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DE2729226A1 - Two-layer plastics film for safety glass - with polyurethane layer from co-polyester diol to reduce crystallisation - Google Patents

Two-layer plastics film for safety glass - with polyurethane layer from co-polyester diol to reduce crystallisation

Info

Publication number
DE2729226A1
DE2729226A1 DE19772729226 DE2729226A DE2729226A1 DE 2729226 A1 DE2729226 A1 DE 2729226A1 DE 19772729226 DE19772729226 DE 19772729226 DE 2729226 A DE2729226 A DE 2729226A DE 2729226 A1 DE2729226 A1 DE 2729226A1
Authority
DE
Germany
Prior art keywords
layer
polyurethane
plastic film
bis
diol
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
DE19772729226
Other languages
German (de)
Other versions
DE2729226C2 (en
Inventor
Heinrich Agethen
Paul Gesenhues
Otto Jandeleit
Helmer Raedisch
Wolfgang Schaefer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie de Saint Gobain SA
Original Assignee
Compagnie de Saint Gobain SA
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
Priority claimed from DE2629779A external-priority patent/DE2629779C3/en
Application filed by Compagnie de Saint Gobain SA filed Critical Compagnie de Saint Gobain SA
Priority to DE2729226A priority Critical patent/DE2729226C2/en
Publication of DE2729226A1 publication Critical patent/DE2729226A1/en
Application granted granted Critical
Publication of DE2729226C2 publication Critical patent/DE2729226C2/en
Expired legal-status Critical Current

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B17/10018—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 only one glass sheet
    • 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
    • B32B17/10064—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 at least two glass sheets, only one of which being an outer layer
    • 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
    • B32B17/1077—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 polyurethane
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Plastic film consists of (A) a layer of aliphatic polyurethane cross-linked in 3 dimensions and with self-healing properties, and (B) a layer of thermoplastic polyurethane with linear structure, (B) is made from a co-polyester diol from >=2 branched and/or cycloaliphatic diols. Pref. >=2 different dicarboxylic acids are also used in working the copolyester diol. Used in mfr. of safety glass for use in vehicles, buildings sunglasses, protective masks, visors for safety helmets, etc. Layer (B) is adhered tot he glass by heat and pressure. Formation of crystalline agglomerates in (B) causing clouding of the layer with time, esp. at higher temps., is strongly retarded.

Description

Kunststoffolie mit zweischichtigem Aufbau für die Herstellung einer Sicherheitsgiassceibe Zusatz zu Patentanmeldung P 26 29 779.0 Die Hauptanmeldung betrifft eine Sicherheitsglasscheibe, die auf einer oder auf beiden Oberflächen mit einer kratzerartige Eindrücke selbst wieder ausheileiiden Kunststoffolie auf der Basis eines dreidimensional vernetzten aliphatischen Polyurethans versehen ist, wobei diese Kunststoffolie einen zweischichtigen Aufbau hat, indem sie auf der mit der Unterlage verbundenen Seite im wesentlichen linearpolymere Verknüpfung und thermoplastische Eigenschaften aufweist, und mit der Unterlage unter Anwendung von Wärme und Druck verbunden ist. Plastic film with a two-layer structure for the production of a Safety glass addition to patent application P 26 29 779.0 The main application relates to a safety glass pane that is on one or both surfaces with a scratch-like impression on the self-healing plastic film the base of a three-dimensionally crosslinked aliphatic polyurethane is provided, this plastic film has a two-layer structure in that it is on the with the side connected to the base essentially linear polymeric linkage and thermoplastic Has properties, and with the base under the application of heat and pressure connected is.

Gemäß der Hauptanmeldung kann die Schicht mit in wesentlichen linearpolymerer Verknüpfung aus einem Polyurethan bestehen, das aus einem Polyester-Polyol auf der Basis von Diolen und einem aliphatischen Diisocyanat hergestellt ist.According to the main application, the layer can be made with essentially linear polymer Linkage consist of a polyurethane, which consists of a polyester-polyol on the Based on diols and an aliphatic diisocyanate is made.

