DK163039B - LAMINATED SAFETY PANEL - Google Patents
LAMINATED SAFETY PANEL Download PDFInfo
- Publication number
- DK163039B DK163039B DK337184A DK337184A DK163039B DK 163039 B DK163039 B DK 163039B DK 337184 A DK337184 A DK 337184A DK 337184 A DK337184 A DK 337184A DK 163039 B DK163039 B DK 163039B
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- DK
- Denmark
- Prior art keywords
- polyol
- isocyanate
- layer
- component
- isocyanate component
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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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
- B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
- B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
- B32B17/10908—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form
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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
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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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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7825—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing ureum groups
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
- Glass Compositions (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Surface Treatment Of Glass (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Optical Communication System (AREA)
- Jib Cranes (AREA)
Abstract
Description
DK 163039 BDK 163039 B
Opfindelsen angår en hidtil ukendt lamineret rude indeholdende en glaslamel og et transparent formstoflag, hvor det transparente formstoflag viser energiabsorberende egenskaber og indre beskyttelse defineret ved en 5 ridsemodstand på mere end 20 g målt med ERICHSEN-apparat type 413 og en sådan slidmodstand ifølge den europæiske norm R43, at klarhedsafvigeisen er mindre end 4%, og hvor formstoflaget ved en tykkelse på mindst ca. 0,5 mm viser en flydetærskelspænding σ ved -20°C lavere end 2 y qThe invention relates to a novel laminated pane containing a glass lamella and a transparent plastic layer, wherein the transparent plastic layer shows energy-absorbing properties and internal protection defined by a scratch resistance of more than 20 g measured with ERICHSEN type 413 apparatus and such wear resistance according to the European standard R43, that the clarity deviation is less than 4%, and wherein the plastic layer at a thickness of at least approx. 0.5 mm shows a flow threshold voltage σ at -20 ° C lower than 2 y q
10 eller lig 3 daN/mm , en brudspænding aD ved +20 C10 or equal to 3 daN / mm, a breaking voltage aD at +20 C
2 K2 K
større end eller lig 2 daN/mm , en brudforlængelse ved +20°C beliggende mellem 250 og 5001, en modstand mod begyndende iturivning R ved +20°C større end eller cl lig 9 daN/mm.greater than or equal to 2 daN / mm, a rupture extension at + 20 ° C located between 250 and 5001, a resistance to initial tearing R at + 20 ° C greater than or cl equal to 9 daN / mm.
15 Laminerede ruder betegnet sikkerhedsruder består i almindelighed af to glaslameller og et mellemliggende lag med energiabsorberende egenskaber, sædvanligvis af polyvinylbutyral. En af ulemperne ved denne type lamineret rude, når den anvendes som køretøjsforrude, er at 20 kanterne af det indvendige knuste glas, der fremkommer i tilfælde af sammenstød med hovedet af en person, der sidder i køretøjet, kan forårsage flænger og andre beskadigelser. Det er derfor for eksempel i de franske patentskrifter nr. 2.187.719 og 2.251.608 foreslået på denne 25 indvendige glaslamel at anbringe en formstoflamel dannet i det væsentlige af en termohærdelig polyurethan, der har antisønderrivende egenskaber. Endvidere er denne formstoflamel selvhelende, dvs. det er et materiale, hos hvilket overfladerifter eller lokale aftryk hurtigt for-30 svinder, idet forsvindingshastigheden er en funktion af riftens art og formstofmaterialets temperatur.15 Laminated panes designated security panes generally consist of two glass louvers and an intermediate layer of energy absorbing properties, usually of polyvinyl butyral. One of the drawbacks of this type of laminated pane when used as a vehicle windshield is that the 20 edges of the inside broken glass that appear in the event of a collision with the head of a person sitting in the vehicle can cause tears and other damage. For example, it is proposed, for example, in French Patent Nos. 2,187,719 and 2,251,608 to this inner glass laminate to apply a plastic laminate formed essentially of a thermosettable polyurethane having anti-tearing properties. Furthermore, this plastic lamella is self-healing, ie. it is a material in which surface tears or local imprints quickly disappear, the rate of disappearance being a function of the nature of the tear and the temperature of the plastic material.
Der er også for eksempel i fransk patentskrift nr. 2.398.606 foreslået en lamineret rude indeholdende en glaslamel, et termoplastisk lag med energiabsorberende 35 egenskaber og et belægningslag, der er selvhelende og modstandsdygtigt mod ridsning og dannet i det væsentlige af en termohærdelig polyurethan. Ved denne rudetype opfylder hvert af lagene en bestemt funktion, idet detAlso, for example, in French Patent No. 2,398,606, a laminated pane containing a glass lamella, a thermoplastic layer having energy-absorbing properties and a coating layer that is self-healing and scratch-resistant and formed essentially of a thermoset polyurethane are proposed. In this type of pane, each of the layers fulfills a specific function in that
DK 163039 BDK 163039 B
2 termoplastiske lag i det væsentlige opfylder, den funktion at absorbere energi, men ikke er tilstrækkeligt modstandsdygtigt mod slid eller ydre midler, og belægningslaget opfylder den funktion at' beskytte det energiabsor-5 berende lag, men derimod ikke udviser gode energiabsorberende egenskaber.2 thermoplastic layers essentially fulfill the function of absorbing energy, but are not sufficiently resistant to abrasion or external agents, and the coating layer fulfills the function of protecting the energy-absorbing layer, but does not exhibit good energy-absorbing properties.
Der er tidligere for eksempel i US patentskrifterne nr.Previously, for example, U.S. Pat.
3.509.015 og 3.808.077 foreslået laminerede ruder indeholdende en glaslamel og et enkelt formstoflag med ener-10 giabsorberende egenskaber. Denne rudetype har tilsyneladende aldrig været fuldt tilfredsstillende, utvivlsomt på grund af utilstrækkelig modstandsdygtighed mod slid og ridsning af det som udvendigt lag anvendte formstoflag.3,509,015 and 3,808,077 proposed laminated panes containing a glass lamella and a single plastic layer having energy-absorbing properties. This type of pane has apparently never been fully satisfactory, undoubtedly due to insufficient resistance to abrasion and scratching of the plastic layer used as the outer layer.
15 Det er alment accepteret, at en lamineret rude- struktur indeholdende et enkelt formstoflag, der på én gang har energiabsorberende egenskaber og god modstandsevne mod ridsning og mod angreb fra ydre midler, næppe ville have mulighed for at fungere tilfredsstillende.15 It is generally accepted that a laminated pane structure containing a single plastic layer, which at one time has energy-absorbing properties and good resistance to scratching and attack by external agents, would hardly be able to function satisfactorily.
