem zweiten Prozeßschritt m einem Autoklaven bei Temperaturen von ca. 130 - 145°C und Drucken von mindestens 11 bar zu der eigentlichen Verbundsicherheitsscheibe verpreßt. Dieses Verfahren wird beispielsweise der Einleitung der EP 0 331 648 A2 beschrieben. Der Wassergehalt der verwendeten PVB-Folie beeinflußt die Klebkraft des Verbundes maßgeblich. Üblicherweise wird ein Wassergehalt von 0,40 bis 0,55 Gew.-% der Folie - mit sehr geringen Toleranzen - eingehalten. Bedingt durch den Einsatz eines Autoklaven ist dieser bekannte Zweistu- fen-Prozeß relativ aufwendig und erfordert eine hohe Investiti- on, so daß er für kleine Produktionsmengen unrentabel ist.A two-stage manufacturing process is generally used for the production of composite safety disks. In a first step, a so-called pre-composite consisting of the two glass panes and the adhesive film arranged between them, usually made of PVB, is produced. This pre-composite is pressed in a second process step in an autoclave at temperatures of approx. 130 - 145 ° C and pressures of at least 11 bar to the actual composite safety disc. This method is described, for example, in the introduction to EP 0 331 648 A2. The water content of the PVB film used significantly influences the bond strength of the composite. A water content of 0.40 to 0.55% by weight of the film is usually maintained - with very small tolerances. Due to the use of an autoclave, this known two-stage process is relatively complex and requires a high investment, so that it is unprofitable for small production quantities.
Aus der EP 0 331 648 A2 ist ein gattungsgemaßes autoklavenfreies Verfahren zur Herstellung von Verbundsicherheitsscheiben bekannt. Bei diesem bekannten Verfahren werden die Glasscheiben mit der zwischenliegenden PVB-Folie m einem luftdichten, eva- kuierten Sack bei erhöhter Temperatur durch den äußeren Luftdruck zusammengeklebt. Aus dieser Schrift ist ebenfalls bekannt, daß die verwendete PVB-Folie zur Vermeidung von Blasen im Verbund einen möglichst geringen Wassergehalt haben sollte. Allerdings ist die erreichbare Haftung zwischen den Schichten des Verbundes, insbesondere für den Baubereich, nicht immer ausreichend hoch.EP 0 331 648 A2 discloses an autoclave-free method of this type for producing composite safety disks. In this known method, the glass panes are glued together with the intermediate PVB film in an airtight, evacuated sack at elevated temperature by the external air pressure. It is also known from this document that the PVB film used should have the lowest possible water content in order to avoid bubbles in the composite. However, the adhesion that can be achieved between the layers of the composite, especially for the construction sector, is not always sufficiently high.
Aus der DE 24 10 153 C3 ist ein Verfahren zur Einstellung der Haftkraft von weichmacherhaltigen teilacetalisierten Polyvmyl- alkoholen mit siliciumfunktionellen und silicium-organofunktio- nellen Silanen bekannt, wobei die siliciumfunktionellen Silane die Haftung mindern und die silicium-organofunktionellen Silane die Haftung erhohen. Der Effekt ist bei üblichen Prozessen allerdings nicht sehr hoch.DE 24 10 153 C3 discloses a method for adjusting the adhesive force of plasticized partially acetalized polyalcohols with silicon-functional and silicon-organofunctional silanes, the silicon-functional silanes reducing the adhesion and the silicon-organofunctional silanes increasing the adhesion. However, the effect is not very high in normal processes.
Aufgabe Aufgabe der vorliegen Erfindung ist es, ein Verfahren zur Herstellung von Verbundsicherheitsscheiben, bestehend aus zumindest zwei Glasscheiben und einer Zwischenschicht aus weichma¬ cherhaltigem teilacetalisiertem Polyvinylalkohol, m einem einstufigen, autoklavenfreien Verfahren zur Verfugung zu stellen, das mit ausreichender Prozeßsicherheit zu blasenfreien Verbund- sicherheitsscheiben hoher Haftung fuhrt, die insbesondere die Anforderungen für den Baubereich erfüllen.OBJECT The object of the present invention is a process for the production of composite safety glass, consisting of at least two glass panes and an intermediate layer of weichma ¬ cherhaltigem partially acetalized polyvinyl alcohol, m a single-stage, autoklavenfreien method for jointing to provide that with sufficient process safety bubble-free laminated safety glass high liability, which in particular meet the requirements for the construction sector.
