NZ208854A

NZ208854A - Glass/polyurethane laminated pane

Info

Publication number: NZ208854A
Application number: NZ208854A
Authority: NZ
Inventors: J-L Bravet; D Colmon; G Daude; M-J Moncheaux
Original assignee: Saint Gobain Vitrage
Priority date: 1983-07-11
Filing date: 1984-07-10
Publication date: 1987-11-27
Also published as: BR8403426A; DK337184A; PT78883A; IL72360A; NO161967C; FI842766A; FR2549037B1; NO842804L; AU3045684A; PT78883B; NO161967B; EP0131523B1; PH26588A; DK163039B; AU575059B2; ZA845292B; DK163039C; IE841759L; SU1491326A3; HU194770B

Abstract

1. A laminated pane comprising only a glass sheet and a layer of transparent plastics material, characterised in that the layer of transparent plastics material has properties of absorption of energy and interior protection defined by a scratch resistance greater than 20 g measured with the Erichsen type 413 apparatus and an abrasion resistance according to European Standard R43 such that the haze difference is less than 4% and at a thickness of about 0.5 mm a flow stress sigma y at -20 degrees C not exceeding 3 daN/mm**2 , a rupture stress sigma R at +20 degrees C of at least 2 daN/mm**2 , a lengthening at rupture epsilon R at +20 degrees C from 250% to 500%, and a tear resistance Ra at +20 degrees C of at least 9 daN/mm**2 , and in that the layer of plastics material is formed essentially of a polyurethane obtained by continuous reactive casting on a flat horizontal support of a reaction mixture of an isocyanate component and a polyol component, the isocyanate component comprising at least one aliphatic or cycloaliphatic di-isocyanate or a di-isocyanate prepolymer, this component having a viscosity measured at +40 degrees C less than about 5 Pas, the isocyanate component containing urea functions, the content of urea being up to 10% of the total weight of isocyanate component, the urea content preferably being from 5 to 7%, and the polyol component comprising at least one long difunctional polyol of molecular weight from 500 to 4000 and at least one short polyol as a chain lengthening agent, the ratio of isocyanate group equivalents to hydroxyl group equivalents is about 1, and the proportions between the different polyols are selected so that the number of hydroxyl group equivalents due to the short diol represents from 20 to 70% of the total hydroxyl groups.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £08854 No.: Date: 208854 ! Pr K-VS3 filKt KWrSlj - ..6.516 H.i io ftaifiJUiAo, '. fiaqc'ag/OZ F > ?.?. .HC.V.»«?. 1^)02. Mili iiHAWjliliS NEW ZEALAND PATENTS ACT, 19S3 COMPLETE SPECIFICATION LAMINATED SAFETY PANE I/We. SAINT-GOBAIN VITRAGE of "Les Miroirs", 18 avenue d'Alsace, 92400 Courbevoie, France, a French Company, hereby declare the invention for whichW/ we pray that a patent may be granted to and the method by which it is to be performed, to be particularly described in and by the following statement:- - 1 - (followed by page -la-) 7 .. a '• *•? 208854 -1a- Laminated Safety Pane The invention relates to a new laminated pane comprising a glass sheet and a single layer of plastics material. 5 Laminated panes known as safety panes are generally composed of two glass sheets and an intermediate layer having the property of absorbing energy, generally of polyvinylbutyral. One of the disadvantages of this type 10 of laminated pane when it is used as a windscreen for a vehicle, is that in the case of impact of the head of the occupant of the vehicle with the pane the edges of the internal glass sheet which is broken may cause lacerations and other injuries. This is why it has been suggested for 15 example in UK Patent specifications 1436884 and 1461817 to apply to this glass sheet inside the vehicle a sheet of plastics material formed essentially of a thermohardening polyurethane which has anti-laceration properties. Further, this sheet of plastics material is 20 self-healing, that is to say it is of a material in which superficial damage or local impressions disappear rapidly, the speed of disappearance being a function of the nature of the damage and the temperature of the plastics material. 25 It has also been suggested for example in UK Patent specification 1576394 to provide a laminated pane comprising a glass sheet, a thermoplastics layer having properties of absorbtion of energy and a self-healing 30 coating layer resistant to scratches formed essentially of a thermohardening polyurethane. In this type of pane each of the layers fulfills a particular function, the thermoplastics layer fulfilling essentially the function of absorbing energy but being insufficiently p#sis;tiant__to 35 abrasion or other exterior effects and the coatinj fulfilling the function of protection of th^R'"layer cv absorbing energy but not having itself good projfet*ties of \\ Z r] energy absorption. | m70CTJ9Q/ 208S54 -2- It has already been suggested for example in Patent Publications US-3 509 015 and US-3 808 077 to provide laminated panes comprising a glass sheet and a single layer of plastics material having properties of absorption 5 of energy. This type of pane has not apparently given entire satisfaction, probably because of an insufficient resistance to abrasion and scratching of the layer of plastics material used as the external layer. 