20 Fagmanden på området finder en vis uforenelighed mellem den energiabsorberende funktion og den modstandsevne mod ridsning, som et enkelt lag skulle kunne opfylde. For at et lag skal vise energiabsorberende egenskaber, er det alment accepteret, at det skal vise en i det væsentlige 25 termoplastisk karakter. For at et lag skal have god modstandsevne mod ridsning er det derimod opfattelsen, at det skal udvise en i det væsentlige termohærdelig karakter med en tværbundet struktur. Disse med termoplastisk eller termohærdelig karakter forbundne mekaniske egenska-30 ber er for eksempel beskrevet i fransk patentskrift nr. 2.398.606 og i europæisk patentskrift nr. 0.054.491.One skilled in the art will find some incompatibility between the energy-absorbing function and the scratch resistance that a single layer should be able to fulfill. For a layer to exhibit energy-absorbing properties, it is generally accepted that it must exhibit a substantially thermoplastic character. On the other hand, for a layer to have good scratch resistance, it is believed that it must exhibit a substantially thermosetting character with a cross-linked structure. These mechanical properties associated with thermoplastic or thermoset are described, for example, in French Patent No. 2,398,606 and in European Patent No. 0.054,491.
Der er nu fundet et enkelt formstoflag, der i en lamineret rudestruktur, hvori det er forbundet med en glaslamel, opfylder den energiabsorberende funktion, be-35 skytter mod glassplinter og yderligere udviser en god modstand mod slid og ridsning samt mod forskellige angreb fra ydre midler.A single plastic layer has now been found which, in a laminated pane structure in which it is connected to a glass lamella, fulfills the energy-absorbing function, protects against glass splinters and further exhibits good resistance to abrasion and scratching as well as to various attacks by external means. .
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3 I overensstemmelse hermed er den laminerede rude ifølge opfindelsen ejendommelig ved, at formstoflaget er dannet hovedsageligt af en polyurethan vundet ved kontinuert reaktiv udhældning på en plan horisontal 5 bærer af en reaktionsblanding af en isocyanat-komponent og en polyol-komponent, idet isocyanat-komponenten indeholder mindst ét alifatisk eller cycloalifatisk diiso-cyanat eller en diisocyanat-præpolymer, hvilken komponent har en viskositet målt ved 40°C lavere end ca. 500 Pa*s, 10 hvorved isocyanat-komponenten indeholder urinstof-funktioner, idet urinstofindholdet kan nå op på 10% af den totale vægt af isocyanat-komponenten og fortrinsvis er beliggende mellem 5 og 7%, og polyol-komponenten indeholder mindst én lang difunktionel polyol med en mole-15 kylvægt beliggende mellem 500 og 4000 og mindst én kort diol som kædeforlængende middel, idet isocyanat-komponenten og polyol-komponenten er anvendt i sådanne mængder, at forholdet mellem isocyanat-ækvivalentgrupperne og hydroxy-ækvivalentgrupperne er omtrent lig 1, 20 hvorved blandingsforholdene mellem de forskellige poly-oler er valgt således, at antallet af hydroxy-ækvivalentgrupper, der skyldes den korte diol, repræsenterer 20-70% af de totale hydroxygrupper.Accordingly, the laminated pane of the invention is characterized in that the plastic layer is formed mainly of a polyurethane obtained by continuous reactive pouring on a planar horizontal support of a reaction mixture of an isocyanate component and a polyol component, the isocyanate component contains at least one aliphatic or cycloaliphatic diisocyanate or a diisocyanate prepolymer, which component has a viscosity measured at 40 ° C lower than ca. 500 Pa * s, 10 wherein the isocyanate component contains urea functions, the urea content being able to reach 10% of the total weight of the isocyanate component and preferably being between 5 and 7% and the polyol component containing at least one long difunctional polyol having a molecular weight located between 500 and 4000 and at least one short diol as a chain extender, the isocyanate component and the polyol component being used in such amounts that the ratio of the isocyanate equivalent groups to the hydroxy equivalent groups is approximately equal to 1, 20 whereby the mixing ratios of the various polyols are selected such that the number of hydroxy equivalent groups resulting from the short diol represents 20-70% of the total hydroxy groups.
Ved reaktiv udhældning forstås udhældning i form 25 af et lag eller en film af en flydende blanding af komponenterne i form af monomere eller præpolymere efterfulgt af en polymerisation af denne blanding ved indvirkning af varme. Denne reaktive udhældning, der bibringer laget dets gode mekaniske og optiske egenskaber, er be-30 skrevet mere detaljeret i det følgende.Reactive pouring means pouring in the form of a layer or film a liquid mixture of the components in the form of monomers or prepolymers followed by a polymerization of this mixture by the action of heat. This reactive pour which imparts to the layer its good mechanical and optical properties is described in more detail below.
Blandingsforholdene for polyurethanens komponenter er valgt således, at der fortrinsvis opnås et støkiometrisk ækvilibreret system, dvs. at forholdet mellem ækvivalentgrupperne NCO tilvejebragt med diisocyanat-kompo-35 nenten og ækvivalentgrupperne OH tilvejebragt af polyol-komponenten, dvs. den eller de lange polyoler og den eller de korte dioler, er af størrelsesordenen 1. Når for-The mixing ratios of the polyurethane components are chosen such that a stoichiometric equilibrated system is preferably obtained, i.e. that the ratio of the equivalent groups of NCO provided with the diisocyanate component to the equivalent groups of OH provided by the polyol component, i.e. the long polyol (s) and the short diol (s) are of the order of 1. When
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4 holdet NC0/0H er lavere end 1, gælder det, at jo mere det aftager, i desto højere grad bliver de for anvendelsen ønskede mekaniske egenskaber hurtigt utilfredsstillende. Når alle polyurethanens komponenter er difunktio-5 nelle, er den nedre gramse for forholdet NC0/0H, for opnåelse af tilfredsstillende mekaniske egenskaber, beliggende ved ca. 0,9. Når mindst én af komponenterne er tri-funktionel, kan nævnte nedre grænse sænkes til ca. 0,8.4 the NC0 / 0H is lower than 1, the more it decreases, the sooner the mechanical properties desired for use become rapidly unsatisfactory. When all the components of the polyurethane are difunctional, the lower gram of the ratio of NC0 / OH, to obtain satisfactory mechanical properties, is located at approx. 0.9. When at least one of the components is tri-functional, said lower limit can be lowered to approx. 0.8.