Gegenstand der Erfindung sind weiter verbesserte zweischichtige Kunststoffolien der zuletzt genannten Art, deren Schicht tnit im wesentlichen linearpolymerer Verknüpfung aus Polyurethan den Anforderungen, die an eine Sicherheitsglasscheibe gestellt werden, in besonders hohem Maße entspricht.The invention relates to further improved two-layered ones Plastic films of the last-mentioned type, the layer of which is essentially linear-polymeric made of polyurethane to meet the requirements placed on a safety glass pane, corresponds to a particularly high degree.

Sicherheitsglasscheiben werden nämlich in großem Umfang für Zwecke benutzt, bei denen sie eine verzerrungsfreie Durchsicht, eine hohe Transparenz und eine minimale Trübung aufweisen müssen. Diese Eigenschaften dürfen sich im Laufe der Zeit nicht verändern.Safety glass panes are namely used on a large scale for purposes used in which they have a distortion-free view, a high transparency and must be minimally cloudy. These properties are allowed to develop in the course not change over time.

Der Erfindung liegt die Aufgabe zugrunde, Schichten mit im wesentlichen linearpolymerer Verknüpfung aus weichmacherfreiem Folyurethan zu schaffen, die insbesondere eine hohe und gleichbleibende Transparenz und eine minimale und sich im Lafe der Zeit nicht erhöhende Trübung aufweisen.The invention is based on the object of essentially having layers to create linear polymeric linkage from plasticizer-free polyurethane, in particular a high and constant transparency and a minimum and in the Lafe der Show no increasing turbidity over time.

Gemäß der Erfindung wird dieses Ziel dadurch erreicht, daß das für die Herstellung der Polyurethanschicht mit linearpolymerer Verknüpfung verwendete Polyester-Polyol ein Mischpolyester-Diol auf der Basis von wenigstens zwei verscniedenen, zumindest teilweise in der Kohlenstoffgrundkette alkylverzweigten und/oder cycloaliphatischen Diolen ist.According to the invention this object is achieved in that the for used the production of the polyurethane layer with linear polymer linkage Polyester-polyol a mixed polyester-diol based on at least two different, at least partially alkyl-branched and / or cycloaliphatic in the carbon base chain Diolen is.

Hierfür eignen sich insbesondere folgende Diole: 1.2-Äthandiol, 1.2-Propandiol, 1.3-Propandiol, 1.2-Butandiol, 1.3-Butandiol, 1.4-Butandiol, 2.2-Dimethyl-1.3-propandiol, 1.6-Hexandiol, 2-Methyl-2.4-pentandiol, 3-Methyl-2.4-pentandiol, 2-Äthyl-1.3-hexandiol, 2.2.4-Trimethyl-1.3-pentandiol, Diäthylenglykol, Triäthylenglykol, Polyäthylenglykole, Dipropylenglykol, Tripropylenglykol, Polypropylenglykole, 2.2-Bis(4-hydroxycyclohexyl)propan ( = hydriertes Bisphenol A).The following diols are particularly suitable for this: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2.2-dimethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2.2.4-trimethyl-1,3-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycols, Dipropylene glycol, tripropylene glycol, polypropylene glycols, 2,2-bis (4-hydroxycyclohexyl) propane (= hydrogenated bisphenol A).

Durch die Verwendung derartiger Mischpolyester-Diole für die Herstellung des für die linearpolymer verknüpfte Schicht verwendeten Polyurethans wird ein unregelmäßiger linearer Aufbau der Moleküle begünstigt, deren ieigung zur Bildung von tristallartigen Agglomeraten beim Abkühlen aus der Schmelze bzw. im Laufe der Zeit, insbesondere bei noneren Temperaturen, stark herabgesetzt ist. Gerade solche kristallinen Agglomerate, deren räumliche Ausdehnung bis zu einigen tausend Angström, also bis in die Größenordnung der Wellenlänge des sichtbaren Lichtes, rechen kann, sind es, die die Trübung des Materials bewirken, weil an ihnen das Licht gebrochen und gestreut wird.By using such mixed polyester diols for the production of the polyurethane used for the linear polymer linked layer becomes an irregular one linear structure of the molecules favors their tendency to form tristallic Agglomerates when cooling from the melt or over time, in particular at noner temperatures, is greatly reduced. Precisely such crystalline agglomerates, their spatial extent up to a few thousand angstroms, i.e. up to the order of magnitude the wavelength of visible light, it is the opacity of the Materials because the light is refracted and scattered on them.

Die Gefahr der Bildung derartiger kristalliner Agglomerate ist gerade bei solchen Polymeren besonders nocn, bei denen man keine Weichmacher einsetzen kann, oder bei denen der Einsatz von Weichmachern nachteilig ist. in relativ hoher Weichmacheranteil nämlich wirkt sich auf die Transparenz und Trübungsfreiheit günstig aus, weil auch dadurch die Bildung von kristallinen Strukturen verhindert wird. Die thermoplastische Polyurethanschicht der erfindungsgemäßen Kunststoffolie enthält jedoch keinen Weichmacher, da sich die Gegenwart von Weichmachern a'.s troblematisch erwiesen hat, und sie wird außerdem beim Aufkaschieren verhältnismäßig langsamen Aufheiz- bzw. Abkühlvorgängen ausgesetzt, so daß unter diesen Umständen hier relativ günstige Voraussetzungen für die Bildung kristalliner Strukturen gegeben sind.The danger of the formation of such crystalline agglomerates is straight especially in the case of polymers that do not use plasticizers can, or where the use of plasticizers is disadvantageous. in relatively high The proportion of plasticizer has a positive effect on transparency and freedom from haze because this also prevents the formation of crystalline structures. The thermoplastic polyurethane layer of the plastic film according to the invention contains however, no plasticizer, as the presence of plasticizers is problematic has proven, and it is also relatively slow when laminating Exposed heating or cooling processes, so that under these circumstances here relatively favorable conditions for the formation of crystalline structures are given.

Es hat sich gezeigt, daß sich eine weitere Verbesserung des gewünschten Effektes erreichen läßt, wenn in Weiterbildung des Erfindungsgedankes das Mischpolyester-Diol unter Verwendung von wenigstens zwei verschiedener. Dicarbonsäuren hergestellt ist. Hierfür eignen sich insbesondere die folgenden Dicarbonsäuren: Malonsäure, Bernsteinsäure, Glutersäure, Adipinsäure, Korksäure, Sebacinsäure. Im gleichen Sinne wirkt der Zusatz eines oder mehrerer Lactone zu der Dicarbonsäure-Diol-Reaktion, wobei sich insbesondere folgende Lactone hierfür eignen: gamma-Butyrolacton, gamma-Valerolacton, delta-Valerolacton und epsilon-Caprolacton.It has been shown that a further improvement of the desired Effect can be achieved if, in a further development of the inventive concept, the mixed polyester-diol using at least two different. Dicarboxylic acids is produced. The following dicarboxylic acids are particularly suitable for this: malonic acid, succinic acid, Gluteric acid, adipic acid, suberic acid, sebacic acid. The addition works in the same way one or more lactones to the dicarboxylic acid-diol reaction, in particular the following lactones are suitable for this: gamma-butyrolactone, gamma-valerolactone, delta-valerolactone and epsilon-caprolactone.

Um eine noch höhere Beständigkeit gegen Trübungserscheinungen zu erhalten, kann in zweckmäßiger weiterer Ausgestaltung der Erfindung das linearverknüpfte Polyurethan unter Verwendung von wenigstens zwei verschiedenen, in der Kohlenstoffgrundkette alkylverzweigten und/oder cycloaliphatischen Diisocyanaten nergestellt sein. Fiir diesen Zweck eignen sich insbesondere die folgenden Diisocyanate: Bis(4-isocyanatocyclohexyl)methan, Bis(3-methyl-4-isocyanatocyclohexyl)methan, 2.2-Bis(4-isocyanatocyclohexyl)propan, 3-Isocyanatomethyl-3.5.5-trimethylcyclohexylisocyanat (= Isophorondiisocyanat IPDI), 2.2.4- und 2.4.4-Trimethylhexandiisocyanat, 1.3-Bis(Isocyanatomethyl)benzol).In order to obtain an even higher resistance to cloudiness, can, in an expedient further embodiment of the invention, the linearly linked polyurethane using at least two different ones in the carbon backbone branched alkyl and / or cycloaliphatic diisocyanates. For The following diisocyanates are particularly suitable for this purpose: bis (4-isocyanatocyclohexyl) methane, Bis (3-methyl-4-isocyanatocyclohexyl) methane, 2.2-bis (4-isocyanatocyclohexyl) propane, 3-isocyanatomethyl-3.5.5-trimethylcyclohexyl isocyanate (= isophorone diisocyanate IPDI), 2.2.4- and 2.4.4-trimethylhexane diisocyanate, 1.3-bis (isocyanatomethyl) benzene).

Nach einem bevorzugten Ausführungsbeispiel wird die erfindungsgemäße Kunststoffolie mit zweischichtigem Aufbau wie folgt hergestellt: Es wird als Gießmasse für die Herstellung der dreidimensional vernetzten Polyurethanschicht ein Reaktionsansatz wie folgt hergestellt: - 1000 g eines durch Kondensation von 1.2-Propylenoxid mit 2.2-Bis(hydroxymethyl-1-butanol) hergestellten Polyäthers mit einem Molekulargewicht von etwa 450 und einem Gehalt an freien CH-Gruppen von 10,5 bis 12 % (z.B. das unter dem Handelsnamen DES@S@@ 55) @ bekannte Produkt der Firma BAYER AG@ -23 g 2.6-Di-tert.-butyl-4-methylphenol (z.B. das unter dem Handelsnamen IONOL bekannte Produkt der SHELL-CHEMIE), - 1000 g eines Biurets von 1.6-Hexandiisocvanat mit einem Gehalt an freien NCO-Gruppen von 21 bis 22 /o (z.B. das unter dem Handelsnamen DESMODUR N/100 bekannte Produkt der Firma BAYER AG) werden unter Vermeidung der Bildung von Luftolasen durch entgasen bei Unterdruck homogen gemischt. Diese Masse eignet sich zun Auftragen auf eine Gießunterlage beispielsweise mit einem Abstreichgießkopf.According to a preferred embodiment, the invention Plastic film with a two-layer structure is produced as follows: It is used as a casting compound a reaction approach for the production of the three-dimensionally crosslinked polyurethane layer prepared as follows: - 1000 g of a by condensation of 1,2-propylene oxide with 2.2-bis (hydroxymethyl-1-butanol) produced polyethers with a molecular weight of about 450 and a content of free CH groups of 10.5 to 12% (e.g. the one below the trade name DES @ S @@ 55) @ known product from BAYER AG @ -23 g of 2,6-di-tert-butyl-4-methylphenol (e.g. the SHELL-CHEMIE product known under the trade name IONOL), - 1000 g of a biuret of 1,6-hexanediisocvanate with a content of free NCO groups from 21 to 22 / o (e.g. the product known under the trade name DESMODUR N / 100 from BAYER AG) are degassed by avoiding the formation of air bubbles mixed homogeneously at negative pressure. This mass is suitable for applying to a Casting pad, for example, with a skimmer head.

Zur Herstellung der linearverknüpften thermoplastischen Schich wird zunächst in an sich bekannter Weise in Stickstoffatmosphäre ein mit Isocyanaten reagierender Polyester dadurch hergestellt, daß man in einem EdelstzEl-Reaktionsbehälter 145 Gew.-T. Adipinsäure und 50 Gew.-T. Sebacinsäure mit 145 Gew.-I # -Caprolacton, 120 Gew.-Z. 2.2-Dimethyl-1.3-propandiol und CO Gew.-T. 1.4-Butandiol in Gegenwart von 25 Gew.-T. Xylol und 0,25 Gew.-T. Dibutylzinndilaurat bei einer Temperatur von 180° C azeotrop verestert. Nach Abspaltung von ca. 22,5 Gew.-l Reaktionswasser werden zur Vorbereitung der Kettenverlängerung 18 Gew.-T. 1.4-Butandiol sowie anschließend 400 Gew.-T. Xylol hinzugefügt. Nachdem die Temperatur auf 800 C abgesenkt worden ist, werden unter starkem Rühren hintereinander 150 Gew.-T.For the production of the linearly linked thermoplastic layer first in a manner known per se in a nitrogen atmosphere with isocyanates reactive polyester produced by placing in a stainless steel reaction vessel 145 parts by weight Adipic acid and 50 parts by weight. Sebacic acid with 145 wt. I # caprolactone, 120 wt. 2.2-dimethyl-1.3-propanediol and CO parts by weight. 1,4-butanediol in the presence from 25 parts by weight Xylene and 0.25 parts by weight. Dibutyltin dilaurate at a temperature of Azeotropically esterified at 180 ° C. After about 22.5% by weight of water of reaction have been split off to prepare the chain extension 18 parts by weight 1,4-butanediol and then 400 parts by weight Xylene added. After the temperature has been lowered to 800 C. is, with vigorous stirring successively 150 parts by weight.

Bis(4-isocyanatocyclohexyl)methan und 50 Gew.-T. 3-Isocyanatomethyl-3.5.5-trimethylcyclohexylisocyanat zugefügt.Bis (4-isocyanatocyclohexyl) methane and 50 parts by weight. 3-isocyanatomethyl-3.5.5-trimethylcyclohexyl isocyanate added.

Nach Tem#raturerhöhung auf 1000 C resultiert aus dem erhaltene Additionsprodukt das linearverknüpfte thermoplastische Polyurethanharz. Die Weiterpolymerisation wird fortgesetzt, bis das Molekulargewicht des Polyurethanharzes auf mindestens 40.000, bevorzugt jedoch aber 50.000 angestiegen ist. Flach Abkühlung auf 70° C oder weniger wird zunächst mit 3000 Gew.-T. Methyläthylketon, und bei einer Temperatur unter 30° C mit 3000 Gew.- Tetrahydrofuran weiterverdünnt, so daß der Festkörpergehalt des Polyurethanharzes in der Lösung ca. 10 Gew.-% beträgt.After the temperature has been increased to 1000 ° C., the resulting addition product results the linearly linked thermoplastic polyurethane resin. The further polymerization continues until the molecular weight of the polyurethane resin is at least 40,000, but preferably 50,000 has risen. Flat cooling to 70 ° C or less is initially with 3000 parts by weight. Methyl ethyl ketone, and at a temperature below 30 ° C with 3000 wt. Tetrahydrofuran further diluted so that the solids content of the polyurethane resin in the solution is approx. 10% by weight.

Die Herstellung der zweischichtigen Kunststoffolie erfolgt dur Auftragen der vorstehend beschriebenen Lösung auf die zuerst hergestellte dreidimensional vernetzte Schicht, .3. -it Hilfe eines Abstreichgießers, und anschließende Verdampfung des enthaltenen Lösungsmittelgemisches im Trockenkanal bei einer erhöhten Temperatur.The two-layer plastic film is produced by applying the solution described above to the first three-dimensional cross-linked layer, .3. -with the help of a skimmer, and subsequent evaporation of the solvent mixture contained in the drying tunnel at an elevated temperature.

Die so hergestellte zweischichtige Kunststoffolie wird von der Gießunterlage abgezogen. Sie kann dann unter Anwendung von wärme und Druck auf die Trägerscheibe, bei der es sich um eine Silikatglasscheibe oder um eine Kunststoffplatte handeln kann, aufkaschiert werden.The two-layer plastic film produced in this way is removed from the casting base deducted. You can then apply heat and pressure to the carrier disc, which is a silicate glass pane or a plastic plate can be laminated.

Falls die erfindungsgemäßen Folien auf eine Glasunterlage aufkaschiert werden, dienen sie in erster Linie als Splitterschutz und verhindern jeden Kontakt mit den Glasbruchstücken.If the films according to the invention are laminated onto a glass substrate they serve primarily as splinter protection and prevent any contact with the broken glass.

Die erfindungsgemäßen Folien können jedoch mit besonderem Vorteil auch auf Kunststoffplatten aufkaschiert werden, wobei sie in diesem Falle die Funktion einer 'Kratzfestbeschichtung' übernehmen.However, the films according to the invention can be used with particular advantage can also be laminated onto plastic panels, in which case they function take over a 'scratch-resistant coating'.

Die Kunststoffolien nach der Erfindung zeigen eine gute Haftun auf Polykarbonaten, beispielsweise auf dem unter der Bezeichnung LEXAN im Handel erhältlichen Produkt der Fa. GENERAL ELECTRIC, und können ebenso als gut haftende Schutzschichten auf Platten oder Folien aus einen Polyester, Polyacrylat, Polyamid, Celluloseester oder Polyvinylchlorid aufgebracht werden.The plastic films according to the invention show good adhesion Polycarbonates, for example on the one commercially available under the name LEXAN Product from GENERAL ELECTRIC, and can also be used as well-adhering protective layers on sheets or foils made of a polyester, polyacrylate, polyamide, cellulose ester or polyvinyl chloride can be applied.

Mit der erfindungsgemäßen Schutzfolie versehene Sicherheitsglasscheiben eignen sich nicht nur als Fahrzeugverglasungen od für die Anwendung im Hochbau, sonder ebenso mit besonderem Vorteil als Brillengläser, Schutzmasken, Visiere für Schutzhelme, Schutzschilde, Panzergläser u.a.m.Safety glass panes provided with the protective film according to the invention are not only suitable as vehicle glazing or for the application in building construction, but also with particular advantage as glasses, protective masks, Visors for protective helmets, protective shields, armored glass, etc.

Claims (11)

Patentansprüche 1. Kunststoffolie mit zweischichtigem Aufbau, deren eine Schicht aus einem dreidimensional vernetzten aliphatischen Polyurethan mit selbstheilenden Eigenschaften, und deren andere Schicht aus einem linearpolymere Verknüpfung und thermoplastische Eigenschaften aufweisenden Polyurethan besteht, das aus einem Polyester-Polyol auf der Basis von Diolen und einem aliphatischen Diisocyanat hergestellt ist, für die Herstellung einer Sicherheitsglasscheibe nach Patentanmeldung P 26 29 779.0, d a d u r c h g e k e n n -z e i c h n e t , daß das für die Herstellung der Polyurethanschicht mit linearpolymerer Verknüpfung verwendete Polyester-Polyol ein Mischpolyester-Diol auf der Basis von wenigstens zwei verschiedenen, zumindest teilweise in der Kohlenstoffgrundkette alkylverzweigten und/oder cycloaliphatischen Diolen ist. Claims 1. Plastic film with a two-layer structure, whose a layer of a three-dimensionally crosslinked aliphatic polyurethane with self-healing properties, and its other layer made of a linear polymer Linkage and thermoplastic properties exhibiting polyurethane is made, the one made from a polyester-polyol based on diols and an aliphatic one Diisocyanate is produced, for the production of a safety glass pane according to Patent application P 26 29 779.0, d a d u r c h g e k e n n -z e i c h n e t that that used for the production of the polyurethane layer with linear polymer linkage Polyester-polyol a mixed polyester-diol based on at least two different, at least partially alkyl-branched and / or cycloaliphatic in the carbon base chain Diolen is. 2. Kunststoffolie nach Anspruch 1, dadurch gekennzeichnet, daß das Mischpolyester-Diol unter Verwendung von wenigstens zwei verschiedenen Dicarbonsäuren hergestellt ist. 2. Plastic film according to claim 1, characterized in that the Mixed polyester diol using at least two different dicarboxylic acids is made. 3. Kunststoffolie nach Anspruch 1 und 2, dadurch gekennzeichnet, daß das linearverknüpfte Polyurethan unter Verwendung von wenigstens zwei verschiedenen, in der Kohlenstoffgrundkette alkylverzweigten und/oder cycloaliphatischen und/oder alkylverzweigt-cycloalipatischen Diisocyanaten hergestellt ist. 3. Plastic film according to claim 1 and 2, characterized in that that the linearly linked polyurethane using at least two different, in the carbon base chain alkyl-branched and / or cycloaliphatic and / or branched alkyl-cycloaliphatic diisocyanates. 4. Kunststoffolie nach Anspruch 3, dadurch gekennzeichnet, daß bei Verwendung von mehr als 85 % cycloaliphatischem Diisocyanat wenigstens zwei der für die Herstellung des Mischpolyester-Diols verwendeten Diole alkylverzweigte und/oder cycloaliphatische Diole sind 4. Plastic film according to claim 3, characterized in that at Use of more than 85% cycloaliphatic diisocyanate at least two of the for the preparation of the mixed polyester diol used diols alkyl-branched and / or are cycloaliphatic diols 5. Kunststoffolie nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das linearverknüpfte Polyurethan unter Zusatz von einen oder mehreren Lactonen hergestellt ist.5. Plastic film according to one or more of claims 1 to 4, characterized in that the linearly linked polyurethane is made with the addition of one or more lactones. 6. Verfahren zur Herstellung einer Kunststoffolie nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das für die Herstellung der Polyurethanschicht mit linearpolymeren Verknüpfung verwendete Mischpolyester-Diol unter Verwendung von zwei oder mehr der folgenden Diole hergestellt wird: 1.2-Äthandiol, 1.2-Propandiol, 1.3-Propandiol, 1.2-Butandiol, 1.3-Butandiol, 1.4-Butandiol, 2.2-Dimethyl-1.3-Propandiol, 1.6-Hexandiol, 2-Methyl-2.4-Pentandiol, 3-Methyl-2.4-Pendantiol, 2-Äthyl-1.3-Hexandiol, 2.2.4-Trimethyl-1.3-Pendantiol, Diäthylenglykol, Triäthylenglykol, Polyäthylenglykole, Dipropylenglykole, Tripropylenglykole, Polypropylenglykole, 2.2-Bis(4-hydroxyclohexyl)propan.6. A method for producing a plastic film according to one or several of claims 1 to 5, characterized in that the for the production mixed polyester-diol used in the polyurethane layer with linear polymer linkage is made using two or more of the following diols: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2.2-dimethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-2,4-pendantiol, 2-ethyl-1,3-hexanediol, 2.2.4-trimethyl-1.3-pendantiol, diethylene glycol, triethylene glycol, polyethylene glycols, Dipropylene glycols, tripropylene glycols, polypropylene glycols, 2,2-bis (4-hydroxyclohexyl) propane. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das für die Herstellung der Polyurethanschicht mit linearpolymerer Verknüpfung verwendete Mischpolyester-Diol ein Molekulargewicht von etwa 500 bis 4000, und vorzugsweise etwa 1000 bis 2000, aufweist.7. The method according to claim 6, characterized in that the for used the production of the polyurethane layer with linear polymer linkage Interpolyester-diol has a molecular weight of about 500 to 4000, and preferably about 1000 to 2000. 8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das Mischpolyester-Diol unter Verwendung von zwei oder mehr der folgenden Dicarbonsäuren hergestellt wird: Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Sebacinsäure.8. The method according to claim 7, characterized in that the mixed polyester diol is made using two or more of the following dicarboxylic acids: Malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid. 9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß zur Polyaddition des Mischpolyester-Diols zum Polyurethan zwei oder mehr der folgenden aliphatischen Diisocynate verwendet werden: Bis(4-isocyanatocyclohexyl)methan, Bis(3-methyl-4-isocyanatocyclohexyl)methan, 2.2-Bis(4-isocyanatocyclohexyl)propan, 3-Isocyanatomethyl-3.5.5-trimethylcyclohexylisocyanat 2.2.4- und 2.4.4-Trimethyl-1.6-hexandiisocyanat, 1.6-Hexandiisocyanat, 1.3-Bis(Isocyanatomethyl)benzol. 9. The method according to claim 7 or 8, characterized in that for the polyaddition of the mixed polyester diol to the polyurethane, two or more of the following aliphatic diisocyanates are used: bis (4-isocyanatocyclohexyl) methane, bis (3-methyl-4-isocyanatocyclohexyl) methane, 2.2-bis (4-isocyanatocyclohexyl) propane, 3-isocyanatomethyl-3.5.5-trimethylcyclohexyl isocyanate 2.2.4- and 2.4.4-trimethyl-1.6-hexane diisocyanate, 1.6-hexane diisocyanate, 1.3-bis (isocyanatomethyl) benzene. 10. Verfahren nach Anspruch 7 bis 9, dadurch gekennzeichnet, daß das Mischpolyester-Diol durch Copolykondensation von Adipinsäure und Sebacinsäure mit 2.2-Dimethylpropandiol-1.3 und Butandiol-1.4 unter Zusatz von 6 - Caprolacton hergestellt, und mit Bis(4-isocyanatocyclohexyl)methan und 3-Isocyanatomethyl-3.5.5-trimethylcyclohexylisocyanat copolyaddiert wird.10. The method according to claim 7 to 9, characterized in that the Mixed polyester diol through copolycondensation of adipic acid and sebacic acid with 2.2-dimethylpropanediol-1.3 and butanediol-1.4 with the addition of 6 - caprolactone produced, and with bis (4-isocyanatocyclohexyl) methane and 3-isocyanatomethyl-3.5.5-trimethylcyclohexyl isocyanate is copolyadded. 11. Verfahren nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Verhältnis der NCC-Gruppen zu den OH-Gruppen der Reaktanten höchstens gleich 1, und vorzugsweise etwa 0,8 bis 0,9, beträgt.11. The method according to one or more of claims 1 to 10, characterized characterized in that the ratio of the NCC groups to the OH groups of the reactants is at most equal to 1, and preferably about 0.8 to 0.9.
DE2729226A 1976-07-02 1977-06-29 Plastic film with a two-layer structure as a cover layer for safety glass panes based on polyurethane Expired DE2729226C2 (en)

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DE2629779A DE2629779C3 (en) 1976-07-02 1976-07-02 Process for the production of a two-layer film with self-healing properties using polyurethanes as a shatterproof layer on safety glass
DE2729226A DE2729226C2 (en) 1976-07-02 1977-06-29 Plastic film with a two-layer structure as a cover layer for safety glass panes based on polyurethane

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0190517A1 (en) * 1984-12-06 1986-08-13 Saint-Gobain Vitrage International Self-restoring coating for safety glass articles, particularly those which are exposed to outdoor conditions
FR2644468A1 (en) * 1989-03-20 1990-09-21 Saint Gobain Vitrage POLYURETHANE LAYER HAVING ENERGY ABSORBER PROPERTIES AND USE IN SECURITY GLAZING
CN108559052A (en) * 2018-04-19 2018-09-21 清华大学 Crosslinking polyurea elastomer with self-healing properties and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE782332A (en) * 1971-04-20 1972-10-19 Saint Gobain SAFETY SHEET GLASS

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE782332A (en) * 1971-04-20 1972-10-19 Saint Gobain SAFETY SHEET GLASS

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
In Betracht gezogene ältere Anmeldungen: DE-OS 26 29 779 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0190517A1 (en) * 1984-12-06 1986-08-13 Saint-Gobain Vitrage International Self-restoring coating for safety glass articles, particularly those which are exposed to outdoor conditions
FR2644468A1 (en) * 1989-03-20 1990-09-21 Saint Gobain Vitrage POLYURETHANE LAYER HAVING ENERGY ABSORBER PROPERTIES AND USE IN SECURITY GLAZING
EP0389354A1 (en) * 1989-03-20 1990-09-26 Saint-Gobain Vitrage International Polyurethane layer having energy absorbing properties and its use in laminated safety glass
CN108559052A (en) * 2018-04-19 2018-09-21 清华大学 Crosslinking polyurea elastomer with self-healing properties and preparation method thereof

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