10 It is known in a general way that a structure of a laminated pane comprising a single layer of plastics material having simultaneously the properties of absorbing energy and a good resistance to scratching and to attack by exterior agents was unlikely to be 15 satisfactory. In fact, for a man in the art there exists a certain incompatibility between the functions of absorbing energy and resistance to scratching for a single layer. For the layer to have properties of absorption of energy it is believed that it has to have an essentially 20 thermoplastic character. On the other hand, for the layer to have a good resistance to scratching it is believed that it has to have an essentially thermohardening character with a cross-linked structure. These mechanical properties associated with thermoplastic or 25 thermohardening characteristics are described for example in UK Patent specification 1576394 and European Patent Publication 054491. There has now been found a single layer of plastics 30 material which, in a laminated pane structure in which it is associated with a glass sheet fulfills the function of absorbing energy, protection against fragments of glass and which also has a good resistance to abrasion and scratching and to different attacks from exterior agents. 35 The layer according to the invention is formed process which is continuous by reactive casting on^m^flat horizontal support from which it may be detached, of a "7 OCT 1987 ' : v ■ 0 38 -3- reaction mixture of an isocyanate component and a component having active hydrogens, notably a polyol component, the isocyanate component comprising at least one aliphatic diisocyanate or a cycloaliphatic-diisocyanate or a diisocyanate prepolymer, this component having a viscosity measured at 40°C less than about 5000 centipoises and the polyol component comprising at least one long polyol which is difunctional of molecular weight from 500 to 4000 and at least one short diol as a chain lengthening agent. By reactive casting is meant casting in the form of a layer or film of a liquid mixture of components in the monomeric or prepolymeric state followed by polymerisation of this mixture by heating. This reactive casting which forms the layer having good mechanical and optical properties will be described more completely in the following description. The proportions of components of the polyurethane are chosen to obtain preferably a balanced stoichiometric system, that is to say the ratio of equivalent NC0 groups provided by the diisocyanate component to equivalent OH groups provided by the polyol component, that is to say the long polyol or polyols and the short diols is of the order of 1. When the ratio NC0/0H is less than 1, the more it decreases the more the desired mechanical properties for this application become less satisfactory. When all the components of the polyurethane are difunctional the lower limit of the NC0/0H ratio for obtaining satisfactory mechanical properties is about 0.9. When one of the components at least is trifunctional this low limit may be lowered to about 0.8. When the ratio NC0/0H is greater than 1, the more it increases and the greater become certain mechanical properties of the layer obtained by reactive casting, for example the layer becoming more rigid, but given the higher cost of the isocyanate component with respect of that of the polyol component, -4- the choice of a ratio NCO/OH substantially equal to 1 is a good compromise between the properties obtained and the cost. 5 The proportions between the long polyol and the short diol may vary as a function of the desired properties as indicated in the following, the number of OH group equivalents due to the short diol however representing generally from 20 to 70$ of the total group equivalents of 1 o the mixture forming the polyol component in the case where the ratio of OH groups is of the order of 1. When the proportion of short diol is increased, the layer is hardened and its modulus is generally increased. 