Når forholdet NCO/OH er større end 1, gælder det, at jo 10 mere det stiger, desto mere forstærkes visse mekaniske egenskaber hos det lag, der vindes ved reaktiv udhæld-ning, idet laget for eksempel bliver mere stift, men i betragtning af at isocyanat-komponenten er mere kostbar end polyol-komponenten, er valget af et forhold NCO/OH 15 i det væsentlige lig 1 et godt kompromis mellem de opnåede egenskaber og omkostningerne.When the ratio of NCO / OH is greater than 1, the more it increases, the more certain mechanical properties of the layer obtained by reactive pouring are reinforced, for example, the layer becomes more rigid, but considering that the isocyanate component is more expensive than the polyol component, the choice of a ratio of NCO / OH 15 is essentially equal to a good compromise between the properties obtained and the cost.
Blandingsforholdene mellem den lange polyol og den korte diol kan variere som funktion af de Ønskede egenskaber, som omtalt nedenfor, men antallet af ækvivalent-20 grupper OH stammende fra den korte diol repræsenterer som nævnt 20-70% af de totale ækvivalentgrupper fra den blanding, der udgør polyol-komponenten i. det tilfælde, hvor forholdet mellem ækvivalentgrupperne NCO og grupperne OH er af størrelsesordenen 1. Når mængden af 25 kort diol hæves, bliver laget hårdere, og dets modul hæves i almindelighed.The mixing ratios of the long polyol to the short diol may vary as a function of the desired properties, as discussed below, but as mentioned, the number of equivalent groups of OH derived from the short diol represents 20-70% of the total equivalent groups of that mixture. constituting the polyol component in the case where the ratio of the equivalent groups of NCO to the groups of OH is of the order of 1. When the amount of 25 short diol is raised, the layer becomes harder and its module is generally raised.
De i forbindelse med den foreliggende opfindelse anvendelige diisocyanater vælges navnlig blandt følgende difunktionelle alifatiske isocyanater: hexamethylendi-30 isocyanat (HMDI), 2,2,4-trimethyl-l,6-hexandiisocyanat (TMDI), bis-4-isocyanatocyclohexylmethan (Hylene W), bis-3-methyl-4-isocyanatocyclohexylmethan, 2,2-bis-(4-isocyanatocyclohexyl)propan, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanat (IEDI), m-xylylendiisocya-35 nat (XDI), m- og p-tetramethylxylylendiisocyanat (m- og p-TMXDI), trans-cyclohexan-l,4-diisocyanat (CHDI), 1,3-(diisocyanatomethyl)-cyclohexan (hydrogeneret XDI).In particular, the diisocyanates useful in the present invention are selected from the following difunctional aliphatic isocyanates: hexamethylenedi isocyanate (HMDI), 2,2,4-trimethyl-1,6-hexanedisocyanate (TMDI), bis-4-isocyanatocyclohexylmethane (Hylene W ), bis-3-methyl-4-isocyanatocyclohexylmethane, 2,2-bis (4-isocyanatocyclohexyl) propane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IEDI), m-xylylenediisocyanate (XDI), m- and p-tetramethylxylylene diisocyanate (m- and p-TMXDI), trans-cyclohexane-1,4-diisocyanate (CHDI), 1,3- (diisocyanatomethyl) -cyclohexane (hydrogenated XDI).
Der anvendes fortrinsvis IPDI, navnlig på grund af fabrikationsomkostningerne.Preferably, IPDI is used, especially because of the manufacturing cost.
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Som nævnt anvendes til formstoflaget i den laminerede rude ifølge opfindelsen en isocya- ponent indeholdende urinstof-funktioner. Disse -of-funktioner forbedrer visse mekaniske egenskaber 5 ru. laget. Indholdet af urinstof kan repræsentere op til ca. 10% af den totale vægt af isocyanat-komponenten med urinstof-funktioner. Urinstofindholdet ligger fortrinsvis mellem 5 og 7% af den totale vægt af nævnte komponent. Af ovennævnte grund anvendes fortrinsvis 3-iso-10 cyanatomethyl-3,5,5-trimethylcyclohexylisocyanat indeholdende urinstoffunktioner (IPDI og derivater).As mentioned, for the plastic layer in the laminated pane of the invention, an isocyan component containing urea functions is used. These -of features enhance certain mechanical properties 5 rough. layer. The content of urea can represent up to approx. 10% of the total weight of the isocyanate component with urea functions. The urea content is preferably between 5 and 7% of the total weight of said component. For the above reason, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate containing urea functions (IPDI and derivatives) is preferably used.
De anvendelige lange polyoler vælges blandt poly-etherdioler eller polyesterdioler med en molekylvægt på 500-4000, idet polvesterdiolerne er esterificeringspro-15 dukter af en disyre, såsom adipinsyre, ravsvre, palmitin-syre, azelainsyre, sebacinsyre eller o-phthalsyre, og en diol, såsom ethylenglycol, 1,3-propandiol, 1,4-butandiol eller 1,6-hexandiol, og polyetherdiolerne har den almene formel:The useful long polyols are selected from polyether diols or polyester diols having a molecular weight of 500-4000, the polyester diols being esterification products of a diacid such as adipic acid, succinic acid, palmitic acid, azelaic acid, sebacic acid or ophthalic acid, and a diol. , such as ethylene glycol, 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol, and the polyether diols have the general formula:
20 Bi0<CH2>Å0HBi0 <CH2> Å0H
hvor n = 2-6, og m som molekylvægten er beliggende i området 500-4000, eller polyetherdiolerne har den almene formel: CH0 I 0where n = 2-6, and m as the molecular weight is in the range of 500-4000, or the polyether diols have the general formula:
H{OCH - CH,+ OHH {AND - CH, + OH
m Hl 25 hvor m som molekylvægten er beliggende i området 500-4000. Der kan også anvendes polycaprolactondioler.m Hl 25 where m as the molecular weight is in the range 500-4000. Polycaprolactone diols can also be used.
Der anvendes fortrinsvis en polytetraraethylenglycol (n = 4) med en molekylvægt omtrent på 1000.Preferably, a polytetraraethylene glycol (n = 4) having a molecular weight of about 1000 is used.
