DE2729226C2 - Plastic film with a two-layer structure as a cover layer for safety glass panes based on polyurethane - Google Patents
Plastic film with a two-layer structure as a cover layer for safety glass panes based on polyurethaneInfo
- Publication number
- DE2729226C2 DE2729226C2 DE2729226A DE2729226A DE2729226C2 DE 2729226 C2 DE2729226 C2 DE 2729226C2 DE 2729226 A DE2729226 A DE 2729226A DE 2729226 A DE2729226 A DE 2729226A DE 2729226 C2 DE2729226 C2 DE 2729226C2
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- Prior art keywords
- polyurethane
- plastic film
- layer
- film according
- polyester
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- 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.)
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- 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
- 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
- B32B17/10064—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
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- 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
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- 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
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- 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)
Description
1.2-Propandiol.1,2-propanediol.
1.2-Butandiol.1,2-butanediol.
1.3-Butandiol.1,3-butanediol.
2.2Dimethyl-l.3-Propandiol.2.2-dimethyl-1.3-propanediol.
2-Methvl-2.4-Pentandiol,2-methyl-2,4-pentanediol,
3-Methyl 2.4-Pentandiol.3-methyl 2,4-pentanediol.
2Äthyl-l.3-Hexandiol.2-ethyl-1,3-hexanediol.
2.2.4■Tπmethyl-1.3-Pentandiol.2.2.4 ■ methyl-1,3-pentanediol.
Dipropylenglykole.Dipropylene glycols.
Tripropylenglykole.Tripropylene glycols.
Polypropylenglykole,Polypropylene glycols,
2.2-Bis(4-hydroxycyclohexyl)propan.2.2-bis (4-hydroxycyclohexyl) propane.
5050
5555
6060
7. Kunststoffolie 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. Plastic film according to claim 6, characterized in that that for the production of the polyurethane layer with linear polymer linkage The mixed polyester diol used has a molecular weight of about 500 to 4000, and preferably about 1000 to 2000.
8. Kunststoffolie nach Anspruch 7, dadurch gekennzeichnet, daß das Mischpolyester-Diol unter Verwendung von zwei oder mehr der folgenden Dicarbonsäuren hergestellt ist:8. Plastic film according to claim 7, characterized in that the mixed polyester diol under Using two or more of the following dicarboxylic acids is made:
Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Sebacinsäure.Malonic acid, succinic acid, glutaric acid, adipic acid, Suberic acid, sebacic acid.
9. Kunststoffolie nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Polyaddition des Mischpolyester-Diols zum Polyurethan unter Verwendung von zwei oder mehr der folgenden alipathischen Diisocyanate durchgeführt ist:9. Plastic film according to claim 7 or 8, characterized in that the polyaddition of the mixed polyester diol to polyurethane using two or more of the following aliphatic diisocyanates is carried out:
Bis(4-isocyanatocyclohexyl)methan,Bis (4-isocyanatocyclohexyl) methane,
Bis(3-methyl-4-isocyanatocyclohexyl)methan,Bis (3-methyl-4-isocyanatocyclohexyl) methane,
2^-Bis(4-isocyanatocyclohexyl)propan,2 ^ -Bis (4-isocyanatocyclohexyl) propane,
3-Isoeyanatomethyl-3.5.5-trimethyIcyclo-3-Isoeyanatomethyl-3.5.5-trimethyIcyclo-
hexylisocyanat.hexyl isocyanate.
2.2.4- und 2.4.4-Trimethy 1-1.6-hexan-2.2.4- and 2.4.4-trimethyl 1-1.6-hexane
diisocyanat,diisocyanate,
! .6- Hexandiisocyanat,! .6- hexane diisocyanate,
13-Bis(Isocyanatomethyl)benzoI.13-bis (isocyanatomethyl) benzoI.
10. Kunststoffolie nach Anspruch 7 bis 9. dadurch gekennzeichnet, daß das Mischpoiyester-Diol durch Copolykondensation von Adipinsäure und Sebacinsäure mit 2.2-Dimethylpropandiol-i.3 und Butandiol-1.4 unter Zusatz von f-Caprolacton hergestellt, und zur Herstellung der Polyurethanschicht mit linearpolymerer Verknüpfung mit Bis(4-isocyanatocyclohexyl)methan und S-Isocyanatomethyl-S.SJj-trimethylcyclohexylisocyanat copolyaddiert ist.10. Plastic film according to claim 7 to 9, characterized in that the Mischpoiyester-Diol by Copolycondensation of adipic acid and sebacic acid with 2.2-dimethylpropanediol-i.3 and butanediol-1.4 produced with the addition of f-caprolactone, and for the production of the polyurethane layer with linear polymer Linkage with bis (4-isocyanatocyclohexyl) methane and S-isocyanatomethyl-S.SJj-trimethylcyclohexyl isocyanate is copolyadded.
11. Kunststoffolie nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Verhältnis der NCO-Gruppen zu den OH-Gruppen der Reaktanten höchstens gleich 1, und vorzugsweise etwa 0.8 bis 0.9, beträgt.11. Plastic film according to one or more of claims 1 to 10, characterized in that the ratio of the NCO groups to the OH groups of the reactants is at most equal to 1, and preferably about 0.8 to 0.9.
Die Erfindung betrifft eine für die Verwendung als Deckschicht für Sicherheitsglasscheiben geeignete Kunststoffolie mit zweischichtigem Aufbau, deren Schicht aus einem dreidimensional vernetzten aliphatischen Polyurethan mit Selbstheileigenschaften, und deren andere mit der Unterlage zu verbindende Schicht aus einem Polyurethan mit im wesentlichen linearpolymerer Verknüpfung und thermoplastischen Eigenschaften besteht und aus einem Polyester-P^'yol auf der Basis von Diolen und einem aliphatischen Diisocyanat hergestellt ist.The invention relates to one suitable for use as a cover layer for safety glass panes Plastic film with a two-layer structure, whose Layer made of a three-dimensionally cross-linked aliphatic polyurethane with self-healing properties, and their another layer to be bonded to the substrate, made of a polyurethane with essentially linear polymer Linkage and thermoplastic properties and consists of a polyester p ^ 'yol on the basis is made from diols and an aliphatic diisocyanate.
Deckschichten für Sicherheitsglasscheiben mit einem derartigen Aufbau aus zwei verschiedenen Polyurethanschichten sind in der älteren, nicht vorveröffentlichten Patentanmeldung DE-OS 26 79 779 vorgeschlagen worden. Cover layers for safety glass panes with such a structure made of two different polyurethane layers have been proposed in the older, unpublished patent application DE-OS 26 79 779.
Bekannt sind Sicherheitsglasscheiben mit einer zweischichtigen Deckschicht, bei denen eine als Energieabsorberschicht dienende Polyurethanfolie mit einer weichen Kratzfestbeschichtung aus einem Polyurethan mit Selbstheileigenschaften versehen, und diese zweischichtige Polyurethanfolie mit der Glasscheibe verbunden wird (BE-PS 782.332). Über die Zusammensetzung der als Energieabsorber dienenden Polyurethanfolie sind hierbei keine näheren Angaben gemacht.Safety glass panes with a two-layer cover layer are known, one of which is used as an energy absorber layer serving polyurethane film with a soft scratch-resistant coating made of a polyurethane with Self-healing properties are provided, and this two-layer polyurethane film is bonded to the glass pane becomes (BE-PS 782.332). About the composition of the polyurethane film used as an energy absorber no further details are given here.
Wenn Sicherheitsglasscheiben der eingangs genannten Art als Sichtscheiben Verwenden finden, werden an ihre optischen Eigenschaften besonders hohe Anforde-If safety glass panes of the type mentioned above are used as viewing panes, they will be used their optical properties are particularly demanding
rungen gestellt. Es hat sich gezeigt, daß im Hinblick auf die optischen Eigenschaften der Sicherheitsglasscheibe der Zusammensetzung der Polyurethanschicht mit linearpolymerer Verknüpfung eine besondere Bedeutung zukommt.struggles. It has been shown that in terms of the optical properties of the safety glass pane of the composition of the polyurethane layer with linear polymer Linking is of particular importance.
Der Erfindung liegt die Aufgabe zugrunde, weiter verbesserte zweischichtige Kunststoffolien für Sicherheitsglasscheiben zu schaffen, bei denen die Schicht aus einem Polyurethan mit im wesentlichen linearpolymerer Verknüpfung eine hohe und gleichbleibende Transparenz und eine minimale Trübung aufweist, die sich im Laufe der Zeit nicht erhöht.The invention is based on the object of further improved two-layer plastic films for safety glass panes to create in which the layer is made of a polyurethane with essentially linear polymer Link has a high and constant transparency and minimal haze, which is in the Not increased over time.
Gemäß der Erfindung wird diese Aufgabe dadurch gelöst, daß das für die Herstellung der Polyurethanschicht mit im wesentlichen linearpolymerer Verknüpfung verwendete Polyester-Polyol ein Mischpolyester-Diol auf der Basis von wenigstens zwei verschiedenen, zumindest teilweise in der Kohlenstoffgrundkette alkylverzweigten und/oder cycloalipathischen Diolen istAccording to the invention, this object is achieved in that the for the production of the polyurethane layer with an essentially linear polymeric linkage, polyester-polyol used a mixed polyester-diol based on at least two different, at least partially alkyl-branched in the carbon base chain and / or cycloaliphatic diols
Als alkylverzwcigte bzw. cycloalipathische Diole eignen sich insbesondere folgende Dioie:Suitable as alkyl-branched or cycloaliphatic diols In particular, the following Dioie:
1.2-Propandiol.1,2-propanediol.
1.2-Butandiol.1,2-butanediol.
13-Butandiol.13-butanediol.
2.2-Dimethyl-13- Propandiol,2,2-dimethyl-1 3- propanediol,
2-MethyI-2.4-Pentandiol.2-methyl-2,4-pentanediol.
3- Methyl-2.4-Pentandiol,3-methyl-2,4-pentanediol,
2-Äthyl-1.3-Hexandiol.2-ethyl-1,3-hexanediol.
2.2.4-Trimethyl-i J-Pentandiol.2.2.4-Trimethyl-i J-pentanediol.
Dipropylengl j ..öle,Dipropylengl j .. oils,
Tripropylenglykole,Tripropylene glycols,
Polypropylengiykole undPolypropylene glycols and
2-2- Bis(4-hydroxycyclohexyl/prop n.2-2-bis (4-hydroxycyclohexyl / prop n.
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 Neigung zur Bildung von kristallartigen Agglomeraten beim Abkühlen aus der Schmelze bzw. im Laufe der Zeit, insbesondere bei höheren Temperaturen, stark herabgesetzt ist. Gerade solche kristallinen Agglomerate, deren räumliche Ausdehnung bis zu einigen tausend Angström, also bis in die Größenordnung der WeI-lenlänge des sichtbaren Lichtes, reichen 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 crystal-like agglomerates when cooling from the melt or over time, especially at higher temperatures, is greatly reduced. Precisely such crystalline agglomerates, their spatial extent up to a few thousand Angstrom, i.e. up to the order of magnitude of the wavelength of visible light, it is they that cause the opacity of the material because of them the light is refracted and scattered.
Die Gefahr der Bildung derartiger kristalliner Agglomerate ist gerade bei solchen Polymeren besonders hoch, bei denen man keine Weichmacher einsetzen kann, oder bei denen der Einsatz von Weichmachern nachteilig ist. Ein relativ hoher Weichmacheranteil nämlich wirkt sich auf die Transparenz und Trübungsfreiheit günstig aus, weil auch dadurch die Bildung von kristall!- nen Strukturen verhindert wird. Die thermoplastische Polyurethanschicht der erfindungsgemäßen Kunststofffolie enthält jedoch kein Weichmacher, da sich die Gegenwart von Weichmachern als problematisch erwiesen hat, und sie wird außerdem beim Aufkaschieren verhältnismäßig langsam Aüfheiz- bzw. Abkühlvorgängen ausgesetzt, so daß unter diesen Umständen hier relativ günstige Voraussetzungen für die Bildung kristalliner Strukturen gegeben sind.The risk of the formation of such crystalline agglomerates is particularly particular with such polymers high, where no plasticizers can be used, or where plasticizers are used is disadvantageous. A relatively high proportion of plasticizer affects the transparency and freedom from haze favorable, because this also prevents the formation of crystalline structures. The thermoplastic However, the polyurethane layer of the plastic film according to the invention does not contain any plasticizer, since the present of plasticizers has proven to be problematic, and it also becomes proportionate when lamination is carried out slowly exposed to heating or cooling processes, so that under these circumstances it is relatively cheap 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 Erfindungsgedankens das Mischpolyester-Diol unter Verwendung von wenigstens zwei verschiedenen Dicarbonsäuren hergestellt ist Hierfür eignen sich insbesondere die folgenden Dicarbonsäuren: Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure und 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-ValeroIacton und epiylon-Caprolacton. It has been shown that the desired effect can be further improved if in Further development of the inventive concept, the mixed polyester diol is made using at least two different dicarboxylic acids for this purpose the following dicarboxylic acids are particularly suitable: malonic acid, succinic acid, glutaric acid, adipic acid, Suberic acid and sebacic acid. The addition of one or more lactones to the has the same effect Dicarboxylic acid-diol reaction, the following lactones being particularly suitable for this: gamma-butyrolactone. gamma-valerolactone, delta-valerolactone and epiylon-caprolactone.
ίο LJm 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 cycloalipathischen Diisocyanaten hergestellt sein. Für diesen Zweck eignen sich insbesondere die folgenden Diisocyanate:ίο LJm to obtain an even higher resistance to cloudiness can be expediently further Embodiment of the invention the linearly linked polyurethane using at least two various alkyl-branched in the carbon base chain and / or cycloaliphatic diisocyanates. Are particularly suitable for this purpose the following diisocyanates:
Bis(4-isocyanatocyclohexyl)methan,
Bisil-methyl^-isocyanatocyclohexyljmethan,
2_>-Bis(4-isocyanatocyciohexyi)propan,
3-Isocyanatomethyl-3.5.5-trimethylcyclohexylisocyanat
(= Isophorondiisocyanat IPDI),
2.2.4- und 2.4.4-Trimethylhexandiisocyanat,
1 J-Bis(lsocyanatomethyl)benzol).Bis (4-isocyanatocyclohexyl) methane,
Bisil-methyl ^ -isocyanatocyclohexyljmethane,
2 _> - bis (4-isocyanatocyciohexyi) propane,
3-isocyanatomethyl-3.5.5-trimethylcyclohexyl isocyanate (= isophorone diisocyanate IPDI),
2.2.4- and 2.4.4-trimethylhexane diisocyanate,
1 J-bis (isocyanatomethyl) benzene).
Nach einem bevorzugten Ausführungsbeispiel wird die erfindungsgemäße Kunststoffolie mit zweischichtigem Aufbau wie folgt hergestelltAccording to a preferred embodiment, the plastic film according to the invention is made with two-layer Structure made as follows
Es wird als Gießmasse für die Herstellung der dreidimensional vernetzten Polyurethanschicht ein Reaktionsansatz wie folgt hergestellt:It is used as a casting compound for making the three-dimensional crosslinked polyurethane layer a reaction mixture is produced as follows:
— 1000 g eines durch Kondensation von 1.2-Propylenoxid mit 2.2-Bis(hydroxymethyl-l-butano!) hergestellten Polyethers mit einem Molekulargewicht von etwa 450 und einem Gehalt an freien OH-Gruppen von 10,5 bis 12%.- 1000 g of one produced by the condensation of 1,2-propylene oxide with 2.2-bis (hydroxymethyl-1-butano!) made polyethers with a molecular weight of about 450 and a content of free OH groups of 10.5 to 12%.
— 23 g 2.6-Di-tert.-butyl-4-meihylphenol.
— 0.5 g Dibutylzinndilaurat, und- 23 g of 2,6-di-tert-butyl-4-methylphenol.
- 0.5 g dibutyltin dilaurate, and
— 1000 g eines Biurets von 1.6-Hexandiisocyanat mit einem Gehalt an freien NCO-Gruppen von 21 bis 22%- 1000 g of a biuret of 1.6-hexane diisocyanate with a content of free NCO groups of 21 to 22%
werden unter Vermeidung der Bildung von Luftblasen durch Entgasen bei Unterdruck homogen gemischt.
Diese Masse eignet sich zum Auftragen auf eine Gießunterlage beispielsweise mit einem Abstreichgießkopf.
Zur Herstellung der linearverknüpften thermoplastisehen Schicht wird zunächst in an ν h bekannter Weise
in Stickstoffatmosphäre ein mit Isocyanaten reagierender Polyester dadurch hergestellt, daß man in einem
Edelstahl-Reaktionsbehälter 145 Gew.-T. Adipinsäure und 50 Gew.-T. Sebacinsäure mit 145 Gew.-T. f-Caprolacton.
120 Gew.-T. 2.2·Dimethyl-1.3-propandiol und 80
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.-T. Reaktionswasser werden zur
Vorbereitung der Ketten Verlängerung 18 Gew.-T. 1.4-Butandiol sowie anschließend 400 Gew.-T. Xylol hinzugefügt.
Nachdem die Temperatur auf 80° C abgesenkt worden ist, werden unter starkem Rühren hintereinander
150 Gew.-T. Bis(4-isocyanatocyclohexyl)meihan undare mixed homogeneously by degassing at negative pressure, avoiding the formation of air bubbles. This mass is suitable for application to a casting base, for example with a pouring head.
To produce the linearly linked thermoplastic layer, a polyester which reacts with isocyanates is first produced in a manner known from ν h in a nitrogen atmosphere by placing 145 parts by weight in a stainless steel reaction vessel. Adipic acid and 50 parts by weight. Sebacic acid with 145 parts by weight. f-caprolactone. 120 parts by weight 2.2 · Dimethyl-1,3-propanediol and 80 parts by weight. 1,4-butanediol in the presence of 25 parts by weight. Xylene and 0.25 parts by weight. Dibutyltin dilaurate esterified azeotropically at a temperature of 180 ° C. After splitting off about 22.5 parts by weight Water of reaction are 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 80 ° C., 150 parts by weight are added one after the other with vigorous stirring. Bis (4-isocyanatocyclohexyl) meihan and
S5 50 Gew.-T. 3-Isocyanatomethyl-3.5.5-trimethylcyclohexylisocyanat zugefügt.S5 50 parts by weight 3-isocyanatomethyl-3.5.5-trimethylcyclohexyl isocyanate added.
Nach Temperaturerhöhung auf 100°C resultiert aus dem erhaltenen Additionsprodukt das linearverknüpfteAfter increasing the temperature to 100 ° C., the result is the addition product obtained the linearly linked
thermoplastische Polyurethanharz. Die Weiterpolymerisation wird fortgesetzt, bis das Molekulargewicht des Polyurethanharzes auf mindestens 40 000, bevorzugt jedoch über 50 000 angestiegen ist. Nach Abkühlung auf 700C oder weniger wird zunächst mit 3000 Gevv.-T. Methyläthylketon, und bei einer Temperatur unter 300C mit 3000 Gew.-T. Tetrahydrofuran weiterverdünnt, so daß der Festkörpergehalt des Polyurethanharzes in der Lösung ca. :0 Gew.-°/o beträgt.thermoplastic polyurethane resin. The further polymerization is continued until the molecular weight of the polyurethane resin has risen to at least 40,000, but preferably above 50,000. After cooling to 70 0 C or less is first with 3000 Gevv.-T. Methyl ethyl ketone, and at a temperature below 30 0 C with 3000 parts by weight. Tetrahydrofuran is further diluted so that the solids content of the polyurethane resin in the solution is approx. 0% by weight.
Die Herstellung der zweischichtigen Kunststoffolie erfolgt durch Auftragen der vorstehend beschriebenen Losung auf die zuerst hergestellte dreidimensional vernetzte Schicht, z. B. mit Hilfe eines Abstreichgießers, und anschließende Verdampfung des enthaltenen Lösungsmittelgemisches im Trockenkanai bei einer erhöhten Temperatur.The two-layer plastic film is produced by applying the methods described above Solution onto the three-dimensionally crosslinked layer produced first, e.g. B. with the help of a skimmer, and subsequent evaporation of the contained solvent mixture in the dry sewer 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 handein kann, aufkaschiert werden. The two-layer plastic film produced in this way is peeled off the casting base. You can then take Applying heat and pressure to the support sheet, which is a sheet of silicate glass or around a plastic plate can be laminated on by hand.
Falls die erfindungsgemäßen Folien auf eine Glasunterlage aufkaschiert werden, dienen sie in erster Linie ais Splitterschutz und verhindern jeden Kontakt mit den Glasbruchstücken. Die erfindungsgemäßen Folien können jedoch mit besonderem Vorteil auch auf Kunststoffplatten aufkaschiert werden, wobei sie in diesem Falle die Funktion einer »Kratzfestbeschichtung« übernehmen. If the films according to the invention are laminated onto a glass substrate, they are primarily used as splinter protection and prevent any contact with the broken glass. The films according to the invention can however, they can also be laminated to plastic plates with particular advantage, in which case they take on the function of a "scratch-resistant coating".
Die Kunststoffolien nach der Erfindung zeigen eine gute Haftung auf Polykarbonaten und können ebenso als gut haftende Schutzschichten auf Platten oder Folien aus einem Polyester. Polyacrylat, Polyamid, Celluloseester oder Polyvinylchlorid aufgebracht werden.The plastic films according to the invention show good adhesion to polycarbonates and can do the same 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 Fahrzeugverglasung oder für die Anwendung im Hochbau, sondern ebenso mit besonderem Vorteil als Brillengläser, Scnutzmasken. Visiere für Schutzhelme, Schutz-Schilde, 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 use in building construction, but also with particular advantage as spectacle lenses, protective masks. Visors for protective helmets, protective shields, Bulletproof glasses, etc. m.
4545
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2729226A1 DE2729226A1 (en) | 1979-01-11 |
| DE2729226C2 true DE2729226C2 (en) | 1985-07-04 |
Family
ID=25770654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2729226A Expired 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 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2729226C2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2574396B1 (en) * | 1984-12-06 | 1987-01-02 | Saint Gobain Vitrages Sa | COATING LAYER HAVING SELF-HEALING PROPERTIES FOR WINDOWS ESPECIALLY EXPOSED TO ATMOSPHERIC AGENTS |
| FR2644468B1 (en) * | 1989-03-20 | 1992-12-31 | Saint Gobain Vitrage | POLYURETHANE LAYER HAVING ENERGY ABSORBER PROPERTIES AND USE IN SECURITY GLAZING |
| CN108559052B (en) * | 2018-04-19 | 2020-10-30 | 清华大学 | Cross-linked polyurea elastomer with self-repairing performance and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR192924A1 (en) * | 1971-04-20 | 1973-03-21 | Saint Gobain | LAMINATED SAFETY GLASS |
-
1977
- 1977-06-29 DE DE2729226A patent/DE2729226C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2729226A1 (en) | 1979-01-11 |
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| 8162 | Independent application | ||
| 8178 | Suspension cancelled | ||
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