Darstellung der ErfindungPresentation of the invention
Die Erfindung lost diese Aufgabe durch die Verwendung einer weichmacherhaltigen teilacetalisierten Polyvmylalkohol-Folie mit einem Wassergehalt von weniger als 0,35 Gew.-%, bezogen auf die Masse der Folie, und einem wirksamen Gehalt eines die Haftung erhöhenden silicium-organofunktionellen Silans in einem einstufigen, autoklavenfreien Verfahren.The invention achieves this object by using a plasticizer-containing partially acetalized polyvinyl alcohol film with a water content of less than 0.35% by weight, based on the mass of the film, and an effective content of an adhesion-increasing silicon-organofunctional silane in a one-step, autoclave-free process.
Die teilacetalisierten Polyvinylalkohole können in an sich bekannter Weise durch Verseifung von Polyvinylacetat und anschließende Acetalisierung mit Aldehyden, wie z. B. Formaldehyd, Acetaldehyd, Propionaldehyd, Butyraldehyd u. dgl . hergestellt werden. Sie enthalten meist noch etwa 0,5 bis 5 Ge- wichtsprozent, insbesondere etwa 0,5 bis 1,2 Gewichtsprozent, Acetylgruppen, berechnet als Vinylacetatreste . Auch andere Po- lyvinylester von aliphatischen Säuren mit bis zu 9 C-Atomen können verseift und anschließend acetalisiert werden. Teilbuty- ralisierter Polyvinylalkohol (PVB) wird bevorzugt verwendet. Bezüglich der verwendbaren Polymere wird ergänzend auf die DE 24 10 153 C3 verwiesen.The partially acetalized polyvinyl alcohols can be prepared in a manner known per se by saponification of polyvinyl acetate and subsequent acetalization with aldehydes, such as, for. B. formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like. the like getting produced. They usually still contain about 0.5 to 5 percent by weight, in particular about 0.5 to 1.2 percent by weight, of acetyl groups, calculated as vinyl acetate residues. Other polyvinyl esters of aliphatic acids with up to 9 carbon atoms can also be saponified and then acetalized. Partialized polyvinyl alcohol (PVB) is preferred. With regard to the polymers that can be used, reference is also made to DE 24 10 153 C3.
Die für das erfindungsgemäße Verfahren eingesetzte Folie enthält Weichmacher in Mengen von vorzugsweise 20 bis 40 Gew.-%. Beispiele für verwendbare Weichmacher sind Triethylenglykol-di- (2-ethylbutyrat) , Di-n-hexyl-adipat (DHA) und bevorzugt Trie- thylenglykol-bis-n-heptanoat (3G7) .The film used for the process according to the invention contains plasticizers in amounts of preferably 20 to 40% by weight. Examples of plasticizers that can be used are triethylene glycol di (2-ethylbutyrate), di-n-hexyl adipate (DHA) and preferably triethylene glycol bis-n-heptanoate (3G7).
Der Wassergehalt der Klebefolie wird erfindungsgemäß auf einen Wert von weniger als 0,35 Gew.-%, bevorzugt von gleich oder weniger als 0,30 Gew.-%, jeweils bezogen auf die Masse der Folie, eingestellt. Der erfindungsgemäß einzuhaltende Wassergehalt dient zum einen zur Vermeidung von Bläschen in den fertigen Verbundsicherheitsscheiben, er beeinflußt zusammen mit den zugesetzten silicium-organofunktionellen Silanen darüber hinaus in synergistischer Weise die Haftung zwischen der Klebefolie und den Glasscheiben.According to the invention, the water content of the adhesive film is adjusted to a value of less than 0.35% by weight, preferably equal to or less than 0.30% by weight, in each case based on the mass of the film. The water content to be observed according to the invention serves, on the one hand, to avoid bubbles in the finished composite safety panes, and together with the added silicon-organofunctional silanes, it also synergistically influences the adhesion between the adhesive film and the glass panes.