30 De anvendelige kædeforlængende midler er korte di- oler, såsom ethylenglycol, 1,2-propandiol, 1,3-propandi-ol, 1,2-, 1,3- eller 1,4-butandiol, 2,2-dimethyl-l,3-propandiol (neopentylglycol), 1,5-pentandiol, 1,6-hexandiol, 1,8-octandiol, 1,10-decandiol, 1,12-dodecandiol, 35 cyclohexandimethanol, bisphenol A, 2-methyl-2,4-pentandi-ol, 3-methyl-2,4-pentandiol, 2-ethyl-l,3-hexandiol, 2,2,4-trimethyl-l,3-pentandiol, diethylenglycol, tri-ethylenglycol, tetraethylenglycol, 2-butyn-l,4-diol, 1,4-The useful chain extender agents are short diesels, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 2,2-dimethylene. 1,3-propanediol (neopentyl glycol), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, cyclohexanedimethanol, bisphenol A, 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, tetraethylene glycol, 2 -butyn-1,4-diol, 1,4-
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6 butendiol og decyndiol substituerede og/eller etherifi-cerede7 hydroquinon-bis-hydroxyethylether, bisphenol A etherificerede med to eller fire grupper propylenoxid, dimethylolproponsyre. I almindelighed gælder, at jo kor-5 tere diolen er, desto hårdere er laget.6 butenediol and decyndiol substituted and / or etherified 7 hydroquinone bis hydroxyethyl ether, bisphenol A etherified with two or four groups of propylene oxide, dimethylol proponic acid. In general, the shorter the diol, the harder the layer.
Der anvendes fortrinsvis 1,4-butandiol, der er et godt kompromis for opnåelse af et lag, der hverken er for hårdt eller for blødt, og som ønskes til den foreliggende anvendelsestype.Preferably, 1,4-butanediol is used which is a good compromise to obtain a layer that is neither too hard nor too soft and which is desired for the present type of application.
10 Som nævnt i formstoflaget i den laminerede rude ifølge opfindelsen hovedsageligt dannet ved reaktiv udhældning på en plan horisontal bærer, hvilken reaktive udhældning, der allerede er beskrevet i fransk patentskrift nr. 2.442.128 for opnåelse af et termohærdeligt polyurethanlag ud fra en blanding af 15 trifunktionelle komponenter, på overraskende måde i tilfældet ifølge opfindelsen med difunktionelle udgangskomponenter tilvejebringer et lag, der ikke er fuldstændigt termoplastisk, når forholdet mellem grupperne NC0/0H er i det væsentlige lig eller større end 1.As mentioned in the plastic layer of the laminated pane according to the invention, formed mainly by reactive pouring on a flat horizontal support, which reactive pouring already described in French Patent No. 2,442,128 to obtain a thermosettable polyurethane layer from a mixture of 15 trifunctional components, surprisingly in the case of the invention with difunctional starting components, provide a layer that is not completely thermoplastic when the ratio of the groups NC0 / OH is substantially equal to or greater than 1.
20 Den reaktive udhældning indebærer en hurtig poly merisationsreaktion for at laget skal dannes inden for tidsrum, der er forenelige med en industriel fabrikation.The reactive pouring involves a rapid polymerization reaction for the layer to form within periods compatible with an industrial fabrication.
Dette nødvendiggør en forhøjet temperatur af størrelsesordenen ca. 100-140°C, hvilket er en temperatur, ved 25 hvilken sekundære forgreningsreaktioner forekommer, der tilvejebringer for eksempel allophanat- og/eller biuret-grupper mellem urethankæderne, såsom:This necessitates an elevated temperature of the order of approx. 100-140 ° C, which is a temperature at which secondary branching reactions occur, for example providing allophanate and / or biuret groups between the urethane chains, such as:
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7 — R-NH-CO-O-R' - O —7 - R-NH-CO-O-R '- O -
OCN - R - NCOOCN - R - NCO
— R-NH-CO-O-R* - O — 5 ___ — R M - CO^ O - R* - O — ' i / ' CO # allophanat • NH / » \ > R / v- "- R-NH-CO-O-R * - O - 5 ___ - R M - CO ^ O - R * - O - 'i /' CO # allophanate • NH / »\> R / v-"
10 NH10 NH
CO · \ — R- N - CO - R* - O- 15 1Ί eller — R" - NH - CO - NH - R" —CO · \ - R - N - CO - R * - O - 1Ί or - R "- NH - CO - NH - R" -
20 OCN - R - NCO20 OCN - R - NCO
-R" - NH - CO - NH - R" --R "- NH - CO - NH - R" -
^ I^ I
— R" JY- C0~- NH V R" — i 1 /- R "YY-C0 ~ - NH V R" - i 1 /
i COin CO
. 1 ^ 25 *VNH biuret. 1 ^ 25 * VNH biuret
RR
NHNH
iin
COCO
— R" - N - CO - NH - R“— 30 Under disse operationsbetingelser er det vundne produkt, selv med difunktionelle komponenter, når forholdet NCO/OH er i det væsentlige lig eller større end 1, som ovenfor angivet, ikke fuldstændigt termoplastisk.- R "- N - CO - NH - R" - 30 Under these operating conditions, the product obtained, even with difunctional components, when the ratio NCO / OH is substantially equal to or greater than 1, as indicated above, is not completely thermoplastic.
Det er i virkeligheden usmelteligt og uopløseligt i de 35 fleste opløsningsmidler for polyurethaner, såsom tetra-hydrofuran eller dimethylformamid. Dette er ingen ulempe, da laget allerede er dannet. Tværtimod opnås som enIt is in fact immiscible and insoluble in most solvents for polyurethanes such as tetrahydrofuran or dimethylformamide. This is no disadvantage as the layer is already formed. On the contrary, obtained as one
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8 fordel forbedrede mekaniske egenskaber for laget, navnlig hvad angår flydetærskelspændingen brudspændingen brudforlængelsen eR, modstanden mod begyndende itu-rivning R_, ridsemodstanden målt ved ERICHSEN-test som8 advantage improved mechanical properties of the layer, in particular with respect to the flow threshold stress fracture stress fracture elongation eR, resistance to initial tearing R_, the scratch resistance measured by ERICHSEN test as
Cl 5 nedenfor beskrevet, eller slidmodstanden, sammenlignet med et ækvivalent system polymeriseret ved lav temperatur, hvor der kun sker en lineær polykondensation.Cl 5 described below, or the wear resistance, compared to an equivalent system polymerized at low temperature where only linear polycondensation occurs.