15 Suitable diisocyanates which may be used in the invention are chosen especially from the difunctional aliphatic isocyanates following: hexamethylenediisocyanate (HMDI), 2,2,4-trimethyl 1,6-hexanediisocyanate (TMDI), bis 4-isocyanatocyclohexylmethane (Hylene W) bis 3-methyl-4-20 isocyanatocyclohexylmethane, 2,2 bis (4- isocyanatocyclohexyl) propane, 3-isocyanatomethyl-3,5»5 trimethylcyclohexyl-isocyanate (IPDI), m- xylylenediisocyanate (XDI), m-and p- tetramethylxylylenedi-isocyanate (m- and p- TMXDI), 25 trans-cyclohexane-1,4 diisocyanate (CHDI), and 1,3 (diisocyanatomethyl)-cyclohexane (hydrogenated XDI). IPDI is preferably used especially for reasons of cost. 30 According to one of the aspect of the invention there is used an isocyanate component containing urea functions. These urea functions improve certain mechanical properties of the layer. The content of the urea may be up to about "\Q% of - the total weight of the isocyanate 35 component having urea functions. Preferably the content of the urea is from 5 to 7% by weight of the total of said component. For the reason mentioned previously there is -?088 -5- preferably used 3-isocyanatomethyl-3,5,5- trimethylcyclohexylisocyanate comprising urea functions (IPDI and derivatives thereof). 5 The long polyols which are suitable are chosen from polyether diols and polyester diols of molecular weight 500 to 4000; the polyesterdiols being products of esterification of a diacid such as adipic acid, succinic acid, palmitic acid, azelaic acid, sebacic acid, 10 orthophthalic acid and a diol such as ethyleneglycol, propanediol -1,3, butanediol -1,4, hexanediol -1,6, and polyetherdiols of general formula H £° (CH2>r} m 0H 15 where n = 2 to 6; m is such that the molecular weight is situated in the range 500 to 4000, or polyether-diols of general formula: 20 CH3 H £ OCH - CH2 3 „ OH where m is such that the molecular weight is also situated in the range 500 to 4000. It is also possible to use 25 polycaprolactonediols. There is used preferably a polytetramethyleneglycol (n = 4) of molecular weight also equal to about 1000. 30 The lengthening agents for chains which may be used are the short diols such as ethyleneglycol, propanediol-1,2, propanediol-1,3, butanediol-1,2, -1,3 and -1,4, dimethyl-2,2-propanediol-1,3 (neopentylglycol), pentanediol-1,5, hexanediol-1,6, • octanediol-1,8, decanediol-1,10, 35 dodecanediol-1,12, cyclohexanedimethanol, bisphenol A, methyl-2 pentanediol-2,4, methyl-3 pentanediol- 2,4, ethyl- 2 hexane-diol-1,3, trimethyl-2,2,4-pentanediol-1,3, diethylene-glycol, triethyleneglycol, tetraethyleneglycol, butyne-2-diol-1,4, and substituted /' 203854 -6- and/or etherified decynediol, hydroquinone-bis-hydroxyethylether, bisphenol A etherified by two or four propylene oxide groups and dimethylolpropiortic aoid. In general the shorter the diol the harder the layer. 5 There is preferably used butanediol-1,4 which is a good compromise to obtain a layer which is neither too hard nor too soft which is desired for this type of application. 10 One of the characteristics of the layer according to the invention is that it is obtained by reactive casting on a flat horizontal support, this reactive casting being already described in UK Patent specification 2038228 for obtaining a layer of thermohardening polyurethane from 15 a mixture of trifunctional components providing in surprising manner, according to the invention, in the case of difunctional starting components, a layer which is not entirely thermoplastic when the group NCO/OH ratio is substantially equal to or greater than 1. 20 Reactive casting implies a rapid polymerisation reaction so that the layer may be formed in a time compatible with industrial . manufacture. This requires a higher temperature, preferably greater than about 80°C and preferably of the order of about 100 to 140°C, the 25 temperature at which the secondary reactions of branching which are produced creating for example allophanate groups or biurets between the polyurethane chains, such as: 10 2088 -7- or - R" - NH - CO - NH - R" . OCN - R - NCO - R" - NH - CO - NH - R" - r.-l - R" - N - CO - NH 7 R" - ' I 'CO • I NH . - ' biuret ■•y * / NH « CO - r" - h - CO - NH - R" - 15 In these operating conditions, even with difunctional components, when the NCO/OH ratio is substantially equal to or greater than 1, as indicated before, the product obtained is not completely thermoplastic; in fact it is infusible and insoluble in the majority of solvents for 20 polyurethanes such as tetrahydrofuran and dimethylformamide. This does not present any disadvantage when the layer is already formed; on the contrary advantage is taken of the improved mechanical properties for the layer especially regarding the stress at the start 25 of flow y, the stress at rupture R, elongation at rupture R, and resistance to the start of tearing R , the a resistance to scratching measured in the ERIKSEN test as described below, or the resistance to abrasion, in comparison with an equivalent system polymerised at low 30 temperature when only a linear polycondensation is produced. 35 When the NCO/OH ratio is less than 1 and of the order of 0.8 to 0.9, a reticulation of the type described above is produced only to an insignificant extent. 303354 -8- In one embodiment of the layer of polyurethane according to the invention, the polyol component may contain a small proportion of at least one polyol of functionality greater than two and especially the monomeric aliphatic triols 5 such as glycerol, trimethylolpropane, triols having polyether chains and polycaprolactone triols, the molecular weight of these triols generally being from 90 to 1000,and mixed polyether/polyester polyols of functionality greater than 2, for example of functionality 10 from 2 to 3- The addition of a polyol of functionality greater than 2 gives supplementary bridging connections between the polyurethane chains and may thus increase the cohesion of the layer. 15 The proportions of the long polyol, the short diol and possibly the polyol of functionality greater than 2 may vary according to the desired properties. There are generally chosen proportions such that for one hydroxyl equivalent the long polyol represents about 0.3 to 0.45 20 equivalent, the short diol about 0.2 to 0.7 equivalent and the polyol of functionality greater than 2, about 0 to 0.35 equivalent. In these conditions the layer has the following mechanical characteristics measured according to standards*AFNOR/NFT 46.002, 51 034 and 54 108. 25 A stress at the start of flow (Ty at -20°C less than or p equal to 3 daN/mm , A stress at rupture R at + 40°C greater than or equal 2 to 2 daN/mm , 30 An elongation at rupture £ R at +20°C from 250 to 500$, A resistance to the start of tearing Ra at +20°C greater than or equal to 9 daN/mm thickness, 35 A resistance to scratching greater than 20 g measured according to the test described below, * available on request Resistance to abrasion, with a difference in haze less than 4$ measured according to the abrasion test indicated below. 5 According to one of the aspects of the invention, a part of the polyol component may be replaced by a different product having active hydrogens such as an amine. According to another embodiment of the layer of plastics 1 o material according to the invention, the isocyanate component may contain within limited proportions, for example less than about 15$ in NCO equivalents, at least one triisocyanate such as a isocyanate biuret or a triisocyanurate. 15 To fulfill all the functions which are demanded, the polyurethane layer according to the invention should have a thickness generally greater than 0.4mm and preferably greater than 0.5mm. 20 The layer according to the invention may contain various additives which generally serve to facilitate manufacture by reactive casting. It may contain a catalyst such as a tin catalyst for example tin dibutyldilaurate, 25 tributyltin oxide, tin octoate, an organomercuric catalyst, for example mercuricphenylester, an amine catalyst such as for example diazabicyclo-(2,2,2)-octane, and 1,8-diazabicyclo (5,4,0)-1 decene-7. The layer may contain stabilisers such as bis (2,2,6,6-tetramethyl-4-30 piperidyl)sebacate, and a phenolic antioxidant. The layer may also contain a spreading agent such as a silicone resin, a fluoroalkyl ester, or an acrylic ester. 35 Examples of manufacture of laminated panes and the layer of plastics material used for this manufacture are described in the following. 208854 -10. Example 1 To make the layer of plastics material, there is first prepared the polyol component by mixing a 5 polytetramethylene glycol of molecular weight 1000 (for example the product sold commercially under the name Polymeg 1000 by the QUAKER OATS company, with butanediol-1,4, the proportions of the two constituents being such that the polytetra-methyleneglycol contributes 0.37 10 equivalent of hydroxyl groups whereas the butanediol-1,4 contributes 0.63. To the polyol component there is added a stabiliser in an amount of 0.5$ by weight of the total weight of polyol 15 component and isocyanate component, a spreading agent in an amount of 0.05$ by weight calculated in the same way and a dibutyltin dilaurate catalyst in an amount of 0.02$ by weight calculated in the same way. 20 The isocyanate component used is 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) having urea functions obtained by partial hydrolysis of IPDI and having a content of NCO groups of about 31-5$ by weight. 25 The components are used in quantities such that the NCO/OH ratio is 1. After degassing under vacuum of the components, the mixture brought to 40°C is cast by means of a casting head such as that described in UK Patent specification 1562767 on a movable glass support covered 30 with a separating agent. There is thus formed a layer of homogeneous thickness of about 0.755 mm thickness which is subjected to a polymerisation cycle, that is to say a temperature of 120°C for about 25 minutes. 35 After polymerisation, the layer is removed^ from the support of glass and forms a sheet which may be stored or used just after for manufacture of laminated panes. ■ <">l \~7 OCT 1987 j y 2088 5 To make the pane there is assembled a sheet of plastics material with a sheet of 2.6mm thickness of heated glass. The glass may possibly be hardened or tempered. This assembly may be carried out in two stages, a first stage consisting of a preliminary assembly obtained by passage of the elements forming the pane between two rollers of a calendar and it is possible to use for this purpose a device described in European Patent Publication 0015209, and a second stage consisting of putting the laminated product in an autoclave where, for about one hour it is subjected to a pressure of about 10 bars at a temperature of about 13°C. This autoclave cycle may possibly be replaced by a stoving cycle at normal pressure. The pane obtained has an excellent optical quality and a perfect transparency. The adhesion obtained between the glass sheet and the sheet of plastics material is measured by a peel test described below. There is cut a strip of 5cm width from the covering layer. The end of the strip is unstuck and there is applied thereto a pulling force perpendicular to the surface of the glass at a pulling speed of 5 cm per minute. The operation is carried out at 20°C. There is noted the pulling force required for unsticking of the strip. Operating in this way there is obtained a pulling force of 10 daN/5cm. Trials for resistance to shock at different temperatures are carried out on the pane made according to the example. A first trial for -resistance to shock is carried out at +20°C with a steel ball weighing 2.260 kg (heavy ball test) which is allowed to fall onto the central part of a square glass sample of 30.5 cm side, held on a rigid frame. There is determined the approximate height for 7 208854 30 -12- which 90$ of the samples tested at the chosen temperature resist fall of the ball without the ball passing through. For the laminated pane according to the example, the value 5 obtained is 12 metres. Another trial for resistance to shock is carried out with a steel ball of 0.227 kg weight at 38mm diameter. One trial is carried out at a temperature of -20°C. Another 10 trial is carried out at a temperature at +40°C. The values obtained are respectively 12 and 11 metres. ★ Taking account of European standard R43 which is in force, the desired results are at least 4 metres for the heavy 15 ball, at least 8.5 metres for the light ball at -20°C and at least 9 metres for the light ball at +40°C. The resistance to scratching is measured by a known scratch test called MAR resistance test which is carried 20 out with an ERICHSEN apparatus, type 413* There is measured the loading applied on a diamond head to introduce a persistent scratch on the layer of plastics material assembled with a glass support. The load should be greater than or equal to 20 grams for the layer of 25 plastics material to have the property of being self-healing . The resistance to scratching measured according to this test, for the pane according to the example is 32 grams. The resistance to abrasion is measured according to European standard R43* For this purpose, an assembled sample of pane is subjected to abrasion by means of an abrasive mill. After 100 rotations in abrasion, there is 35 measured with a spectrophotometer the difference in _ haziness between the abraded part and non-abradartase&rt. f The difference in haziness CAhaze) has to be^pfes thanoj for the layer to have anti-abrasive qualitie/l * details available on request w-7 OCT 1987 7 03854 -13- The layer according to the example has a difference in haze of 0.9^$. The pane according to the example has all the 5 characteristics which render it suitable for use as a vehicle windscreen. Example 2 10 The procedure of Example 1 is followed except that the polyol component is formed of a mixture of polytetra-methylene glycol of molecular weight 1000, butanediol-1,4 and polycaprolactonetriol (for example the product sold commercially under the name Niax 301 by UNION CARBIDE) in 15 respective proportions such that for one total hydroxyl equivalent, there is used 0.35, 0.45 and 0.20 hydroxyl equivalent. There is made a layer of 0.70mm thickness. The pane 20 obtained shows mechanical and optical characteristics which are completely satisfactory. The values measured in different tests are as follows: - an adhesion of 11 daN/5cm, values of 8 metres with 25 a heavy ball, 11 at 11 metres respectively with a light ball at -20°C and + i»0°C. a resistance to scratching of 35 g and a difference in haze on abrasion of 1.2$. 