Die erfindungsgemäß eingesetzten, die Haftung erhöhenden silicium-organofunktionellen Silane sind an sich z.B. aus der DE 24 10 153 C3 bekannt, so daß hiermit auf diese Schrift Bezug genommen werden kann. Während der Zusatz von die Haftung erhöhenden silicium- organofunktionellen Silanen im üblichen Autoklavenprozeß nur eine mäßige Steigerung der Haftung Folie/Glas bewirkt, hat sich überraschend herausgestellt, daß die gleichen Silanverbindungen bei Anwendung eines autoklavenfreien Verfahrens eine mehrfach höhere Wirkung aufweisen. Dieses wird nachfolgend anhand von Beispielen und Vergleichsbeispielen sowie der Zeichnung verdeutlicht .The silicon-organofunctional silanes used to increase the adhesion are known per se, for example from DE 24 10 153 C3, so that reference can be made to this document. While the addition of silicon organofunctional silanes which increase the adhesion in the customary autoclave process only brings about a moderate increase in the adhesion of film / glass, it has surprisingly been found that the same silane compounds have a multiple-fold effect when using an autoclave-free process. This is illustrated below using examples and comparative examples as well as the drawing.
Kurze Beschreibung der Zeichnung Es zeigen dabeiBrief description of the drawing
Fig. 1 den Druck- und Temperaturverlauf vs . Zeit nach Beispielen 1, 2 und Vergleichsbeispiel 3; Fig. 2 den Druck- und Temperaturverlauf vs . Zeit nach Vergleichsbeispielen 4 bis 6; Fig. 3 eine schematische Darstellung einer Versuchseinrichtung für einen Kompressionsschertest.Fig. 1 shows the pressure and temperature curve vs. Time according to Examples 1, 2 and Comparative Example 3; Fig. 2 shows the pressure and temperature curve vs. Time according to comparative examples 4 to 6; Fig. 3 is a schematic representation of an experimental device for a compression shear test.
Wege zur Ausführung der Erfindung und VergleichsbeispieleWays of Carrying Out the Invention and Comparative Examples
Beispiel 1 (erfindungsgemäß)Example 1
Durch ein Verfahren gemäß der EP 0 185 863 Bl, Beispiel 1, wird eine beidseitig aufgerauhte PVB-Klebefolie hergestellt. Als Weichmacher wird dabei Triethylenglykol-bis-n-heptanoat (3G7) verwendet. Dem Weichmacher wird als silicium-organofunktio- nelles Silan ein γ-Aminopropyltriethoxysilan in einer Menge von 0,03 Gew.-%, bezogen auf die Masse der Folie, zugesetzt. Der Wassergehalt der PVB-Klebefolie wurde auf 0,29 Gew.-% eingestellt. Zwei ebene Silikatglasscheiben und die PVB-Klebefolie werden anschließend in einem einstufigen, autoklavenfreien Va¬ kuumverfahren, wie es in der EP 0 331 648 A2 beschrieben wird, zu einer Verbundsicherheitsscheibe verarbeitet. Die Verfahrens- parameter waren dabei wir folgt: Tabelle 1A PVB adhesive film roughened on both sides is produced by a method according to EP 0 185 863 B1, Example 1. Triethylene glycol bis-n-heptanoate (3G7) is used as the plasticizer. A γ-aminopropyltriethoxysilane is added to the plasticizer as silicon-organofunctional silane in an amount of 0.03% by weight, based on the mass of the film. The water content of the PVB adhesive film was set at 0.29% by weight. Two flat silicate glass sheets and the PVB adhesive film are then kuumverfahren in a single stage, autoklavenfreien ¬ Va, as described in EP 0331648 A2, processed into a laminated safety glass. The process parameters were as follows: Table 1
Figure imgf000007_0001
Figure imgf000007_0001
Der genaue zeitliche Ablauf ist in Fig. 1 näher dargestellt.The exact chronological sequence is shown in more detail in FIG. 1.
Beispiel 2:Example 2:
Nach dem gleichen Verfahren wie in Beispiel 1 werden Verbundsicherheitsscheiben hergestellt, wobei jedoch Di-n-hexyl-adipat (DHA) als Weichmacher verwendet wird.Composite safety panes are produced by the same method as in Example 1, but using di-n-hexyl adipate (DHA) as a plasticizer.
Vergleichsbeispiel 3:Comparative Example 3:
Nach dem gleichen Verfahren wie in Beispiel 1 werden Verbundsicherheitsscheiben hergestellt, wobei jedoch kein Silan verwendet wird.Composite safety panes are produced using the same procedure as in Example 1, but no silane is used.
Vergleichsbeispiele 4 bis 6:Comparative Examples 4 to 6:
Weite Verbundsicherheitsscheiben werden wie in den Beispielen 1 bis 3 hergestellt, wobei die Herstellung des Verbundes jedoch nach dem herkömmlichen zweistufigen Autoklaven-Prozeß erfolgt. Der Druck- und Temperaturverlauf ist in Fig. 2 dargestellt.Large composite safety panes are produced as in Examples 1 to 3, but the composite is produced using the conventional two-stage autoclave process. The pressure and temperature curve is shown in Fig. 2.
Versuchsauswertung :Test evaluation:
Die so hergestellten Verbundsicherheitsscheiben werden einem Standard-Kompressionsschertest unterworfen, der eine quantita¬ tive Beurteilung der Glas/Folien-Haftung erlaubt. Dabei werden die zu prüfenden Verbundsicherheitsscheiben unter einem Winkel von 45° in eine zweiteilige Prüfapparatur eingespannt. Die obe¬ re Hälfte wird mit einer stetig steigenden, genau vertikal nach unten gerichteten Kraft beaufschlagt, bis es zu einer Absche¬ rung innerhalb des Prüfkörpers, d. h. der zu prüfenden Verbund- Sicherheitsscheibe, kommt. Die hierzu verwendete Prüfemrichtung ist schematisch m Fig. 3 wiedergegeben. Die Prufparameter waren wie folgt:The laminated safety glass thus produced are subjected to a standard compression shear test that allows a quantita tive ¬ assessment of the glass / film adhesion. The composite safety washers to be tested are clamped at an angle of 45 ° in a two-part test apparatus. The obe ¬ re half is exactly vertically subjected to a steadily increasing, downwardly directed force until tion to a Absche ¬ within the test specimen, that is to be tested laminated safety glazing, comes. The test device used for this is shown schematically in FIG. 3. The test parameters were as follows:
Figure imgf000008_0001
Figure imgf000008_0001
Für jedes Beispiel wird die bei der Abscherung ausgeübte Kraft von zehn gleichen Prüfkörpern gemittelt. Zur Beurteilung der Streubreite der einzelnen Messungen wird weiterhin die Standar- dabweichung der einzelnen Messungen berechnet.For each example, the force exerted during shear is averaged from ten identical test specimens. To assess the spread of the individual measurements, the standard deviation of the individual measurements is also calculated.
Die Versuchsergebnisse sind m der Tabelle 3 wiedergegeben. Bei sämtlichen Beispielen wurde ein Wassergehalt von ca. 0,29 Gew.% der Folie bei der Herstellung des Verbundes eingehalten. The test results are shown in Table 3. In all of the examples, a water content of approximately 0.29% by weight of the film was maintained during the production of the composite.
Tabelle 3 : Ergebnisse KompressionsschertestTable 3: Results of the compression shear test
Figure imgf000009_0001
Figure imgf000009_0001
Ein Vergleich der Ergebnisse von Vergleichsbeispiel 6 mit Vergleichsbeispiel 3 (untere Zeile in Tabelle 3) verdeutlicht, daß bei Verwendung herkömmlicher Klebefolien die Kompressionsscherkräfte bei Anwendung eines autoklavenfreien Prozesses gegenüber einem Autoklavenprozeß auf etwa 30% des Ausgangswertes abfal¬ len. Vergleicht man hingegen die Ergebnisse der Vergleichsbei¬ spiele 4 und 5 mit den erfindungsgemäßen Beispielen 1 und 2 (obere und mittlere Zeilen in Tabelle 3) , ergibt sich eine fast gleichbleibende Haftung bei Anwendung eines autoklavenfreien Prozesses gegenüber einem Autoklavenprozeß.A comparison of the results of Comparative Example 6 with Comparative Example 3 (lower line in Table 3) illustrates that when using conventional adhesive sheets ¬ len compression shear forces during application of a autoklavenfreien process over an autoclave process on about 30% of the initial value wastes for. On the other hand, if you compare the results of comparative examples 4 and 5 with examples 1 and 2 according to the invention (upper and middle rows in table 3), there is almost constant liability when using an autoclave-free process compared to an autoclave process.
Bei einem Vergleich der Ergebnisse des Vergleichsbeispiels 6 mit den Vergleichsbeispielen 4 und 5 (rechte Spalte in Tabelle 3) , die die bekannte Verwendung von klebefolien mit und ohne Silanzusätzen im herkömmlichen Autoklavenprozeß betreffen, er¬ kennt man eine Zunahme der Kompressionsscherkräfte um ca. 12% bzw. 22% durch die Silanzusätze . Vergleicht man aber die Ergeb¬ nisse von Vergleichsbeispiel 3 mit den erfindungsgemäßen Bei- spielen 1 und 2 (mittlere Spalte in Tabelle 3) , so ergibt sich beim autoklavenfreien Prozesses eine Erhöhung der Haftung durch die Zugabe der Silane von 250% bzw. 330%, also eine mehr als zehn mal so hohe Wirkung der Silanzusätze beim autoklavenfreien Prozeß ! Diese Wirkung der an sich bekannten Silanzusätze ist völlig überraschend. Sie ermöglicht es, dem an sich bekannten autoklavenfreien Prozeß zur Herstellung von Verbundsicherheitsscheiben eine breitere Anwendung zu erschließen. Insbesondere ist es damit auch möglich, Verbundsicherheitsscheiben für den Baubereich mit höherer Prozeßsicherheit herzustellen. When comparing the results of Comparative Example 6 with Comparative Examples 4 and 5 (right column in Table 3), relating to the known use of adhesive films with and without