MXPA97000106A - Enhanced polyurethane resin sheet and laminated product that the emp - Google Patents

Abstract

A sheet of smooth and transparent interlaced polyurethane resin prepared from a curable reaction composition, which consists of a mixture of high molecular weight polyol (A) consisting of a polyester polyol and / or a polycarbonate polyol as its main components, and which contains a diol and a trivalent or higher valent polyol, the average hydroxyl value of the mixture is from 40 to 120, and the equivalent ratio of (the highest trivalent polyol or valent) / (the diol) is from 0.1 to 0.8, a substantially bivalent chain extender (B) in an amount of from 1.9 to 6.0 equivalents per equivalent of the polyol mixture (A), and a substantially bivalent alicyclic or aliphatic polyisocyanate compound (C) in an amount from 0.8 to 1.2 equivalents per equivalent of the sum of the mixture of polyol (A) and the chain extender (B), as its main components

Description

HOLY RESIN OF REINFORCED PQLIURETHANE AND LAMINATED PRODUCT WHICH IT EMPLOYS DESCRIPTIVE MEMORY The present invention relates to an interlaced polyurethane resin sheet or has a self-healing property and high mechanical properties. Particularly, it relates to an interlaced polyurethane resin sheet, which is capable of providing excellent penetration resistance within a wide range of temperatures, even in a relatively thin thickness when used for laminated safety glass. The laminated safety glass having a layer of a flexible synthetic resin is known as a polyurethane resin provided on one side of an inorganic glass sheet (hereinafter referred to simply as glass) or a sheet of laminated glass . The sheet of laminated glass is a laminate having two sheets of glass laminated with an interlayer of v.gr », a polyvinyl butyral resin interposed therebetween. The laminated safety glass having a layer of a resin interleaving polyurethane (which may be also called as curable polyurethane resin to heat or crosslinked polyurethane resin) formed on one side of a sheet of laminated glass, described, for example in JP-B-59-8775.

The role of the polyurethane resin in + relative to the laminated safety glass described in such publication is that of preventing damage to the skin by fractured glass fragments when a human body collides with the laminated safety glass (ie antilaceration property). In addition, a common synthetic resin is prone to receive scratch marks by eg, scratches. While this ream of entangled polyurethane has a self-healing property (also called a self-healing coat). The self-healing property is a property where when a scratch mark is formed on the surface of the interlaced polyurethane resin, the mark naturally disappears over time. The interlaced polyurethane ream having such a property is known from (3P-B-55-6657). However, an interlaced polyurethane ream such as that described in such publication is inadequate in mechanical properties. Laminated security glass requires mechanical properties such as resistance to penetration and an energy-absorbing property at the time of collision of a human body. Laminated safety glass consisting of a layer of laminated glass and a layer for this interlaced polyurethane layer is useful as laminated glass and has such mechanical properties as those required for laminated safety glass. However, it is not possible to replace this sheet of laminated glass with a single sheet of glass to obtain a laminated safety glass. With the purpose of reducing the weight of an automobile, the laminated safety glass employing a single sheet of cp & il is more advantageous than laminated safety glass employing the previous laminated glass sheet, as a window material for a car. Also for other implications, such laminated safety glass is economically superior. In the case of laminated safety glass that employs a single glass pane, laminated safety glass requires a resilient, flexible coating that has high mechanical properties to meet the mechanical properties required for safety glass laminate. As such a synthetic resin material, a polyamide butyral resin or a thermoplastic polyurethane ream is, for example, suitable. However, such material is susceptible to scratches on its surface, and its property as that of solvent resistance (hereinafter referred to as surface property) is inadequate. Consequently, some surface protection is required. For such surface protection it is known to use an interlaced polyurethane resin having the aforementioned surface property (v., JP-B-57-27050, CJP-A-53-27671 and 3P-A-57-17S57). In such prior art, in cps + that of laminated security using a single sheet of glass, a relatively thin layer (at least 0.5 rn) of a polyurethane resin or thermoplastic resin functions as a layer for mechanical improprieties, and a The above-mentioned interlaced polyurethane resin layer, mentioned at a thickness of at least 0.4 nm, works as a protective layer for the thermoplastic polyurethane resin layer (JP-fi-53-27671). It is disclosed that in a laminated safety glass having a similar structure using a sheet of laminated glass, the layer of a thermoplastic polyurethane resin operates as an adhesive layer and can therefore be a thin layer. The fact that a thin layer is required to impart mechanical properties on a laminated safety glass employing a single sheet of glass has several difficulties. First, the sheet that constitutes this layer must be an excellent sheet in optical properties, which has a smooth surface and a uniform thickness. For example, by a method in which a polyvinyl butyral resin or a thermoplastic polyurethane ream is laminated by extrusion molding, fine irregularities are likely to form on the surface, or a change in the thickness of the sheet is also prone. to occur, while it is difficult to obtain a sheet that fully satisfies the optical properties. The interlaced polyurethane resin can be easily formed into a sheet having excellent optical properties by melting. However, a thermoplastic polyurethane resin can not be easily melt laminated, since the viscosity of the starting material mixture is high. Melt rolling is a method in which a mixture of starting material is melted and solidified into a smooth surface for rolling. A method may be conceivable wherein the mixture of thermoplastic polyurethane resin starting material is diluted with a solvent to reduce the viscosity, followed by the melt. However, by means of the method, it is difficult to obtain a relatively thin ho, although a ho a thin can be obtained. In view of these problems, the present inventors considered it economically advantageous and from the point of view of production techniques, that the flexible synthetic resin layer of a laminated safety glass is constituted substantially by a single layer of resin material. synthetic, and have conducted an investigation for an interlaced polyurethane resin, which has the aforementioned surface property and mechanical properties, and which is suitable for melting. As a result, an interlaced polyurethane resin having properties suitable for the production of laminated security glass has been previously proposed (ZJP-A-61-177241 and JP-A-61-281118). However, such an interlaced polyurethane resin is inadequate in penetration resistance, especially when formed in a thin film, and furthermore, its impact resistance at low temperatures is inadequate.

It is an object of the present invention to provide a hoop of entangled polyurethane resin having such improved properties. The present invention provides a smooth and transparent interleaved polyurethane resin sheet prepared from a curable reaction composition, which consists of a high molecular weight polyol blend (A) consisting of a polyester polyol and / or a polyol. of polycarbonate as its main components, and containing a diol and a trivalent polyol or higher valent, the average hydroxyl value of the mixture is 40 to 120, and the equivalent ratio of (the trivalent or higher valent polyol) / (the diol) is 0.1. at 0.8, a substantially bivalent chain extender (B) in an amount of from 1.9 to 5.0 equivalents per equivalent of the polyoi mixture (A), and a substantially bivalent aliphatic or alicyclic or alicyclic compound (C) in an amount of from 0.8 to 1.2 equivalents per equivalent of the sum of the mixture of polyol (A) and the chain extender (B), as well as its main components. The curable reaction composition may further contain a silane compound (D) in an amount of from 0.001 to 10% by weight, based on the total weight of the components, A, B and C. The interlaced polyurethane resin sheet is particular and preferably used for a laminated product having a layer structure consisting of at least two layers including a layer of the interlaced polyurethane resin sheet on the side and an inorganic crystal layer on the other side. Furthermore, it is particular and preferably used for a laminated product having a layer structure consisting of at least three layers including a first surface layer made of a synthetic resin, an interlayer made of the aforementioned interlaced polyurethane resin sheet. and a second layer of surface made of inorganic crystal. Now, the present invention will be described in greater detail with reference to the preferred embodiments. A polyurethane resin is obtained by the reaction of an active polyvalent and a hydrogen-containing compound, particularly a polyol, with a compound containing the polyvalent isocyanate group (hereinafter referred to as a polyisocyanate compound). When these two types of compounds are bivalent, a thermoplastic polyurethane resin is obtainable. When one of these two types of compounds exceeds the bivalent, an interlaced polyurethane resin is obtainable. The physical properties of the entangled polyurethane resin are mainly influenced by the type of the active compound containing hydrogen. In general, a polyurethane resin elastomer having high mechanical properties, can be obtained by the combined use of an active compound containing high molecular weight hydrogen and an active compound containing low molecular weight hydrogen known as an extender. chain or? interlacing agent. However, as a result of a study by the present inventors, it has been found that it is extremely difficult to ob + ener the highly mechanical properties of the interlaced polyurethane ream within a wide range of temperatures. Specifically, an interlaced polyethene ream having high mechanical properties at room temperature is usually deficient in impact resistance at low temperatures and the flexibility is markedly uneven at temperatures. In fact, polyurethane + entangled annea resins having excellent mechanical properties within a wide range of temperatures are relatively limited types of polyurethane resins. In the present invention, the interlaced polyurethane ream is required to be a polyurethane resin prepared from a curable reaction composition, which consists of the following starting materials. 1. A mixture of relatively high molecular weight polyol (A) and an active compound containing low molecular weight hydrogen (hereinafter referred to as a chain extender (B)) are used in combination. If the ex + chain linker (B) is not incorporated, it tends to be difficult to obtain an interlaced polyurethane ream having high mechanical properties. 2. - The mixture of polyol (A) is required to be a mixture of a diol and a polyol + r? Valen + eo valen + e higher, in which the average hydroxyl value is from 40 to 120, and the equivalent ratio of (the high-valent or trivalent polyol) / (the diol) is within the range of from 0.1 to 0.8. In this case, 1 mole of a compound in which the number of active hydrogen atoms or isocyanate groups per molecule is n, corresponds to the equivalents of n. If the average hydroxyl value is more than + 120, the impact resistance at low temperatures will be low, and if it is less than 40, the self-healing property tends to be difficult to obtain. If the equivalent ratio is greater than 0.8, the mechanical properties tend to be low, and if it is less than 0.1, the self-healing properties tend to be difficult to obtain. The hydroxyl value is used as a numerical value referring to the molecular weight of the polyols, because when a diol and? N polyvalent trivalent or higher valent are used in combination, the influence of their molecular weights on the physical properties can not be simply represented by the average value of their molecular weights. The above polyol mixture A preferably consists of a combination of a diol having the average hydroxyl value of from 35 to 75 and a higher trivalent or valent polyol having the average hydroxyl value of from 50 to 300. If the average hydroxyl value of the diol is higher than this scale, the resistance to penetration at low temperatures tends to be low. It is particularly preferred that the diol has the average hydroxyl value of from 45 to 65. Furthermore, it is particularly preferred that the higher trivalent or valent polyol has the average hydroxyl value of from 150 to 250. Each of the diol and the polyol trivalent or higher valent can be in combination of two or more respective members. In such a case, the individual polyols may have hydroxyl values outside the previous scale, as long as the average hydroxyl value is within the previous scale. However, the upper limit of the hydroxyl value of each polyol is 400, so it can be distinguished from the chain extender which will be described later herein. The average hydroxyl value in the combination of such higher trivalent or higher diols and polyols is rn? And preferably from 60 to 90, and the equivalent ratio of such (higher trivalent or higher valent polyols) / (diols) is very preferentially from 0.20 to 0.50. 3. The chain extender (B) is a substantial bivalent compound. The polyisocyanate compound C is also a substantially divalent polyisocyanate compound. In this case, "substantially bivalent" means that the number of functional groups does not exceed approximately 2.1. If the number of functional groups exceeds this level, the mechanical properties + Lenden to be low. 4. The quantity of the chain extender per equivalent of polyol mixture is 1.9 to 5.0 equivalents. If the amount is greater than this scale, a property of self-healing + ißnde to be difficult to obtain and the resistance to impact at low temperatures tends to deteriorate. If the amount is lower than this scale, the resistance to penetration at room temperature tends to be inadequate when formed in a thin film. The amount of chain extender B per equivalent of the above polyol mixture fl is nu and preferably from 2.2 to 4.5 equivalents. 5. The amount of the polyalkylene compound + or C per equivalent of the sum of the mixture of polyol A and the chain extender B is substantially equivalent, particularly from 0.8 to 1.2 equivalents. As the diol and the trivalent polyol or are higher in the above polyol mixture A, a polyester polyol and / or a polycarbonate polyol are selected as their main polyols (i.e., more than half of all polyols). A polyoxypropylene polyol can not be used in large quantities in view of the mechanical properties of the interlaced polyurethane resin. Particularly and preferably, the polyol consists essentially of a polyester polyol and / or a polycarbonate + polyol. However, if a polyester polyol is used alone, it is possible that there are some difficulties in the water resistance of the interlaced polyurethane resin. On the other hand, a polycarbonate polyol has a high viscosity, and its simple use is prone. to have a problem when it is going to be laminated by melting. Accordingly, it is very preferred to use both in combination. At present, polycarbonate polyol products commercial types are a bit limited, and the aforementioned problem exists. However, if a polycarbonate polyol having an appropriate low viscosity is available, such a polycarbonate polyol can be used * only. At present, the portion of the polycarbonate polyol based on all polyols is preferably at least 15% by weight, particularly preferably at least 25% by weight. A trivalent or higher valent polycarbonate polyol may be used if available. In the present, in view of the problem with respect to the viscosity and the availability of the polycarbonate polyol, the. The polyol is preferably a combination of three compounds, that is, a higher functional or trifunctional polyester polyol, a polycarbonate diol and a polyester diol, whereby the best interlaced polyurethane resin can be obtained. However, the suitable polyol is not limited to such a combination, if such restrictions will be removed. At present, the average hydroxyl value of the polycarbonate diol is from 35 to 75, and its ratio based on all the diols, is preferably from? 5 to 75% by weight, particularly preferably from 25 to 60% in the . As the polycarbonate polyol can be used an ob-polycarbonate diol -benible by the use of ethylene glycol, dithylene glycol, dipropylene glycol, 1,4-butane diol, neopentyl glycol, 1,6-hexane diol, dimethanol of cyclohexane or other aliphatic or alicyclic bivalent alcohol, or a polycarbonate polyol which is obtainable bivalent, also using a small amount of trivalent or more valent alcohol in combination. In addition, an open ring polymer of a cyclic carbonate compound can also be used. It is known to use a polyurethane ream prepared using a polio! of polycarbonate for laminated security glass (e.g., 3P-B-55-19249, 3P-A-49-98818, P-A-51-144491 and JP-A-59-22197). In the present invention, the polycarbonate polyols such as those described in these references to the prior art can be used. The preferred polycarbonate polyols rnuy are poly (1,6-hexancarbonate) diol and poly (1, 6-hexane / l, 4-d? Rne +.? Lec? Clohexane carbonate) diol. Co or the polyester polyol, a polio is very useful! of polyester having polyhydric alcohol residues and polybasic carboxylic acid residues, or a polyol of + ol that has residues of hydroxycarboxylic acid. Preferred as above is a polyester polyol having dihydropic alcohol residues or the dihydric alcohol residues a small amount of tpphpco alcohol residue plus a small amount of alcohol + r? H? Dpco or polyhydric alcohol at + o, and residues of dibasic acid. For example, a poly ester polyol having residues of ethylene glycol, diethylene glycol, propylene glycol, diol of 3-? Net? L-l, 5-? In <is useful.and, dipropylene glycol, 1,4-butane diol, neoponthyl glycol, 1,6-hexane diol, glycerol, trirnethylolpropane or hexane triol, and residues of adipic acid, azelaic acid, sebasic acid or f + alic acid. Preferred with the latter is a polyester polyol obtained by the addition of a cyclic ester such as e-caprolactone (hereinafter referred to as caprolactone) or a hydroxy-caproic acid, to the aforementioned polyhydric alcohol, or water or a polyvalent compound. . In addition, the polyester polyols described in the aforementioned prior art references can be used, particularly in JP-A-53-27671 and ZJP-A-57-176157. Moreover, like the materials generally described, polyester polyols of the type described in e.g., "Plastic Material Lecture (2) Polyure + hane Resins" published by Nikkan Kogyo Shinbun, p. 56-61 And p. 133-168, can be mentioned. Preferred as the polyester polyol is a poly (1,4-butylbenadipate) polyol, a polyol (et? Lene adipate), a poly (1,4-butylene? Azelate) polyol, a polyol of poly (caprol actone) or a polyol of poly (3-me + i lpen + i len adipate). As the trivalent or higher valent polyol, a triol is preferred, and a poly (caprolactone) triol is particularly proffered. A? Oi? (Ox? Tetramethylene) polyol is usually lower than the two types of polyols described above in terms of mechanical properties or weather resistance. However, it is superior to a polyester polyol in terms of water resistance and is useful as a substitute for a part of the polyester polyol. However, it is usually better not to use it. Other polyols (such as polyoxypropylene polyols or polybutadiene polyols) that are different from those described above are not usually used. Even if they are used for some purposes, they should not be used as main polyols. However, an excellent polyol can be incorporated in mechanical properties, weather resistance, water resistance or viscosity if the case requires it. Chain extender B is preferably composed of at least one diol or diarynin with a molecular weight not greater than 280. Particularly preferred is a diol having a molecular weight of at least 160. An active compound containing basal weight hydrogen trivalent molecular or higher valent such as a triol of ba or molecular weight can be incorporated in a very small amount. However, the chain extender is usually composed of + or only one bivalent compound. As the former chain-tensioner B, they can specifically be used, for example, as ethylene glycol, diethylene glycol, 1,3-propane diol, 1,4-butane diol, neopentyl glycol, 1,5-pentane diol, dioxide. of 1,6-hexane or cyclohexane dimethanol. Instead of, or in addition to said diol, a dihydroxy carboxylic acid or diamine, such as dirnethylol acetic acid, dimethyloxypropionic acid, diaryninodicyclohexylmethane or isoporondynarin can be used. A preferred chain extender is an aliphatic C2-8 diol or an alicyclic diol, and particularly preferred is a 1,4-butane diol, cyclohexane dimethanol or a mixture thereof. It is particularly preferred that part or all is cyclohexane dimethanol. The dirne + anol of cyclohexane is preferably in form -1.4, but may be in the form -1.3, in form -1.2 or in form -1.1, or a mixture of two or more of these four types. As the polyisocyanate compound O, an aliphatic or alicyclic polyisocyanate substantially bivalent is used. In a specific form, this may be, for example, bi (cyclohexyl isocyanate) of 4'-rnetylene, isophorone diisocyanate, cyclohexane diisocyanate, tetramethylene diieocyanate, hexarnetylene diisocyanate or a bivalent modified product thereof (as a modified product type). prepolymer or a modified product of urea). A particularly preferred polyisocyanate compound is bi (cyclohexyl isocyanate) of 4, 4'-methylene or iso-forone diisocyanate. A small amount of a higher non-yellowing trivalent or higher valent polyisocyanate may be incorporated. However, normally, only one bivalent polyisocyanate compound is used. In addition to the main materials described above, small amounts of other additional materials are required in many cases. Particularly, a catalyst and a stabilizer are required in many cases. As the catalyst, a catalyst of the organic metal compound type such as an organic tin compound can be suitably used. As the stabilizer, it is preferred to use one or more selected antioxidants, ultraviolet absorbers and photostabilizers. For example, an hindered phenol compound, an hindered amine compound, a phosphoric acid ester compound, a benzophenone compound or a benzotriazole compound can be used. In addition, depending on the particular purpose, a small amount of eg a dye, a flame retardant, a releasing agent, an adhesion enhancing agent, a surfactant or an odd + electrically conductive agent can be used. . In some cases, a small amount of a diluent agent for reagents may be employed, but usually such diluting agent is not required. The entangled polyurethane resin is prepared using the curable reaction composition consisting of the materials described above by a method such as a shot process, a prepolymer process or a sub-prepolymer process. The rolling is carried out by a casting method. It is particularly preferred that the materials are mixed by a shot method and that the resulting mixture is melted on a flat surface, and solidified for rolling (ie, a casting method). Lamination by a casting method is described in the aforementioned prior art references 3P-A-55-105534 and 3P-A-56-162618. As a method of forming the sheet of the present invention, such conventional methods may be employed. The interlaced polyurethane resin sheet of the present invention is required to be transparent and smooth. By melting the above-described curable reaction composition, it is possible to obtain an extremely smooth sheet. On the other hand, by using the curable reaction composition described above as the starting material, a sheet having a high transparency is normally obtained. The thickness of the sheet of the present invention is not particularly particulate, but is preferably 0.1 to 2.0 rn, most preferably 0.2 to 1.2 in. The interleaved polyurethane ream sheet of the present invention has the characteristic that it is capable of providing sufficient penetration resistance with a thinner thickness than that of a conventional interlaced polyurethane resin sheet. However, if the blade is very thin, there may be a case where the mechanical force such as penetration resistance is inadequate when it is used for laminated safety glass. On the other hand, that which is inexcessarily thin, is not economic. The interlaced polyurethane + resin sheet of the present invention is a smooth and transparent one and has the characteristic that it is an interlaced polyurethane resin sheet having a property of self-healing and resistance to penetration. . Such an interlaced polyurethane resin sheet of the present invention is particularly suitable for application to laminated safety glass. In particular, it is particularly preferred to use the interlaced polyurethane ream sheet of the present invention for a laminated product that + involves a layer structure consisting of at least two layers that include a layer of the interlaced polyurethane ream layer. on one side and a layer of the inorganic glass sheet on the other side. further, it is preferably preferred to use it for a laminated product having a layer structure consisting of at least three layers including a first surface layer made of a synthetic resin, an interlayer made of the resin sheet of interlaced polyurethane and a second surface layer made of inorganic crystal. The first surface layer protects the interlayer made of the interlaced polyurethane resin sheet and has good surface properties for the lamination of the interlaced polyurethane resin / inorganic crystal sheet. A synthetic resin excellent in scratch resistance and stain resistance is preferred. Particularly preferred is some interlaced polyurethane resin. The polyurethane resin disclosed in JP-A-64-56717 is also preferred. Specifically, particularly preferred is a surface layer made of a polyurethane, which is obtained by carrying reaction and curing a polyisocyanate compound consisting of a diisocyanate and a higher tri functional or functional polyisocyanate and having an average molecular weight per group functional or per isocyanate group of from 120 to 240, with a polyol component consisting of a diol and a higher tri functional or functional polyol having an average molecular weight per functional group or per hydroxyl group of from 100 to 550 In this case, the Di-Iocyan + -o is preferably an alicyclic diisocyanate or an aliphatic diisocyanate. Specification + .e, the aforementioned diisocyanate can be employed. The higher tri functional or functional polyisocyanate may preferably be a modified specimen product, an isocyanurate modified product or a modified trimethylolpropane product of such a diisocyanate. As the polyol component consisting of a diol and a higher functional or trifunctional polyol, a polyol ester polyol, a polycarbonate polyol or a polyoxytetramethylene polyol are preferred. Particularly preferred is a polyester polyol such as the polycaprolactone polyol. The aforementioned laminated product is preferably prepared by laminating an inorganic glass sheet and the non-interlaced polyurethane resin sheet having a surface layer made of a synthetic resin on one side (hereinafter referred to herein as a preliminary laminated sheet) with an adhesive material interposed between them. Such a preliminary laminate sheet can be prepared, for example, by a method described in JP-A-53-27671. For example, it can be prepared by melting the curable reaction composition of the present invention in a layer made of a certain specific synthetic resin formed in a carrier. The adhesive material to be used for bonding the preliminary laminate sheet and the inorganic glass sheet is preferably selected from thermoplastic polyurethane resins, polyvinyl butyral resins and EVA resins. However, the adhesive material is not particularly 07 limited to such specific examples. EVA resins are resins of a copolymer of ethylene with vinyl acetate, or resins made of partial hydrolysates thereof. As a method for interposing adhesive material, it is preferred to employ a method in which an adhesive layer made of the adhesive material is formed on the side of the polyurethane ream sheet of the preliminary laminate sheet, and subsequently the adhesive layer. The inorganic glass sheet is laminated to the same »As a rne + odo to laminate the ho a of relatively flexible synthetic resin and the inorganic glass sheet, heat pressing is normally employed. For heat pressing, an autoclave is usually used. It is preferred that the air is first removed between the sheets under reduced pressure, and then pressure is applied to press the two sheets together. The two sheets can only be pressed by reduced pressure, or the laminate can be carried out only by pressing. A specific method for rolling is described, for example, in 3P-B-58-12140 or 3P-B-55-14074. It is preferable that the pretreatment is preliminarily applied to the bonding surface of the inorganic crystal to improve adhesion. Specifically, it is preferred to preliminarily coat a tra + .arn? Agent in + or as a silane compound (F). In another way, by preferentially incorporating a silane compound (D) into the adhesive resin material and / or the curable reaction composition, it is possible to obtain a good adhesive property without applying the above-mentioned pre-mineral retardation to the inorganic glass. The method of incorporating it preliminarily into the curable reaction composition is particularly effective. In particular, it is an entangled polyurethane resin prepared using a curable reaction composition, which consists of the polyol (A), the ex + chain linker (B), the polyacrylate compound (O and a compound of silane (D) in an amount of from 0.001 to 10% by weight, based on the total weight of components A, B and C, as their main components, such as the silane compound or the silane compound E, may be useful in the coxy silicone containing an aryl group or a glycidyloxy group.Specific examples include α-aminopropyltrimethoxysilane, t-arn? Noprop? Lrnet? Ld? Rnetox? Sllano, t-glycidyloxypropyl ethoxysilane, and t glycidyloxypropyl-rnet-11-dirnetoxy s The thickness of the layer of the inorganic glass sheet in the laminated product is preferably from 1 to 10 millimeters, particularly preferably from 2 to 5 millimeters, when used as a window material for a automobile, the thickness of the sheet layer of inorganic crystal is preferably from 3 to 5 rnrn. The thickness of the interlaced polyurethane resin sheet is preferably 0.1 to 2.0 mm, as mentioned above. Par + icularly preferable, this is 0.2 to 1.2 rn, when used for laminated safety glass to be used as a window material for a car. The thickness of the adhesive layer made of the adhesive material is preferably less than 0.2 nm, particularly preferably no more than 0.1 nm, most preferably no more than 0.05 nm. The lower limit for the thickness of this layer is not particularly limited, but is usually 0.01 rnrn. The laminated product of the present invention is very suitable for a window material for a motor vehicle, particularly for a windshield glass. However, it is not limited to such a specific application, and is also useful as a window pane for constructions, for those that security is required. The laminated product of the present invention is usually a colorless or colorless transparent product. It may partially have an opaque portion. Now, the present invention will be described in greater detail with reference to the examples. However, it should be understood that the present invention is by no means restricted to such specific examples. In addition, in the present invention, the physical properties were measured by the following methods.

Methods for measuring physical properties Self-healing property: The surface of the interlaced polyetheresin resin was scratched with a small diamond fragment of 10 jjm in diameter or load, while the property of self-healing was represented by the maximum load where the scoring mark formed disappeared within 10 rnin at 25 ° C. The disappearance of the scratch mark was visually evaluated. In the case of inorganic crystal which has no property of self-healing, the maximum load by this method was 5 g. Penetration resistance to + e? N? Era + ura environment: measured by penetration resistance test in accordance with 3TS R3212 »Impact resistance at low temperatures: measured by the impact resistance test at -20 ° C in accordance with 3.TS R3212 »Light transmission, Taber abrasion: in accordance with 3IS K6301.

EXAMPLE OF PREPARATION 1 Preparation of a surface layer made of a synthetic resin excellent in scratch resistance and in stain resistance 50 parts (parts by weight, likewise appended hereinafter) of poly (caprolactone) triol having a hydroxyl value of 196, 40 parts of poly (caprolactone) triol with a hydroxyl value of 540 and 10 parts of poly (caprolactone) diol with a hydroxyl value of 38, were fused or heated to 100 ° C and subsequently stirred and mixed at the same time they were dehydrated and dosaerated under reduced pressure. This polyol mixture was cooled to 80 ° C, and subsequently 6.0 x 10 ~ 3 parts of dibutylthia or dibutylthia (hereinafter referred to as the catalyst), 4, 7 parts of bi (cyclohexylsocyan + o) of 4 , 4'-rnetylene (hereinafter referred to herein as H12MDI), 4.7 parts of isocyanate day of isophorone and 85 parts of a modified isocyanurate product of 1,6-hexane diisocyanate, were added thereto and mixed by stirring misino + -? ern? o. The generation of heat was observed at the beginning of the reaction. When the system became uniform, defoaming was carried out under reduced pressure by stirring at 80 ° C for 3 minutes. This prepolymerized liquid was melted in a glass of treated release glass (500 x 500 mrn), treated with a release agent and taken to reaction for 5 hrs. in a furnace purged with nitrogen at 120 ° C to obtain a transparent surface layer + e with a mirror surface and a thickness of 0.1 rnrn.

EXAMPLE 1 Preparation of 35 parts of poly (1,6-hexane carbonate) diol with a hydroxyl value of 55.55 parts of poly (caprolactone) diol with a hydroxyl value of 55 and 10 parts of + polyol (caprolactone) with a hydroxyl value of 196, were fused under heat at 100 ° C and then agitated and mixed by dehydrating and deaerating under reduced pressure. This polyol mixture was cooled to 80 ° C, and subsequently 6.0 x 10-3 parts of the catalyst, 13.1 parts of 1,4-butane diol, 13.1 parts of 1,4-cyclohexane dimethanol and 80 parts of H-12MDI , were they sequentially mind? added and mixed in the same ba or agitation. The generation of heat was observed at the beginning of the reaction. When the system became uniform, defoaming under reduced pressure was carried out by stirring at 80 ° for 3 minutes. This prepolymerized liquid was melted in the surface layer obtained in the preparation example 1 and reacted for 15 hrs. in a furnace purged with nitrogen at 120 ° C to obtain a preliminary laminate with a total thickness of 0.8 nm. In this example, the average hydroxyl value of the polyols was 69, and the amount of the chain extender per equivalent of polyols was 3.8 equivalents. A ream of thermoplastic polyurethane was bonded under pressure to the previous preliminary laminate to form a layer adhesive Then, a glass sheet (3.5 x 500 x 500 rnin) that has its surface pre-treated with t-glycidyloxypropyl priontoxy silane, was prepared, and the preliminary laminate was superimposed on the glass sheet so that the adhesive layer surface would face towards the surface treated side of the glass sheet. This assembly was placed in a rubber bag, and the bag was evacuated at 1 rnrnHg and kept under such reduced pressure for 10 minutes in a 120 ° C oven. Subsequently, the rolled product was taken out of the rubber bag, and attached under pressure under heat for 30 min. in a pressure autoclave under a pressure of 8 kg / cm2 at 130 ° C and then left to cool. The laminated safety glass obtained will be referred to hereinbelow as A-1. In the following examples 2 and 3 and in the comparative examples 1 and 2, laminated security glasses were prepared in the same manner as above, except that the starting materials were changed. The names (A-2, A-3, Xl and X-2) of the respective laminates and their starting materials, the average hydroxyl values of the polyols and the equivalent amounts of the chain extender per equivalent of polyols, are shown below.

EXAMPLE 2 Preparation of A-2 diol of pol i (1,6-hexane carbonate) with a hydroxyl value of 55: 35 parts, poly (3-rnetipentilen adipate) diol with a hydroxyl value of 55: 55 parts, Triol of poly (caprolactone) with a hydroxyl value of 196: 10 parts, Catalyst: 6.0 x 10 ~ 3 parts, V-1,4-butane diol: 9"4 parts, 1,4-cyclohexane dimethanol: 9.4 parts, isophorone diisocyanate: 53 parts, Average hydroxyl value of poliois 69, Equivalent amount of chain extender: 2.8.

EXAMPLE 3 Preparation of poly (1,6-hexane carbonate) diol with a hydroxyl value of 55:35 parts, poly (3-rnetipentylene adipate) diol with a hydroxyl value of 55: 55 parts, Triol of poly (caprolactone) with a hydroxyl value of 310: 10 parts, * Catalyst: 6.0 x 10_3 parts, ? diol of l, 4 ~ butane: 9.5 parts, dirnetanol of 1,4-cyclohexane: 9.5 parts, Isophorone diisocyanate: 56 parts, Average hydroxyl value of polyols 81, Equivalent amount of chain extender: 2.4.

EXAMPLE 4 Preparation of A-4 A preliminary laminate was prepared in the same manner as in Example 1, except that 0.2 parts of t-glycidyloxypropyltrinethoxyethylane were added together with the catalyst and 1,4-butane diol. A thermoplastic polyurethane resin was bonded under pressure to the previous preliminary laminate to form an adhesive layer. Subsequently, a thoroughly cleaned glass sheet (3.5 x 500 x 500 mm) was prepared, and the preliminary laminate was superimposed on the glass sheet for the adhesive layer surface to face towards the glass sheet surface. The assembly was placed in a rubber bag, and the rubber bag was evacuated to approximately 1 mrnHg and kept under reduced pressure for 10 rnin in an oven at 120 ° C. Subsequently, the rolled product was taken out of the rubber bag and pressed under heat for 30 rnin in an autoclave under a pressure of 8 kg / cm2 at 130 ° C and subsequently allowed to cool. The laminated safety glass obtained was designated A-4.

COMPARATIVE EXAMPLE 1 • Preparation of Xl Diol of poly (1,6-hexane carbonate) with a 5-hydroxyl value of 55: 7, 5 parts, Poly (l-S-hexane) diol with? n hydroxyl value of 128: 17.5 parts, poly (caprolactone) diol with a hydroxyl value of 91: 55 parts, Triol of poly (caprolactone) with a hydroxyl value of 196: 10 parts, Catalyst: 6.0 x 10-3 parts, 1,4-butane diol: 7.9 parts, Hi2MDI: 48 parts, Average hydroxyl value of polyols 102, Equivalent amount of chain extender: 1.0.

COMPARATIVE EXAMPLE 2 Preparation of X-2 Poly (1,6-hexane carbonate) diol with a hydroxyl value of 128: 35 parts, Poly (caprolactone) diol with a hydroxyl value of 128: 55 parts, Triol of poly (caprolactone) with a hydroxyl value of 196: 10 parts, 2 Catalyst1: 6.0 x 10 ~ 3 parts, ) '1,4-butane diol: 22.4 parts, H12MDI: 99 parts, Average hydroxyl value of polyols 135, 5 Equivalent amount of chain extender: 2.1 ,.

Physical properties of laminated safety glass The surface properties and resistance to penetration of laminated safety glasses A-1 to X-2 are shown in Table 1.

Table 1 Particularly when used for laminated safety glass, the interlaced polyurethane resin sheet of the present invention provides excellent penetration resistance within a wide range of temperatures, even in a relatively thin thickness. It is particularly excellent in impact resistance at low temperatures.

Claims (14)

NOVELTY OF THE INVENTION CLAIMS

1. - A sheet of smooth and transparent interlaced polyurethane resin prepared from a curable reaction composition, which consists of a mixture of high molecular weight polyol (A) consisting of a polyester polyol and / or a polycarbonate polyol. as its main components, and which contains a diol and a trivalent polyol or higher valent, the. The average hydroxyl value of the mixture is from 40 to 120, and the equivalent ratio of (the trivalent polyol or higher valent) / (the diol) is from 0.1 to 0.8, a substantially bivalent chain extender (B) in an amount from 1.9 to 6.0 equivalents per equivalent of the polyol blend (A), and a substantially bivalent alicyclic or aliphatic polyisocyanate compound (O in an amount of from 0.8 to 1.2 equivalents per equivalent sum of the polyol blend (A ) and the chain extender (B), co or its main components 2.- The sheet of polyurethane resin in cross section according to claim 1, further characterized in that the reaction curable composition also contains a silane compound ( D) in a quantity of 0.001 to 10% by weight, based on the total weight of components A, B and C. 3.- The interlaced polyurethane resin sheet according to claim 1, which is prepared melting the curation composition reaction. 4. The interlaced polyurethane resin sheet according to claim 1, further characterized in that the mixture of polyol (A) contains at least one diol with the average hydroxyl value of from 35 to 75 and at least one polyol. trivalent or higher valent with the average value of hydroxy or from 50 to 300. 5.- The interlaced polyurethane ream ho in accordance with claim 1, further characterized in that the polyol blend (A) contains at least 15% by weight of the polycarbonate polyol. 6. The interlaced polyurethane ream ho in accordance with claim 1, further characterized in that the amount of the chain extender (B) is from 2.2 to 4.5 equivalents per equivalent of the polyol mixture (A). 7. The interlaced polyurethane ream sheet according to claim 1, further characterized in that part or all of the chain extender (B) is cyclohexane dirnetanol. 8. The interlaced polyurethane ream sheet according to claim 1, which has a thickness from 0.1 to 2.0 nm. 9. A laminated product with a layer structure consisting of at least two layers including a layer of a smooth and transparent interlaced polyurethane resin layer prepared from a curable reaction composition, which consists of a mixture of high molecular weight polyol (A) consisting of a polyester polyol and / or a polycarbonate polyol as its main components, and containing a diol and a trivalent or higher valent protein, the average hydroxyl value of the mixture is from 40 to 120, and the equivalent ratio of (trivalent polyol or higher valent) to (the diol) is 0.1 to 0.8, a substantially bivalent chain extender (B) in an amount of from 1.9 to 6.0 equivalents per equivalent of the polyol mixture (A), and a substantially alicyclic or aliphatic polyisocyanate compound of + bivalent (C) in a quantity of from 0.8 to 1.2 equivalents per equivalent sum of the polyol mixture (A) and the cade extender na (B), like its main components, on one side, and an inorganic crystal layer on the other side. 10. The laminated product according to claim 9, further characterized in that the curable reaction composition further contains a silane compound (D) in an amount of from 0.001 to 10% by weight, based on the total weight of the components A, B and C. 11. The laminated product according to claim 9, further characterized in that the inorganic crystal is an inorganic cps + having its surface treated with a silane compound (E). 1

2. A laminated product having a layer structure consisting of at least three layers including a first surface layer made of a synthetic resin, an ontrecapa made of a sheet of smooth interlaced polyurethane resin and ansparente, prepared of a curable reaction composition, which consists of a mixture of high molecular weight polyol (A) consisting of a polyester polyol and / or a polycarbonate polyol as its main components, and containing a diol and trivalent or higher valent polyol, the average hydroxyl value of the mixture is from 40 to 120, and the equivalent ratio of the trivalent polyol or more high) / (the diol) is 0.1 to 0.8, substantially bivalent chain extender (B) in an amount of 1.9 to 6.0 equivalents per equivalent of the polyol mixture (A), and an alicyclic or aliphatic polusocyanate compound Substantially bivalent (C) in an amount of from 0.8 to 1.2 equivalents per equivalent of the sum of the mixture of polyol (A) and the chain extender (B) as its main components, and a second layer of surface made of inorganic glass nico. 1

3. The laminated product according to claim 12, further characterized in that the curable reaction composition further contains a eilane compound (D) in an amount of from 0.001 to 10% by weight, based on the total weight of the components A, B and C. The laminated product according to claim 12, further characterized in that the inorganic crystal is an inorganic crystal having its surface treated with a silane compound (E).