Når forholdet NCO/OH er mindre end 1 og af størrelsesordenen 0,8 til 0,9, sker der kun i ubetydelig 10 grad en tværbinding af den ovenfor beskrevne type.When the NCO / OH ratio is less than 1 and of the order of 0.8 to 0.9, only a negligible degree of cross-linking of the type described above occurs.
Ved en tilvejebringelse af polyurethanlaget i den laminerede rude ifølge opfindelsen kan polyol-komponenten indeholde en lille mængde af mindst én polyol med funktionalitet højere end to og navnlig alifatiske monomere trioler, såsom glyce-•15 rol, trimyhylolpropan, trioler med polyetherkæde, trioler af polycaprolacton, idet molekylvægten af disse trioler i almindelighed er beliggende mellem 90 og 1000, blandede polyether/polyester-polyoler med en funktionalitet større end 2, for eksempel en funktionalitet be-20 liggende mellem 2 og 3. Tilsætning af en polyol med en funktionalitet større end 2 fremmer yderligere broforbindelser mellem polyurethanens kæder og kan således forbedre lagets kohæsion yderligere.By providing the polyurethane layer in the laminated pane of the invention, the polyol component may contain a small amount of at least one polyol having functionality higher than two and especially aliphatic monomeric triols such as glycerol, trimyhylol propane, polyether chain triols, polycaprol triols with the molecular weight of these triplets generally being between 90 and 1000, mixed polyether / polyester polyols having a functionality greater than 2, for example a functionality lying between 2 and 3. Addition of a polyol having a functionality greater than 2 further promotes bridge links between the chains of the polyurethane and thus can further improve the cohesion of the layer.
Blandingsforholdene mellem den lange polyol, den 25 korte diol og eventuelt polyolen med en funktionalitet større end 2 kan variere med de ønskede egenskaber. Der vælges i almindelighed sådanne blandingsforhold, at, for 1 ækvivalent hydroxyl, den lange polyol repræsenterer ca. 0,30 til 0,45 ækvivalent, den korte diol repræsente-30 rer ca. 0,2 til 0,7 ækvivalent, og polyolen med en funktionalitet større end 2 repræsenterer ca. 0 til 0,35 ækvivalent. Under disse betingelser udviser laget de ovenfor nævnte mekaniske karakteristika målt ifølge normerne AFNOR/NFT 46.002, 51.034 og 54.108: 35 En del af polyol-komponenten kan eventuelt erstat tes med et andet produkt med aktive hydrogener, såsom en amin.The mixing ratios of the long polyol, the 25 short diol, and optionally the polyol with a functionality greater than 2 may vary with the desired properties. Generally, such blending ratios are chosen that, for 1 equivalent of hydroxyl, the long polyol represents approx. 0.30 to 0.45 equivalent, the short diol represents approx. 0.2 to 0.7 equivalent, and the polyol having a functionality greater than 2 represents approx. 0 to 0.35 equivalent. Under these conditions, the layer exhibits the aforementioned mechanical characteristics measured according to the standards AFNOR / NFT 46.002, 51.034 and 54.108: 35. Part of the polyol component may optionally be replaced with another product with active hydrogens such as an amine.
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Ifølge en udførelsesform for formstoflaget i den laminerede rude ifølge opfindelsen kan isocyanat-komponenten i begrænsede mængder, for eksempel mindre end ca. 15% i NCO-ækvi-valenter, indeholde et triisocyanat, såsom et bluret af 5 isocyanat eller et triisocyanurat.According to an embodiment of the plastic layer in the laminated pane according to the invention, the isocyanate component can be used in limited quantities, for example less than approx. 15% in NCO equivalents contain a triisocyanate such as a blur of isocyanate or a triisocyanurate.
For at opfylde alle de krævede funktioner skal po-lyurethanlaget ifølge opfindelsen udvise en tykkelse almindeligvis større end 0,4 mm og fortrinsvis større end 0,5 mm.In order to fulfill all the required functions, the polyurethane layer of the invention must have a thickness generally greater than 0.4 mm and preferably greater than 0.5 mm.
10 Laget ifølge opfindelsen kan indeholde forskellige additiver, der i almindelighed tjener til at lette dets fremstilling ved reaktiv udhældning. Det kan indeholde en katalysator, såsom en tinkatalysator, for eksempel di-butyltindilaurat, tributyltinoxid, tinoctoat, en organo-15 kviksølv-katalysator, for eksempel phenylmercuriester, en amin-katalysator, såsom diazabicyclo-(2,2,2)-octan eller l-(l,8-diazabicyclo-(5,4,0))-7-decen. Laget kan indeholde et stabiliseringsmiddel, såsom bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacat eller en phenolisk anti-20 oxidant.The layer of the invention may contain various additives which generally serve to facilitate its preparation by reactive pouring. It may contain a catalyst such as a tin catalyst, for example dibutyltin dilaurate, tributyltin oxide, tin octoate, an organo-mercury catalyst, for example, phenylmercury ester, an amine catalyst such as diazabicyclo- (2,2,2) -octane or L- (l, 8-diazabicyclo (5,4,0)) - 7-decene. The layer may contain a stabilizer such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate or a phenolic antioxidant.
Laget kan ligeledes indeholde et belæggende middel, såsom en siliconeharpiks, en fluoralkyleret ester eller en acrylharpiks.The layer may also contain a coating agent such as a silicone resin, a fluoroalkylated ester or an acrylic resin.
Opfindelsen beskrives nærmere gennem følgende eks-25 empier på fremstilling af laminerede ruder og på det til denne fremstilling anvendte formstoflag.The invention is further described by the following examples in the manufacture of laminated glazing and the plastic layer used for this manufacture.
Eksempel 1Example 1
Til fremstilling af formstoflaget fremstilles for-30 ud polyol-komponenten ved at blande en polytetramethylen-glycol med en molekylvægt på 1000 (for eksempel produktet forhandlet under navnet Polymeg 1000 af firmaet QUAKER OATS) med 1,4-butandiol, idet blandingsforholdene for de to konstituenter er sådanne, at polytetramethylen-35 glycolen tilvejebringer 0,37 ækvivalent af hydroxygrup-per, mens 1,4-butandiolen tilvejebringer 0,63 ækvivalent deraf.To prepare the plastic layer, the polyol component is prepared by mixing a polytetramethylene glycol having a molecular weight of 1000 (for example, the product sold under the name Polymeg 1000 by the company QUAKER OATS) with 1,4-butanediol, the mixing ratios of the two constituents are such that the polytetramethylene glycol provides 0.37 equivalent of hydroxy groups, while the 1,4-butanediol provides 0.63 equivalent thereof.
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10 I polyol-komponenten inkorporeres et stabiliseringsmiddel i en mængde på 0,5 vægt% af den totale masse af polyol-komponenten og isocyanat-komponenten, et belæggende middel i en mængde på 0,05 vægt% beregnet på samme 5 måde og en katalysator af dibutyltindilåurat i en mængde på 0,02 vægt% beregnet på samme måde som ovenfor.In the polyol component, a stabilizing agent is incorporated in an amount of 0.5% by weight of the total mass of the polyol component and the isocyanate component, a coating agent in an amount of 0.05% by weight calculated in the same manner and a catalyst of dibutyltin diurea in an amount of 0.02% by weight calculated in the same manner as above.
Den anvendte isocyanat-komponent er 3-isocyanato-methyl-3,5,5-trimethylcyclohexylisocyanat (IPDI) udvisende urinstoffunktioner,opnået ved partiel hydrolyse af 10 IPDI,og med et indhold af NCO-grupper på ca. 31,5 vægt%.The isocyanate component used is 3-isocyanato-methyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) exhibiting urea functions, obtained by partial hydrolysis of 10 IPDI, and having a content of NCO groups of approx. 31.5% by weight.
Komponenterne anvendes i sådanne mængder, at forholdet NCO/OH er 1. Efter afluftning af komponenterne i vakuum bliver den til 40°C bragte blanding ved hjælp af et udhældningshoved som det i fransk patentskrift nr.The components are used in such quantities that the ratio of NCO / OH is 1. After deaeration of the components in vacuo, the mixture is brought to 40 ° C by means of a pouring head such as that in French patent no.
15 2.347.170 beskrevne udhældt på en mobil glasbærer belagt med et separationsmiddel. På denne måde dannes et lag med en ensartet tykkelse på ca. 0,755 mm, som udsættes for en polymerisationsperiode, dvs. for en temperatur på 120°C i ca. 25 minutter.15,347,170 described poured onto a mobile glass carrier coated with a separation agent. In this way, a layer with a uniform thickness of approx. 0.755 mm, which is subjected to a polymerization period, i.e. for a temperature of 120 ° C for approx. 25 minutes.
20 Efter polymerisation tages laget af glasbæreren og danner en lamel, der kan lagres eller anvendes umiddelbart efter til fremstilling af laminerede ruder.After polymerization, the layer is taken off the glass support to form a slab which can be stored or used immediately after to produce laminated panes.
Til fremstilling af ruden samles formstoflamellen med en lamel af af hærdet glas med en tykkelse på 2,6 mm.To make the pane, the plastic laminate is assembled with a hardened glass slab of 2.6 mm thick.
25 Glasset kan eventuelt gøres hårdt eller hærdes. Denne samling kan foregå i to etaper, idet en første etape består i en præliminær samling ved passage af de i ruden indgående elementer mellem to kalandervalser, hvortil der kan anvendes apparatet beskrevet i europæisk patent-30 skrift nr. 0015209, og en anden etape består i anbringelse af det laminerede produkt i en autoklav, hvori det i ca.25 The glass may be hardened or hardened. This assembly can take place in two stages, a first stage consisting of a preliminary assembly by passing the elements contained in the pane between two calender rolls to which the apparatus described in European Patent No. 0015209 can be used and a second stage consists of in placing the laminated product in an autoclave wherein
1 time udsættes for et tryk på ca. 10 bar ved en temperatur på ca. 135°C. Denne autoklavperiode kan eventuelt erstattes med en periode i ovn uden tryk.1 hour is exposed to a pressure of approx. 10 bar at a temperature of approx. 135 ° C. This autoclave period can optionally be replaced by a period in the oven without pressure.
35 Den vundne rude udviser udmærket optisk kvalitet og perfekt transparens.35 The won pane exhibits excellent optical quality and perfect transparency.
Den opnåede adhæsion mellem glaslamellen og formstoflaget måles ved en afskrælningstest beskrevet nedenfor.The adhesion obtained between the glass slat and the plastic layer is measured by a peel test described below.
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1111
Der afskæres et bånd med en bredde på 5 cm på dækningslaget. Enden af båndet adskilles, og der påføres en trækkraft vinkelret på rudeoverfladen med en hastighed på 5 cm pr.minut. Operationen foretages ved +20°C. Der 5 noteres den middeltrækkraft, der er nødvendig for at adskille båndet. På denne måde fandtes en trækkraft på 10 daN/5 cm.A band with a width of 5 cm is cut on the cover layer. The end of the strip is separated and a traction applied perpendicular to the pane surface at a rate of 5 cm per minute. The operation is performed at + 20 ° C. Note 5 is the mean tensile force required to separate the belt. In this way, a traction force of 10 daN / 5 cm was found.
Chokmodstandsteste ved forskellige temperaturer gennemførtes på den ifølge eksemplet fremstillede rude.Shock resistance tests at various temperatures were performed on the pane manufactured according to the example.
10 En første chokmodstandstest gennemføres ved +20°C10 An initial shock resistance test is performed at + 20 ° C
med en stålkugle på 2,260 kg (test med stor kugle), som får lov at falde på den centrale del af en prøve af lamineret rude med en sidekant på 30,5 cm og holdt på en stiv ramme. Der bestemmes den omtrentlige højde, for 15 hvilken 90% af de testede prøver ved en valgt temperatur modstår kuglens fald uden at blive gennemtrængt.with a steel ball of 2,260 kg (large ball test), which is allowed to fall on the central part of a sample of laminated pane with a side edge of 30.5 cm and held on a rigid frame. The approximate height is determined for which 90% of the samples tested at a selected temperature withstand the drop of the ball without being penetrated.
For den laminerede rude ifølge eksemplet var den opnåede værdi på 12 meter.For the laminated pane according to the example, the value obtained was 12 meters.
En anden chokmodstandstest gennemføres. med en 20 stålkugle på 0,227 kg og en diameter på 38 mm. En test gennemføres ved en temperatur på -20°C. En anden test gennemføres- ved en temperatur på +40°C. De opnåede værdier var på henholdsvis 12 m og 11 m.Another shock resistance test is conducted. with a 20 steel ball of 0.227 kg and a diameter of 38 mm. A test is carried out at a temperature of -20 ° C. Another test is carried out at a temperature of + 40 ° C. The values obtained were 12 m and 11 m respectively.