Silanzusätzen in the conventional autoclave process, he ¬ knows to an increase in the compression shear strength by approximately 12% or 22% through the silane additives. But if we compare the resulting ¬ ratios of comparative example 3 with the inventive examples 1 and 2 play (middle column in Table 3), it follows when autoklavenfreien process to increase the adhesion by the addition of the silanes of 250% and 330%, So more than ten times the effect of the silane additives in the autoclave-free process! This effect of the known silane additives is completely surprising. It makes it possible to open up a broader application to the autoclave-free process known per se for the production of composite safety disks. In particular, it is also possible to manufacture composite safety panes for the construction sector with higher process reliability.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Verbundsicherheitsscheiben, bestehend aus zumindest zwei Glasscheiben und einer Zwischenschicht aus weichmacherhaltigem teilacetalisiertem Polyvinylalkohol, in einem einstufigen, autoklavenfreien Verfahren, gekennzeichnet durch die Verwendung einer weichmacherhaltigen teilacetalisierten Polyvinylalkohol- Folie mit einem Wassergehalt von weniger als 0,35 Gew.-%, bezo- gen auf die Masse der Folie, und einem wirksamen Gehalt eines die Haftung erhöhenden silicium-organofunktionellen Silans .1. Process for the production of composite security panes, consisting of at least two glass panes and an intermediate layer of plasticized partially acetalized polyvinyl alcohol, in a one-step, autoclave-free process, characterized by the use of a plasticized partially acetalized polyvinyl alcohol film with a water content of less than 0.35% by weight. %, based on the mass of the film, and an effective content of a silicon-organofunctional silane which increases the adhesion.
2. Verfahren nach Anspruch 1, gekennzeichnet durch die Verwendung eines Silans der Formel Rn-Si-Ap-Z ,2. The method according to claim 1, characterized by the use of a silane of the formula R n -Si-A p -Z,
II.
R 3-n in derR 3-n in the
R einen hydrolisierbaren Rest - R' einen Alkylrest mit 1 bis 18 C-Atomen,R is a hydrolyzable radical - R 'is an alkyl radical with 1 to 18 carbon atoms,
A einen zweiwertigen Alkylenrest mit 1 bis 10 C-Atomen, der gegebenenfalls verzweigt sein kann, und Z einen funktioneilen Rest, ausgewählt aus der Gruppe bestehend ausA is a divalent alkylene radical with 1 to 10 C atoms, which can optionally be branched, and Z is a functional radical selected from the group consisting of
Figure imgf000011_0001
Figure imgf000011_0001
— -C=C- und- -C = C- and
R" __ -N<R "__ - N <
R'" wobei R" gleich H oder Aminoalkyl mit 2 bis 8 C-Atomen im Alkylrest und R'" gleich H oder R" ist, bedeuten, und - n = 1 bis 3 und p gleich 1 oder im Falle von Z = -CH=CH2 gleich 0 ist. R '"where R" is H or aminoalkyl having 2 to 8 carbon atoms in the alkyl radical and R'"is H or R", and - n = 1 to 3 and p is 1 or in the case of Z = - CH = CH 2 is 0.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als silicium-organofunktionelles Silan γ-Aminopropyltriethoxy- silan eingesetzt wird.3. The method according to claim 1, characterized in that γ-aminopropyltriethoxy silane is used as the silicon organofunctional silane.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das silicium-organofunktionelle Silan in einer Menge von 0,01 bis 0,06 Gew.-%, bezogen auf die Masse der Folie, eingesetzt wird.4. The method according to claim 1, characterized in that the silicon-organofunctional silane in an amount of 0.01 to 0.06 wt .-%, based on the mass of the film, is used.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als teilacetalisierter Polyvinylalkohol ein Polyvinylbutyral- harz mit 12 bis 25 Gew.-% Vinylalkoholresten eingesetzt wird. 5. The method according to claim 1, characterized in that a polyvinyl butyral resin with 12 to 25 wt .-% vinyl alcohol residues is used as the partially acetalized polyvinyl alcohol.
PCT/DE1997/002409 1996-10-21 1997-10-18 Method for producing laminated safety glass windows WO1998017468A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19781146T DE19781146D2 (en) 1996-10-21 1997-10-18 Process for the production of composite safety washers
AU53976/98A AU5397698A (en) 1996-10-21 1997-10-18 Method for producing laminated safety glass windows