30 The pane made according to the example is thus suitable for use as a windscreen. Example 3 35 The procedure of Example 2 is followed except that the proportions between the different polyols are such that for an equivalent total hydroxyl there is used 0.35, 0.55 and 0.10 hydroxyl equivalent respectively for the long </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 2088 5 -in- polyol, the short diol and the triol. There is formed a layer of 0.66 mm thickness. The values measured in different tests are as follows: 5 - an adhesion of 11 daN/5 cm, values of 10 metres with the heavy ball, 13-5 and 13.5 metres with the light ball at -20°C and +40°C respectively, a resistance to scratching of 25 g, and a difference in haze on abrasion 10 of 1.2$. The pane made, according to the example, is thus capable of being used as a windscreen. 15 Example 4 The procedure of Example 1 is followed except that polymerisation of the layer is carried out at a temperature of 60°C only for 20 hours. 20 Trials for resistance to shock give a value with a small ball of -20°C at 6.5 metres which is insufficient. This example, compared with Example 1 shows the effect of 25 the polymerisation temperature used during reactive casting. In this case this temperature is too low. 30 35 / -\5- 2038 WHAT VV/E CLAIM IS: 1. A laminated pane comprising a glass sheet and a transparent surface layer of plastics material, characterised in that the layer of transparent plastics material is formed essentially of a polyurethane obtained by reactive casting continuously on a flat horizontal support of a reaction mixture of an isocyanate component and a polyol component, the isocyanate component comprising at least one aliphatic or cycloaliphatic diisocyanate or a diisocyanate prepolymer, this component having a viscosity, measured at 40°C, less than 5000 centipoises, the polyol component comprising at least one long polyol which is difunctional of molecular weight from 500 to 4000 and at least one short diol having a molecular weight of up to 300 as a chain lengthening agent. 2. Laminated pane according to Claim 1, characterised in that the layer of plastics material has at a thickness of less than 0.5mmya stress at the start of flow CT"y at o 2 -20 C less than or equal to 3 daN/mm , a stress at rupture CT*R at + 40°C greater than or equal to 2 daN/mm^, a lengthening at rupture £ R at +20°C from 250 to 500$ and a resistance to start of tearing R at +20°C greater than'or SL equal to 9 daN/mm. / 203854 -16- 3. Laminated pane according to Claim 1 or Claim 2, characterised in that the isocyanate component contains urea functions, the content of the urea being able to reach 10$ of the total weight of the isocyanate component, 5 preferably this content of urea being from 5 to 7$. 4. Laminated pane according to any one of Claims 1 to 3, characterised in that the isocyanate component comprises 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate. 10 5. Laminated pane according to one of Claims 1 to 4, characterised in that the isocyanate component and the polyol component are used in such quantities that the ratio of equivalent isocyanate groups to equivalent 15 hydroxyl groups is about 1. 6* Laminated pane according to one of Claims 1 to 5, characterised in that the proportions between the different polyols are chosen such that the number of 20 equivalent hydroxyl groups due to the short diol represents 20 to 70$ of the total of the hydroxyl groups. 7. Laminated pane according to one of Claims 1 to 6, characterised in that the isocyanate component is formed 25 essentially of 3-isocyanatomethyl-3,5,5- trimethylcyclohexylisocyanate having urea groups formed by partial hydrolysis and in that the polyol component is formed essentially of polytetramethyleneglycol and butanediol-1,4. 30 8- Laminated pane according to one of Claims 1 to 7, characterised in that the polyol component comprises further at least one polyol of functionality greater than 2. 35 9. Laminated pane according to Claim 8, characterised in that the polyol of a functionality greater than 2 is a T polycaprolactonetriol. "70C: ho; ; ' " " : v '' , • "-«■***** "/ 208854 10. Laminated pane according to one of Claims 8 or 9, characterised in that for one total hydroxyl equivalent, the long polyol contributes 0.30 to 0.45 equivalent, the short diol 0.2 to 0.7 equivalent and the polyol of functionality 5 greater than 2 contributes 0 to 0.35 equivalent. S'Sdf"/ out «P if'iP'Y) 11. Laminated pane according to Claim 1 to 10, characterised in that the polyurethane layer having properties of absorbtion of energy and internal protection 10 comprises a catalyst, spreading agent and a stabiliser. 12. Laminated pane according to one of Claims 1 to 11, characterised in that the layer of transparent plastics 15 material is obtained by a reactive casting using a temperature of polymerisation greater than 80°C. 13. Laminated pane according to one of Claims 1 to 12, characterised in that the isocyanate component further 20 contains at least one triisocyanate. 14. A laminated pane as claimed in claim 1 and substantially as herein described with reference to any embodiment 25 disclosed fn the examples. ^ </div>