Ifølge den gældende europæiske norm R43 er de øn-25 skede resultater på mindst 4 m for den store kugle, mindst 8,5 m for den lille kugle ved -20°C og mindst 9 m for den lille kugle ved +40°C.According to the current European standard R43, the desired results are at least 4 m for the big ball, at least 8.5 m for the small ball at -20 ° C and at least 9 m for the small ball at + 40 ° C.
Ridsemodstanden måles' ved ridsetesten kendt under betegnelsen "MAR resistant test", og som foretages med 30 ERICHSEN-apparat type 413. Der måles den belastning, der skal påføres et diamanthoved for at indføre en varig ridse på formstoflaget samlet med glasbæreren. Belastningen skal være større end eller lig 20 g, for at formstoflaget har den egenskab at være selvhelende.The scratch resistance is measured by the scratch test known under the designation "MAR resistant test" and is made with 30 ERICHSEN type 413 apparatus. The load to be applied to a diamond head is measured to introduce a permanent scratch on the plastic layer together with the glass support. The load must be greater than or equal to 20 g for the plastic layer to have the property of self-healing.
35 Ridsemodstanden målt ved denne test var for ruden ifølge eksemplet på 32 g.The scratch resistance measured by this test was for the pane according to the example of 32 g.
Slidmodstanden måles ifølge den europæiske norm R43. Til dette formål udsættes en samlet rudeprøveThe wear resistance is measured according to European standard R43. For this purpose, a total windscreen sample is exposed
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12 for slid ved hjælp af en slibesten. Efter 100 slidture måles med et spektrofotometer klarhedsafvigelsen mellem den slidte del og den ikke slidte del. Klarhedsafvigelsen (Δ klarhed) skal være mindre end 4%, for at laget 5 har antislid-kvalitet.12 for abrasion using a grindstone. After 100 wear trips, a spectrophotometer deviation of clarity between the worn part and the non-worn part is measured with a spectrophotometer. Clarity deviation (Δ clarity) must be less than 4% for layer 5 to have anti-wear quality.
Laget ifølge eksemplet viste en klairhedsafvigelse på 0,94%.The layer according to the example showed a clearance deviation of 0.94%.
Ruden ifølge eksemplet viste alle de karakteristika, der gør den egnet til anvendelse som køretøjs-for-10 rude.The pane according to the example showed all the characteristics which make it suitable for use as a vehicle front pane.
Eksempel 2Example 2
Der anvendtes samme fremgangsmåde som i Eksempel 1 med den undtagelse, at polyol-komponenten var dannet af 15 en blanding af polytetramethylenglycol med en molekylvægt på 1000, 1,4-butandiol og polycaprolactontriol (for eksempel produktet forhandlet under betegnelsen Niax 301 af firmaet UNION CARBIDE) i sådanne respektive mængder, at der til ialt ét ækvivalent hydroxyl anvendtes 0,35, 0,45 20 og 0,20 ækvivalent hydroxyl.The same procedure was used as in Example 1 except that the polyol component was formed from a mixture of polytetramethylene glycol having a molecular weight of 1000, 1,4-butanediol and polycaprolacton triol (for example, the product sold under the designation Niax 301 by UNION CARBIDE ) in such respective amounts that 0.35, 0.45, 20 and 0.20 equivalent of hydroxyl were used for a total of one equivalent of hydroxyl.
Der blev fremstillet et lag med en tykkelse på 0,70 mm. Den vundne rude viste mekaniske og optiske karakteristika, der var fuldt tilfredsstillende. De ved de forskellige forsøg målte værdier var følgende; 25 - en adhæsion på 11 daN/5 cm, - værdier på henholdsvis 8 m for stor kugle og 11 m og 11 mm for lille kugle ved -20° og +40°C, - en ridsemodstand på 35 g og - en klarhedsafvigelse på 1,2%.A layer having a thickness of 0.70 mm was prepared. The won pane showed mechanical and optical characteristics that were fully satisfactory. The values measured by the different experiments were as follows; 25 - an adhesion of 11 daN / 5 cm, - values of 8 m for large ball and 11 m and 11 mm for small ball at -20 ° and + 40 ° C respectively, - a scratch resistance of 35 g and - a deviation of clarity of 1.2%.
30 Den ifølge dette eksempel fremstillede rude var således egnet til brug som forrude.The pane made according to this example was thus suitable for use as a windshield.
Eksempel 3Example 3
Der anvendtes samme fremgangsmåde som i Eksempel 2 35 med den undtagelse, at blandingsforholdene mellem de forskellige polyoler var sådanne, at der til ialt ét ækvivalent hydroxyl anvendtes 0,35, 0,55 og 0,10 ækvivalent hydroxyl fra henholdsvis den lange polyol, denThe same procedure as in Example 2 35 was used except that the mixing ratios of the different polyols were such that 0.35, 0.55 and 0.10 equivalent of hydroxyl from the long polyol, respectively, were used for a total of one equivalent of hydroxyl.
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8311507 | 1983-07-11 | ||
FR8311507A FR2549037B1 (en) | 1983-07-11 | 1983-07-11 | SAFETY SHEET GLAZING |
Publications (4)
Publication Number | Publication Date |
---|---|
DK337184D0 DK337184D0 (en) | 1984-07-09 |
DK337184A DK337184A (en) | 1985-01-12 |
DK163039B true DK163039B (en) | 1992-01-13 |
DK163039C DK163039C (en) | 1992-06-09 |
Family
ID=9290703
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK337184A DK163039C (en) | 1983-07-11 | 1984-07-09 | LAMINATED SAFETY PANEL |
Country Status (24)
Country | Link |
---|---|
EP (1) | EP0131523B1 (en) |
JP (1) | JPS6071253A (en) |
KR (1) | KR930000775B1 (en) |
AT (1) | ATE31896T1 (en) |
AU (1) | AU575059B2 (en) |
BR (1) | BR8403426A (en) |
CA (1) | CA1261241A (en) |
DE (1) | DE3468647D1 (en) |
DK (1) | DK163039C (en) |
ES (1) | ES534172A0 (en) |
FI (1) | FI77602C (en) |
FR (1) | FR2549037B1 (en) |
HU (1) | HU194770B (en) |
IE (1) | IE57796B1 (en) |
IL (1) | IL72360A (en) |
IN (1) | IN162382B (en) |
MA (1) | MA20175A1 (en) |
NO (1) | NO161967C (en) |
NZ (1) | NZ208854A (en) |
PH (1) | PH26588A (en) |
PT (1) | PT78883B (en) |
SU (1) | SU1491326A3 (en) |
YU (1) | YU43368B (en) |
ZA (1) | ZA845292B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4592947A (en) * | 1984-06-04 | 1986-06-03 | Sierracin Corporation | Low temperature laminatable polyurethane |
FR2576011B1 (en) * | 1985-01-15 | 1991-10-31 | Saint Gobain Vitrage | PROCESS AND DEVICE FOR MANUFACTURING SAFETY GLAZING |
FR2576012B1 (en) * | 1985-01-15 | 1991-11-22 | Saint Gobain Vitrage | PROCESS AND DEVICE FOR MANUFACTURING SAFETY GLAZING |
IT1204812B (en) * | 1986-02-19 | 1989-03-10 | Siv Soc Italiana Vetro | PROCEDURE FOR THE MANUFACTURE OF A SAFETY GLASS FOR VEHICLES AND BUILDINGS, AND PRODUCT SO OBTAINED |
DE3881570T2 (en) * | 1987-03-17 | 1994-02-03 | Asahi Glass Co Ltd | Reactive curable composition and products containing the cured products of this composition. |
DE4021113A1 (en) * | 1990-07-03 | 1992-01-09 | Bayer Ag | Adhesives based on polyols and polyisocyanates |
DE4124839C1 (en) * | 1991-07-26 | 1992-07-09 | Vegla Vereinigte Glaswerke Gmbh, 5100 Aachen, De | |
US5846897A (en) * | 1997-03-19 | 1998-12-08 | King Industries, Inc. | Zirconium urethane catalysts |
FR2827855B1 (en) | 2001-07-25 | 2004-07-02 | Saint Gobain | GLAZING PROVIDED WITH A STACK OF THIN FILMS REFLECTING INFRARED AND / OR SOLAR RADIATION |
EA008369B1 (en) * | 2005-04-12 | 2007-04-27 | Светлана Сергеевна Стацевич | Method of advertising information and information device |
US7595759B2 (en) * | 2007-01-04 | 2009-09-29 | Apple Inc. | Handheld electronic devices with isolated antennas |
FR3013043B1 (en) | 2013-11-08 | 2015-11-20 | Saint Gobain | SUBSTRATE COATED WITH A FUNCTIONAL LAYER STACK HAVING IMPROVED MECHANICAL PROPERTIES |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4024113A (en) * | 1976-04-28 | 1977-05-17 | Ppg Industries, Inc. | Polycarbonate polyurethanes based on particular aliphatic/cycloaliphatic polycarbonates |
DE2629779C3 (en) * | 1976-07-02 | 1985-04-04 | Saint Gobain | Process for the production of a two-layer film with self-healing properties using polyurethanes as a shatterproof layer on safety glass |
FR2385751A1 (en) * | 1977-03-28 | 1978-10-27 | Ppg Industries Inc | Polyurethane free from ether linkages - used for glazing or optical lenses, and hard, flexible and resist to weathering |
FR2442128A1 (en) * | 1978-11-23 | 1980-06-20 | Saint Gobain | PROCESS FOR PRODUCING SHEETS OF PLASTIC MATERIAL |
FR2470682A1 (en) * | 1979-12-06 | 1981-06-12 | Saint Gobain | PROCESS FOR PRODUCING LAMINATES, LAMINATES OBTAINED AND GLUE USED THEREIN |
CA1174577A (en) * | 1980-04-30 | 1984-09-18 | Vernon G. Ammons | Polyurethane composition for safety glass interlayer |
FR2496089A1 (en) * | 1980-12-11 | 1982-06-18 | Saint Gobain Vitrage | SECURITY SHEET GLAZING |
JPS57199649A (en) * | 1981-06-03 | 1982-12-07 | Asahi Glass Co Ltd | Polyurethane sheet and glass-polyurethane laminated sheet |
DE3135672A1 (en) * | 1981-09-09 | 1983-03-24 | Bayer Ag, 5090 Leverkusen | Use of low-viscosity self-curing mixtures for polyurethane interlayers in laminated panes |
FR2549036B1 (en) * | 1983-07-11 | 1985-10-18 | Saint Gobain Vitrage | SAFETY SHEET GLAZING |
-
1983
- 1983-07-11 FR FR8311507A patent/FR2549037B1/en not_active Expired
-
1984
- 1984-07-09 DK DK337184A patent/DK163039C/en not_active IP Right Cessation
- 1984-07-10 IL IL7236084A patent/IL72360A/en not_active IP Right Cessation
- 1984-07-10 DE DE8484401464T patent/DE3468647D1/en not_active Expired
- 1984-07-10 HU HU842694A patent/HU194770B/en not_active IP Right Cessation
- 1984-07-10 FI FI842766A patent/FI77602C/en not_active IP Right Cessation
- 1984-07-10 IN IN496/CAL/84A patent/IN162382B/en unknown
- 1984-07-10 SU SU843791615A patent/SU1491326A3/en active
- 1984-07-10 NO NO842804A patent/NO161967C/en unknown
- 1984-07-10 IE IE1759/84A patent/IE57796B1/en not_active IP Right Cessation
- 1984-07-10 PT PT78883A patent/PT78883B/en unknown
- 1984-07-10 AU AU30456/84A patent/AU575059B2/en not_active Ceased
- 1984-07-10 YU YU1206/84A patent/YU43368B/en unknown
- 1984-07-10 ZA ZA845292A patent/ZA845292B/en unknown
- 1984-07-10 ES ES534172A patent/ES534172A0/en active Granted
- 1984-07-10 BR BR8403426A patent/BR8403426A/en not_active IP Right Cessation
- 1984-07-10 EP EP84401464A patent/EP0131523B1/en not_active Expired
- 1984-07-10 NZ NZ208854A patent/NZ208854A/en unknown
- 1984-07-10 PH PH30957A patent/PH26588A/en unknown
- 1984-07-10 JP JP59141570A patent/JPS6071253A/en active Granted
- 1984-07-10 AT AT84401464T patent/ATE31896T1/en active
- 1984-07-11 KR KR1019840004059A patent/KR930000775B1/en not_active IP Right Cessation
- 1984-07-11 CA CA000458655A patent/CA1261241A/en not_active Expired
- 1984-07-11 MA MA20399A patent/MA20175A1/en unknown
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Legal Events
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PBP | Patent lapsed |