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19643404.1 1996-10-21
DE1996143404 DE19643404A1 (en) 1996-10-21 1996-10-21 Process for the production of composite safety washers

Publications (1)

Publication Number Publication Date
WO1998017468A1 true WO1998017468A1 (en) 1998-04-30

Family

ID=7809342

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1997/002409 WO1998017468A1 (en) 1996-10-21 1997-10-18 Method for producing laminated safety glass windows

Country Status (3)

Country Link
AU (1) AU5397698A (en)
DE (2) DE19643404A1 (en)
WO (1) WO1998017468A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7704342B2 (en) 2001-12-27 2010-04-27 Solutia, Inc. Glass lamination process

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060231189A1 (en) * 2005-04-15 2006-10-19 Solutia, Inc. Low moisture polymer sheets
US7625627B2 (en) * 2005-12-30 2009-12-01 E.I. Du Pont De Nemours And Company Decorative polyvinyl butyral solar control laminates
JP6552730B2 (en) 2015-12-14 2019-07-31 サン−ゴバン グラス フランスＳａｉｎｔ−Ｇｏｂａｉｎ Ｇｌａｓｓ Ｆｒａｎｃｅ Method for bonding laminated glass without using an autoclave
CN114158259A (en) 2020-06-17 2022-03-08 法国圣戈班玻璃厂 Method for laminating composite sheets without autoclave

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625792A (en) * 1970-04-27 1971-12-07 Ppg Industries Inc Fabricating glass-plastic windows
US4144376A (en) * 1974-03-02 1979-03-13 Dynamit Nobel Aktiengesellschaft Process for the production of modified, partially acetalized polyvinyl alcohol films
EP0331648A2 (en) * 1988-03-04 1989-09-06 Attilio Borgna Process for manufacturing laminated glass

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3909876A1 (en) * 1989-03-25 1990-09-27 Huels Troisdorf MOLDING FOR THE PRODUCTION OF FILMS FOR COMPOSITE SAFETY WINDOWS
DE4024330A1 (en) * 1990-07-31 1992-02-06 Huels Troisdorf Photochromic film prodn. for laminated safety glass - by extruding plasticised, acetalised polyvinyl-alcohol contg. photochromic cpds. which are pre-mixed with polymer and-or plasticiser
JP3213979B2 (en) * 1991-09-19 2001-10-02 株式会社ブリヂストン Laminated glass

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625792A (en) * 1970-04-27 1971-12-07 Ppg Industries Inc Fabricating glass-plastic windows
US4144376A (en) * 1974-03-02 1979-03-13 Dynamit Nobel Aktiengesellschaft Process for the production of modified, partially acetalized polyvinyl alcohol films
EP0331648A2 (en) * 1988-03-04 1989-09-06 Attilio Borgna Process for manufacturing laminated glass

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7704342B2 (en) 2001-12-27 2010-04-27 Solutia, Inc. Glass lamination process

Also Published As

Publication number Publication date
DE19781146D2 (en) 1999-09-30
DE19643404A1 (en) 1998-04-23
AU5397698A (en) 1998-05-15

Similar Documents

Publication Publication Date Title
EP1042121B1 (en) Partially acetalised polyvinyl alcohol plasticised sheeting
EP1235683B1 (en) Method and film for producing laminated safety glass panes
DE69935461T2 (en) Interlayer film for laminated glass and laminated glass
WO2011058026A1 (en) Composite glazing having films containing softening agents having low tendency to creep
DE102018004652A1 (en) Resin film for laminated glass and laminated glass and its manufacture
EP1430094B1 (en) Film for composite security disks with self-adhesiveness
DE2646280C2 (en) Plasticized polyvinyl butyral films with reduced adhesion to glass
DE1570868B2 (en) Laminated glass with a plasticizer-containing polyvinyl butyral film as an intermediate layer, the adhesion of which to the glass can be specifically controlled
DE2652427C2 (en)
DE2429032C2 (en) Intermediate layer made of polyvinyl butyral for laminated safety glass
EP0161583B1 (en) Reduction of the adhesion to glass of thermoplastic plasticizers containing polyvinylbutyral moulding compositions
WO1998017468A1 (en) Method for producing laminated safety glass windows
EP0070394B1 (en) Partially acetalized polyvinyl alcohol films containing a plasticizer
DE112019006121B4 (en) Film for glass lamination and process for its production
DE2213982A1 (en) Laminated safety glass interlayer
EP0464070A1 (en) Moulding material for the manufacture of films for laminated glass panes
DE10064373A1 (en) Film containing plasticizer and amide wax, useful as an intermediate layer for laminated safety glass plates, is based on partially acetylated polyvinyl alcohol
DE1596875C3 (en) Laminated glass made of two glass panes and a transparent film made of a thermoplastic material based on plasticizer-containing polyvinyl butyral as an intermediate layer, the glass adhesion of which is adjustable
DE112020002617T5 (en) COMPOSITE FILM FOR BONDING AND TRANSLUCENT LAMINATE WITH THIS FILM
DE112020003097B4 (en) COMPOSITE FILM FOR BONDING AND TRANSLUCENT LAMINATE WITH THIS FILM
DE1596884A1 (en) Transparent film made of thermoplastic material as an intermediate layer for a laminated glazing unit consisting of two panes of glass
DE2302380A1 (en) LAMINATED GLASS PANELS FOR VEHICLES
DE2410153C3 (en) Process for adjusting the adhesive force of partially acetalized polyvinyl alcohol films containing plasticizers on inorganic glasses and their use
DE1596884C3 (en) A transparent film made of thermoplastic material on the basis of plasticized polyvinyl butyral as an intermediate layer for a laminated glass
WO2005005525A2 (en) Film for composite safety glazings, featuring low inherent tack and good adhesion to glass

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DE DK EE ES FI GB GE GH HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE IT LU MC

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REF Corresponds to

Ref document number: 19781146

Country of ref document: DE

Date of ref document: 19990930

WWE Wipo information: entry into national phase

Ref document number: 19781146

Country of ref document: DE

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA