JPH0585345B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminated safety glass suitable as a window material for automobiles, and a method for manufacturing the same.
In particular, the present invention relates to a laminated safety glass in which one glass sheet and one crosslinked polyurethane resin sheet are laminated via an adhesive layer, and a method for manufacturing the same. BACKGROUND OF THE INVENTION Laminated safety glass in which a layer of soft synthetic resin such as polyurethane resin is provided on one side of a single inorganic glass (hereinafter simply referred to as glass) sheet or laminated glass sheet is well known. A laminated glass sheet is a laminate in which two glass sheets are laminated with an interlayer film made of polyvinyl butyral resin or the like interposed therebetween. Laminated safety glass, in which a layer of cross-linked polyurethane resin (also called thermosetting polyurethane resin or reticulated polyurethane resin) is provided on one side of a laminated glass sheet, is produced by, for example,
It is described in the -48775 publication. The role of the cross-linked polyurethane resin layer of the laminated safety glass described in this known example is to prevent the skin from being injured by broken glass pieces when the human body collides with the laminated safety glass (a property called tear resistance). be. Further, while ordinary synthetic resins are easily damaged by scratches, this crosslinked polyurethane resin has self-repairing properties (also referred to as self-restoring properties). Self-healing property refers to the property that when a scratch occurs on the surface of a crosslinked polyurethane resin, the scratch naturally disappears over time. Cross-linked polyurethane resins having this property are known and are described in West German Patent No. 2058504 (see Japanese Patent Publication No. 55-6657) as described in the above-mentioned publication.
However, as described in these known examples, this crosslinked polyurethane resin has insufficient mechanical properties. Laminated safety glass requires mechanical properties such as energy absorption and penetration resistance in the event of a human body collision. Therefore, a laminated safety glass consisting of a layer of laminated glass and a layer of this cross-linked polyurethane resin is useful because the laminated glass has the mechanical properties required for laminated safety glass. Laminated safety glass cannot be constructed in place of glass sheets. In promoting weight reduction of automobiles, laminated safety glass using a single glass sheet is more advantageous as an automobile window material than laminated safety glass using the above-mentioned laminated glass sheets. Even when used for other applications, such laminated safety glass is economical. In the case of laminated safety glass using a single glass sheet, in order to satisfy the mechanical properties of laminated safety glass, the laminated safety glass requires a layer of soft synthetic resin with high mechanical properties. Suitable synthetic resin materials include polyvinyl butyral resins and thermoplastic polyurethane resins. However, these materials are prone to scratches on the surface and have poor properties such as solvent resistance (hereinafter referred to as surface properties).
is not sufficient and some kind of surface protection is required. The use of crosslinked polyurethane resins having the above-mentioned properties for surface protection is known, for example, in Japanese Patent Publication No. 57-27050, Japanese Patent Application Laid-open No. 53
It is described in JP-A-27671, JP-A-57-176157, etc. In this known example, in laminated safety glass using one glass sheet,
A relatively thick (approximately 0.5 mm or more) thermoplastic polyurethane resin layer functions as a mechanical property imparting layer,
The cross-linked polyurethane resin layer having a thickness of about 0.4 mm or more functions as a protective layer for the thermoplastic polyurethane resin layer (see JP-A-53-27671, page 17, upper right column et seq.). In addition, in a laminated safety glass having a similar structure using a laminated glass sheet, it is specified that the thermoplastic polyurethane resin layer functions as an adhesive layer and may be a thin layer. In laminated safety glass using a single glass sheet, the need for a thick mechanical properties imparting layer poses various difficulties. The sheet constituting this layer must have an extremely smooth surface, a uniform thickness, and excellent optical properties. For example, the method of forming polyvinyl butyral resins or thermoplastic polyurethane resins into sheets by extrusion molding tends to cause minute surface irregularities and changes in sheet thickness, making it difficult to obtain sheets that fully satisfy optical properties. Crosslinked polyurethane resins can easily be made into sheets with excellent optical properties by cast molding, but thermoplastic polyurethane resins are not easily made into sheets by cast molding because the viscosity of the raw material mixture is high. Forming into a sheet by cast molding refers to a method in which a raw material mixture is cast onto a smooth surface and solidified to form a sheet. In order to lower the viscosity of the thermoplastic polyurethane resin raw material mixture, a method of diluting it with a solvent and cast molding is considered, but although a thin sheet can be obtained, it is difficult to obtain a relatively thick sheet. If the soft synthetic resin layer of laminated safety glass could be made of substantially one layer of synthetic resin material, it would be extremely advantageous in terms of production technology and economy. This material must have both the above-mentioned surface properties and mechanical properties, and is preferably one that can be formed into a sheet by cast molding. As a result of research and study to find a cross-linked polyurethane resin that has the above-mentioned surface properties and mechanical properties and is easy to cast, the present invention has developed a cross-linked polyurethane resin that has such performance and is suitable for the production of laminated safety glass. This led to the discovery of polyurethane resin. However, this crosslinked polyurethane resin does not have sufficient adhesion to the glass surface and requires an adhesive. However, since this adhesive does not require mechanical properties, a thin layer is sufficient. Therefore, for example, a laminated sheet (hereinafter referred to as a pre-laminated sheet) is made by forming a thin adhesive layer on one side of a sheet of cross-linked polyurethane resin. is first manufactured, and laminated safety glass is manufactured by laminating this pre-laminated sheet and one glass sheet. The present invention relates to a laminated safety glass having a layer of crosslinked polyurethane resin having the above characteristics, and a method for manufacturing the same, and has the following two points. A layer of one inorganic glass sheet, a sheet layer of crosslinked polyurethane resin provided on one side of the layer,
In the laminated safety glass having a layer of adhesive material that adheres both sheet layers, the sheet of cross-linked polyurethane resin has an average hydroxyl value of 70 to 150, (3
The equivalent ratio of (polyol)/(diol)
A cross-linked polyurethane obtained by reacting a relatively high molecular weight diol consisting of a combination of 0.1 to 0.6, a trivalent or higher valence polyol, a substantially divalent chain extender, and a substantially divalent polyisocyanate compound. Laminated safety glass characterized by being a sheet of cross-linked polyurethane resin, which has self-repairing properties, an elongation of about 250% or more, and a breaking strength of about 300 kg/cm ² or more. . In the method of manufacturing laminated safety glass by laminating one inorganic glass sheet and one pre-laminated sheet, the average hydroxyl value of the diol and the trivalent or higher polyol is 70 to 150, (the trivalent or higher polyol )/(diol) equivalent ratio of 0.1 to 0.6, a relatively high molecular weight diol and a trivalent or higher polyol, a substantially divalent chain extender, and a substantially divalent polyisocyanate compound It is a crosslinked polyurethane resin obtained by reacting
A pre-laminated sheet consisting of a sheet of cross-linked polyurethane resin having an elongation of 250% or more and a breaking strength of approximately 300Kg/cm2 or ^more and a layer of adhesive material on one side, and one inorganic glass sheet. A method for producing laminated safety glass, characterized by laminating layers of adhesive material as lamination surfaces. The crosslinked polyurethane resin of the present invention has self-repairing properties that are approximately the same or higher than those of known crosslinked polyurethane resins. In order to have self-healing properties, the measured value must be approximately 25 g or more as determined by the test described below. As described below, the measured value of the crosslinked polyurethane resin in the present invention is in the range of about 80 to 200 g.
The above-mentioned Japanese Patent Publication No. 59-48775 discloses that the crosslinked polyurethane resin used therein has a self-healing property of about 25 to 40 g. The measurement method is considered to be almost the same as the measurement method of the present invention, but the measurement conditions, the circular shape of the diamond chip, etc. may be slightly different. According to other materials (Saint-Gobain technical data), it has been revealed that when an inorganic glass surface is scratched using the above method, scratches occur at approximately 18 to 20 g. When the surface of inorganic glass was scratched using the measurement method of the present invention, a scratch occurred at about 5 g. According to the above publication, the elongation (elongation at break) of the cross-linked polyurethane resin used therein is approximately 100%, and the breaking strength is approximately 204 Kg/cm ² (value converted into units). It has been revealed. In contrast, the crosslinked polyurethane resin of the present invention has an elongation of about 250% or more and a breaking strength of about 300 kg/cm ² or more. As shown in the Examples below, the crosslinked polyurethane resin used in the present invention usually has a
It has an elongation of 300-600% and a breaking strength of about 500-800Kg/ ^cm2 . Moreover, the relationship between elongation and strength up to breakage (relationship represented by a stress-strain curve) exhibits completely different behavior between the crosslinked polyurethane resin of the present invention and the above-mentioned known crosslinked polyurethane resins. This stress strain curve is shown in FIG. 1st
As is clear from the figure, the crosslinked polyurethane resin of the present invention exhibits behavior similar to a thermoplastic polyurethane resin with excellent mechanical strength, and exhibits behavior that is completely different from that of known polyurethane resins. Polyurethane resins are obtained by the reaction of a polyvalent active hydrogen-containing compound, particularly a polyol, and a polyvalent isocyanate group-containing compound (hereinafter referred to as a polyisocyanate compound). When both of these two types of compounds are divalent, a thermoplastic polyurethane resin is obtained, and when at least one of them is more than divalent, a crosslinked polyurethane resin is obtained. The physical properties of crosslinked polyurethane resins are influenced by the type of active hydrogen-containing compound. Generally, polyurethane resin elastomers with high mechanical properties are obtained by using a high molecular weight active hydrogen-containing compound in combination with a low molecular weight active hydrogen-containing compound called a chain extender or a crosslinking agent. However, according to studies conducted by the present inventors, it has been found that the self-healing properties and high mechanical properties of crosslinked polyurethane resins tend to contradict each other. That is, crosslinked polyurethane resins with high mechanical properties have low self-healing properties. Therefore, there are relatively limited types of crosslinked polyurethane resins that have both of these properties.
Specifically, the cross-linked polyurethane resin having self-healing properties is composed of a propylene oxide adduct of trimethylolpropane with a molecular weight of about 450 ( It is limited to crosslinked polyurethane resins obtained by reacting approximately equal amounts of polyether triol with a hydroxyl value of about 374) and a trivalent or higher polyisocyanate compound consisting of a biuret of 1,6-hexamethylene diisocyanate.
On the other hand, the crosslinked polyurethane resin in the present invention must basically be a crosslinked polyurethane resin obtained using the following raw materials. 1. A relatively high molecular weight polyol and a low molecular weight active hydrogen-containing compound (hereinafter referred to as chain extender) must be used together. If a chain extender is not used in combination, a crosslinked polyurethane resin with high mechanical properties cannot be obtained. 2 For the above polyol, it is necessary to use a diol and a trivalent or higher valence polyol in combination, and their average hydroxyl value is about 70 to 150, and the equivalent ratio of (trivalent or higher polyol)/(diol) is in the range of about 0.1 to 0.6. must become. If the average hydroxyl value and the equivalent ratio of both polyols are higher than this, the mechanical properties will decrease, and if it is lower than this, the self-healing property will decrease. 3. The chain extender must be a substantially divalent compound having a functionality of less than about 2.3, especially less than 2.1, and the polyisocyanate compound must also be a substantially divalent polyvalent compound having a functionality of less than about 2.3, especially less than about 2.1. Must be an isocyanate compound. If the number of functional groups is higher than this, mechanical properties will deteriorate. 4 The amount of chain extender per equivalent of polyol is approximately
Must be between 0.4 and 1.8. If it is higher than this, the self-healing property will be lowered, and if it is lower than this, the mechanical properties will be lowered. In addition, as a natural premise for the production of crosslinked polyurethane resins, the total equivalent of the polyol and chain extender is approximately equal to the equivalent of the polyisocyanate compound, and in particular, approximately 0.8 to 1.2 equivalents of the latter is appropriate for 1 equivalent of the former. . Further, the polyisocyanate compound needs to be a non-yellowing polyisocyanate compound. Note that the hydroxyl value is used as a numerical value related to the molecular weight of the polyol. This is because when a diol and a trivalent or higher-valent polyol are used together, the influence of their molecular weights on physical properties cannot be expressed simply by the average value of their molecular weights. The relationship between hydroxyl value and molecular weight is expressed by the following formula. [0HV] = ([a] / [MW]) × 56.1 × 10 ³ [OHV]: Hydroxyl value (mgKOH/g) [a]: Number of functional groups [MW]: Molecular weight The above polyol has a hydroxyl value of approximately 40 to 250, Especially about
Diols of 60 to 150 and hydroxyl values of about 50 to 300, especially about
It is preferable to consist of a combination of polyols having a valence of 100 to 250 and having a valence of 3 or more. Note that the diol and the polyol having a valence of 3 or more may each be a combination of two or more types. In that case, each polyol may be outside the above range as long as the average hydroxyl value is within the above range. However, the upper limit of the hydroxyl value of each polyol does not exceed about 400 in order to distinguish it from the chain extender described below. Preferred diols have a hydroxyl value of about 90 to 100, and are a combination of a diol exceeding the upper limit and a diol below the upper limit, or a combination of a diol below the lower limit and a diol above the lower limit. The most preferred polyol is at least two diols having an average hydroxyl value of about 60 to 130 and an average hydroxyl value of about 150.
~250 at least one trivalent or higher polyol,
Especially the combination of triols. Moreover, the average hydroxyl value in the combination of these diols and polyols having a valence of 3 or more is most preferably about 80 to 140, and the equivalent ratio thereof is most preferably about 0.15 to 0.35. The chain extender comprises at least one diol or diamine having a molecular weight of about 280 or less, and diols having a molecular weight of about 160 or less are particularly preferred. Although a very small amount of a trivalent or more low molecular weight active hydrogen-containing compound such as a low molecular weight triol may be used in combination, it usually consists of only a divalent compound. Above polyol 1
Most preferably, the amount of chain extender to equivalents is about 0.7 to 1.3 equivalents. In addition, when the chain extender is a low molecular weight polyol, the average hydroxyl value of the relatively high molecular weight diol, the trivalent or higher valence polyol, and this low molecular weight polyol is:
Although not particularly limited, a range of about 120 to 250, particularly about 150 to 220, shows the best performance in both mechanical properties and self-healing properties, and is the most suitable as a raw material for the crosslinked polyurethane resin in the present invention. preferable. As the above-mentioned relatively high molecular weight diols and trivalent or higher polyols, polyester polyols, polycarbonate polyols, and poly(oxytetramethylene) polyols are selected as main polyols (that is, as the majority of all polyols). . Polyoxypropylene polyols cannot be used in large quantities because of the mechanical properties of the crosslinked polyurethane resin.
Particularly preferred polyols are polyester polyols and polycarbonate polyols. However, the use of only polyester polyols tends to cause problems in the water resistance of the crosslinked polyurethane resin. On the other hand, polycarbonate polyols have a high viscosity and may cause problems when formed into a sheet by cast molding. Therefore, most preferably both are used in combination. However, polycarbonate polyols have the above-mentioned problems because there are only a few types of commercially available polycarbonate polyols; however, if a suitable low-viscosity polyol can be obtained, it would be possible to use only polycarbonate polyols. It is currently preferred to use a polycarbonate polyol proportion of at least about 15% by weight, particularly about 25% by weight, based on the total polyol. There are currently no commercially available polycarbonate polyols having a valence of 3 or more, but of course they can be used if they are available. Therefore, due to the viscosity problem and the availability of polycarbonate polyols, the best polyol is a crosslinked polyurethane resin that is a combination of trivalent or higher polyester polyols, polycarbonate diols, and polyester diols. bring about. However, if such restrictions are removed, the combination is not limited to this. The currently preferred polycarbonate diol has a hydroxyl value of about 40 to 200, and its proportion to the total diol is about 25 to 75% by weight, particularly about 25 to 60% by weight. Examples of polycarbonate polyols include ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, and other aliphatic or alicyclic divalent or higher alcohols. Polycarbonate diol obtained using 2 and a small amount of trivalent or higher alcohol
Polycarbonate-based polyols exceeding the polyhydric value can be used. Ring-opening polymerization of cyclic carbonate compounds may also be used. It is well known that polyurethane resin using polycarbonate polyol is applied to laminated safety glass; for example,
Publication No. 19249, Japanese Patent Application Laid-Open No. 1972-98818, Japanese Patent Application Publication No. 1973
It is described in JP-A-144492, JP-A-59-22197, etc. In the present invention, polycarbonate polyols as described in these known examples can be used. The most preferred polycarbonate polyol is poly(1,6
-hexane carbonate) diol, and poly(1,6-hexane/1,4-dimethylenecyclohexane carbonate) diol. As the polyester polyol, a polyester polyol having a polyhydric alcohol residue and a polycarboxylic acid residue or a polyester polyol having a hydroxycarboxylic acid residue is suitable. The former is preferably a polyester polyol having a dihydric alcohol residue, or both it and a small amount of a trihydric or higher alcohol residue, and a dibasic acid residue. For example, ethylene glycol,
diethylene glycol, propylene glycol,
Residues such as dipropropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, hexanetriol and residues such as adipic acid, azelaic acid, sebacic acid, phthalic acid, etc. Polyester polyols having groups are suitable. The latter is preferably a polyester polyol obtained by adding a cyclic ester such as ε-caprolactone (hereinafter referred to as caprolactone) or hydroxycaproic acid to the polyhydric alcohol, water, or other polyvalent compound. In addition, the above-mentioned known examples, especially JP-A-53-27671 and JP-A-57-
Polyester polyols described in JP 176157 can be used. Furthermore, as a general description, "Plastic Materials Course [2] Polyurethane Resin" published by Nikkan Kogyo Shimbun, pp. 56-
Examples include the types of polyester polyols described on pages 61 and 133 to 168. The most preferred polyester polyols are poly(1,4-butylene adipate) polyols, poly(ethylene adipate) polyols, poly(1,4-butylene azelate) polyols, and poly(caprolactone) polyols. As the trivalent or higher polyol, especially the triol, a poly(caprolactone) polyol is particularly preferred. In addition to the above polycarbonate polyols and polyester polyols, poly(oxytetramethylene) polyols may be used as the main polyol. Although this polyol is often inferior to the former two in terms of mechanical properties and weather resistance, it is superior in water resistance to polyester polyols, so it can particularly be used as a partial or complete substitute for polyester polyols. However, even if it is used, it is usually preferable not to use it as the main polyol. Other polyols other than these (e.g. polyoxypropylene polyols and polybutadiene polyols)
is not normally used, but even if it is used for some purpose, it is preferably not used as the main polyol. Of course, if there is a polyol that is excellent in terms of mechanical properties, weather resistance, water resistance, viscosity, etc., this does not preclude its use. As the chain extender, diols are preferred as mentioned above, such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4
-butanediol, neopentyl glycol,
1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, etc. can be used. Dihydroxycarboxylic acids and diamines such as dimethylol acetic acid, dimethylol propionic acid, diaminodicyclohexylmethane, and isophorone diamine can be used instead of or together with these. Preferred chain extenders are aliphatic diols having 2 to 6 carbon atoms, with 1,4-butanediol and ethylene glycol being particularly preferred. As the polyisocyanate compound, divalent non-yellowing diisocyanate is used as described above. Specifically, for example, methylene bis(cyclohexyl isocyanate), isophorodiisocyanate, cyclohexane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and divalent modified products thereof (for example, prepolymer type modified products, urea modified products, etc.) There is. Particularly preferred polyisocyanate compounds are 4,4'-methylene-bis(cyclohexylisocyanate) and isophorodiisocyanate. Although a small amount of trivalent or higher non-yellowing polyisocyanate can be used in combination, only divalent polyisocyanate compounds are usually used. Crosslinked polyurethane resins often require small amounts of other auxiliary raw materials in addition to the above-mentioned main raw materials. In particular, catalysts and stabilizers are often essential raw materials.
As the catalyst, an organometallic compound catalyst such as an organotin compound is suitable. As the stabilizer, it is preferable to use one or more of antioxidants, ultraviolet absorbers, light stabilizers, and the like. For example, hindered phenol compounds, hindered amine compounds,
Phosphoric ester compounds, benzophenone compounds, benzotriazole compounds, etc. can be used. In addition, small amounts of colorants, flame retardants, mold release agents, adhesion improvers, etc. may be used depending on the purpose. In some cases, small amounts of diluents such as solvents may be used, but are usually unnecessary. The crosslinked polyurethane resin is produced using the above-mentioned raw materials by a method such as a one-shot method, a prepolymer method, or a quasi-prepolymer method. Forming into sheets is carried out by the casting method. Particularly preferred is a method in which raw materials are mixed by a one-shot method, the mixture is cast onto a smooth surface, and solidified to form a sheet. In addition to the above-mentioned known examples, sheeting by the casting method is disclosed in Japanese Patent Application Laid-Open No. 1986-
It is described in Japanese Patent Application Laid-open No. 105534 and Japanese Patent Application Laid-Open No. 162618/1983. During this sheet formation, it is preferable to manufacture the pre-laminated sheet by subsequently applying an adhesive solution or the like to the surface of the crosslinked polyurethane resin sheet that has solidified to a certain extent or more. Of course, an adhesive layer can be formed on one side of the sheet of the crosslinked polyurethane resin obtained after the crosslinked polyurethane resin is formed into a sheet. The adhesive in this pre-laminated sheet is preferably selected from thermoplastic polyurethane resins, polyvinyl butyral resins, or EVA resins.
EVA resin refers to a resin based on a copolymer of ethylene and vinyl acetate, or a resin made from a partial hydrolyzate thereof. These adhesives have thermoplastic properties and, when pressed against a glass sheet, can deform to follow the surface of the glass sheet. Therefore, the adhesive layer may have irregularities on its surface, and some degree of non-uniformity in thickness is acceptable. In order to prevent the formation of bubbles due to residual air during lamination with a glass sheet, it is an effective means to provide fine irregularities on the surface of the adhesive layer to prevent air from remaining. Incidentally, it goes without saying that the adhesive is not necessarily limited to the above-mentioned synthetic resins. The laminated safety glass of the present invention is preferably manufactured by laminating the above pre-laminated sheet and one glass sheet. In the case of flat glass sheets, it is also possible to first apply an adhesive to the glass surface and then laminate sheets of crosslinked polyurethane resin.
In the case of bent glass sheets such as automobile window materials, it is difficult to employ this method.
It is also possible to simultaneously laminate a cross-linked polyurethane resin sheet and an adhesive sheet onto a glass sheet, but handling the thin adhesive sheet and removing air from the laminated surface is complicated, and the lamination process is also complicated. become Therefore, it is most preferable to use the pre-laminated sheet described above. As a method for laminating a relatively soft synthetic resin sheet and a glass sheet, heating and pressing are usually employed. An autoclave is usually used for heating and pressurizing, and it is preferable to first remove air between the sheets under reduced pressure and then apply pressure to press both sheets. Both sheets can be pressed by only reduced pressure, or laminated by only pressure. As a specific lamination method, for example,
It is described in Japanese Patent Publication No. 55-14074. It is preferable that the adhesive surface of the glass sheet is pretreated in advance to improve adhesiveness, and a suitable pretreatment agent is a silane compound such as an alkoxysilane containing an amino group or a grid group. . The thickness of the glass sheet layer in the laminated safety glass of the present invention is suitably about 1 to 10 mm, particularly 2 to 6 mm. When used as an automobile window material, the thickness of the glass sheet layer is particularly preferably about 3 to 5 mm. The thickness of the cross-linked polyurethane resin layer is approximately 0.2 to 2.0 mm.
In particular, 0.4 to 1.5 mm is suitable. In the case of laminated safety glass used as a window material for automobiles, the thickness is particularly preferably 0.6 to 1.2 mm. The thickness of the adhesive layer is less than about 0.2mm, especially about 0.1
mm or less is appropriate, and 0.05 mm or less is particularly preferable. The lower limit of the thickness of this layer is not particularly limited, but approximately 0.01 mm is appropriate. The laminated safety glass of the present invention is most suitable as a window material for automobiles, especially as a windshield. but,
It is not limited to this use, for example, it can also be used as architectural window glass where safety is required. The laminated safety glass of the present invention is usually a colorless or colored transparent body. Further, some portions may be opaque. The present invention will be explained below with reference to Examples.
The present invention is not limited only to these examples. The method for measuring physical properties in the present invention, the production of a crosslinked polyurethane resin sheet, a comparative sheet, the stress strain curve of the obtained crosslinked polyurethane resin, the production of laminated safety glass, and the physical properties of laminated safety glass will be explained below in order. . [Method for measuring physical properties] Self-healing property: The surface of the crosslinked polyurethane resin is scratched with a loaded diamond chip of 10 μm diameter, and the scratch is expressed as the maximum load at which the scratches can disappear within 10 minutes at 25°C. Disappearance of scratches was determined visually. In the case of inorganic glass that does not have self-healing properties, this method caused scratches under a load of approximately 5 g. Elongation, breaking strength, tensile strength: According to JIS K6301. Light transmittance, Taber abrasion: According to JIS K6301. Penetration resistance: According to JIS R 3212. Passing means that the steel ball did not penetrate, the broken glass was adhered to the sheet, and no glass was observed to scatter. [Manufacture of cross-linked polyurethane resin sheet] A-1: 43.86 parts of poly(1,6-hexane carbonate) diol with a hydroxyl value of approximately 122 [parts by weight,
68.93 parts of poly(caprolactone) diol having a hydroxyl value of about 90.5, and 12.54 parts of poly(caprolactone) triol having a hydroxyl value of about 195.2 were melted by heating at 100°C and then mixed with stirring while being dehydrated and degassed under reduced pressure. After cooling this polyol mixture to 80°C, it was added with 6.0% dibutyltin diurarate [hereinafter referred to as catalyst].
×10 ^-3 parts, 1,4-butadiol 10.02 parts,
and 64.5 parts of 4,4'-methylenebis(cyclohexyl isocyanate) [hereinafter referred to as H ₁₂ MDI] were sequentially added and mixed with stirring.
An exotherm was observed at the beginning of the reaction. When the system became homogeneous, it was degassed under reduced pressure while stirring at 80°C for 3 minutes. This prepolymerization liquid was cast onto a glass sheet (500 x 500 mm) that had been subjected to mold release treatment, and reacted for 15 hours in a nitrogen purge oven at 120°C to obtain a sheet with a thickness of 0.7 mm that was transparent and had a mirror surface. The average hydroxyl value of the three polyols mentioned above is about 112. The obtained crosslinked polyurethane resin sheet is hereinafter referred to as A-1. The elongation of this crosslinked polyurethane resin sheet was 374%, the breaking strength was 771 kg/cm, and the tearing strength was 30 kg/cm. Hereinafter, a crosslinked polyurethane resin sheet was manufactured in the same manner as above except that the raw materials were changed. The name of each sheet (A-2 to A-4), its raw materials, sheet thickness, and average hydroxyl value of the polyol (without chain extender) are shown below. 1,6-hexane carbonate) diol 43.53 parts Poly(caprolactone) diol with a hydroxyl value of approximately 70.79 68.41 parts Poly(caprolactone) triol with a hydroxyl value of approximately 195.2 12.44 parts Catalyst 6.0×10 ^-3 parts 1,4-butanediol 12.44 parts H ₁₂ MDI 63.18 parts Average hydroxyl value of polyol 88.5 Sheet thickness 0.7mm Elongation 415% Breaking strength 655Kg/cm ² Tear strength 38Kg/cm A-3 Poly(1,6-hekasan carbonate) with a hydroxyl value of approximately 57 Diol 63.07 parts Poly(caprolactone) diol with a hydroxyl value of approximately 90.5 99.12 parts Poly(caprolactone) triol with a hydroxyl value of approximately 195.2 18.02 parts Catalyst 8.25×10 ^-3 parts 1,4-butanediol 14.42 parts H ₁₂ MDI 80.37 parts Polyol Average hydroxyl value 89.25 Sheet thickness 1mm Elongation 474% Breaking strength 655Kg/cm ² Tear strength 33Kg/cm A-4 Poly(1,6-hexane carbonate) diol with a hydroxyl value of approx. 54.52 35.68 parts Poly with a hydroxyl value of approx. 90.79 (Caprolactone) diol 124.87 parts Poly(caprolactone) triol with a hydroxyl value of approximately 195.2 17.84 parts Catalyst 8.25×10 ^-3 parts 1,4-butanediol 14.27 parts H ₁₂ MDI 82.34 parts Average hydroxyl value of polyol 94.0 Sheet thickness 1.1 mm Elongation 495% Breaking strength 690Kg/ ^cm2 Tear strength 35Kg/cm A-5 Poly(1,6-hexane carbonate) diol with a hydroxyl value of approx. 53.3 44.54 parts Poly(caprolactone) diol with a hydroxyl value of approx. 91.1 69.99 parts Hydroxyl value About 195.2 Poly(caprolactone) triol 12.73 parts Catalyst 6.0×10 ^-3 parts 1,4-butanediol 11.45 parts H ₁₂ MDI 61.30 parts Average hydroxyl value of polyol 88.3 Sheet thickness 0.7 mm Elongation 504% Breaking strength 707 Kg / ^cm2 Tear strength 48Kg/cm A-6 Poly(1,6-hexane carbonate) diol with a hydroxyl value of approx. 53.3 43.44 parts Poly(caprolactone) diol with a hydroxyl value of approx. 91.1 68.27 parts Poly(caprolactone) triol with a hydroxyl value of approx. 195.2 12.41 parts Catalyst 6.0×10 ^-3 parts 1,4-butanediol 12.41 parts H ₁₂ MDI 63.46 parts Average hydroxyl value of polyol 88.3 Sheet thickness 0.7 mm Elongation 520% Breaking strength 637 Kg/cm ² Tear strength 56 Kg/cm A-7 Poly(1,6-hexane/
1,4-dimethylenecyclohexane carbonate) diol [Polycarbonate diol obtained using 1,6-hexane diol and cyclohexanedimethanol as raw material diol]
22.40 parts Poly(1,6-hexane carbonate) diol with a hydroxyl value of approximately 55.87 22.40 parts Poly(caprolactone) diol with a hydroxyl value of approximately 91.1 70.41 parts Poly(caprolactone) triol with a hydroxyl value of approximately 195.2 12.80 parts Catalyst 6.0×10 ^-3 Part 1,4-butanediol 10.24 parts H ₁₂ MDI 61.74 parts Average hydroxyl value of polyol 101.9 Sheet thickness 0.7mm Elongation 399% Breaking strength 754Kg/cm ² Tear strength 53Kg/cm A-8 Polymer with a hydroxyl value of approximately 128.6 (1,6-hexane/
1,4-dimethylenecyclohexanecarbonate) diol 21.85 parts Poly(1,6-hexane carbonate) diol with a hydroxyl value of approximately 55.87 21.85 parts Poly(caprolactone) triol with a hydroxyl value of approximately 91.1 68.66 parts Poly(caprolactone) with a hydroxyl value of approximately 195.2 Triol 12.48 parts Catalyst 6.0×10 ^-3 parts 1,4-butanediol 11.24 parts H ₁₂ MDI 63.93 parts Average hydroxyl value of polyol 101.9 Sheet thickness 0.7 mm Elongation 387% Breaking strength 626 Kg/cm ² Tear strength 45 Kg/ cm [Comparison ^sheet ] Diol: 10.57 parts H ₁₂ MDI: 63.87 parts Using the above raw materials, a 1 mm thick sheet was produced by the casting method in the same manner as the crosslinked polyurethane resin sheet of A-1. The surface of the obtained thermoplastic polyurethane resin sheet was orange-skinned and could not be optically applied to laminated safety glass at all.
The elongation of this cross-linked polyurethane resin sheet is
690%, breaking strength is 400Kg/ ^cm2 , tear strength is 41Kg/
It was cm. X-2 Poly(butylene adipate) with a hydroxyl value of approximately 90.5
Diol 87.09 parts Poly(caprolactone) triol with a hydroxyl value of approximately 90.5 87.09 parts Catalyst 8.25×10 ^-3 parts 1,4-butanediol 10.45 parts H ₁₂ MDI 93.37 parts 1.1 mm thick sheet made in the same manner as the A-1 sheet A sheet having a mirror surface was obtained. The average hydroxyl value of the polyol is 142.9 (however, the triol/diol equivalent ratio is 1.44). This cross-linked polyurethane resin sheet has an elongation of 230% and a breaking strength of
The tear strength was 380Kg/cm ² and the tear strength was 27Kg/cm. X-3 A cross-linked polyurethane resin sheet (thickness: 0.6 mm) with known self-healing properties was obtained. This cross-linked polyurethane resin sheet
Cross-linked polyurethane resin sheet described in Publication No. 48775 (for composition, see Examples in Japanese Patent Publication No. 55-6657)
(Based on the results of physical property measurements, chemical analysis, etc.) ^-3 parts 1,4-butanediol 9.71 parts H ₁₂ MDI 38.29 Using the above raw materials, a thermoplastic polyurethane resin block was produced by a prepolymer method. This was granulated and then extruded to produce a thermoplastic polyurethane resin sheet with a thickness of 0.5 mm. The elongation of this thermoplastic polyurethane resin sheet is 480%.
The breaking strength was 645 Kg/cm ² and the tearing strength was 98 Kg/cm.
Note that this thermoplastic polyurethane resin sheet is an example of a thermoplastic polyurethane resin sheet with excellent mechanical properties, and has almost no self-healing properties. [Stress-Strain Curve] The stress-strain curves of the crosslinked polyurethane resin sheets A-1 to A-4 and the sheets X-3 and X-4 are shown in FIG. Example [Manufacture of laminated safety glass] An ethanol solution of polyvinyl butyral resin was applied to one side of the cross-linked polyurethane resin sheet of A-1 and dried to obtain a pre-laminated sheet having an adhesive layer with a thickness of about 0.20 mm. Manufactured. A glass plate (3 x 500 x 500 mm) whose surface had been previously treated with γ-glycidoxypropyltrimethoxysilane was prepared, and the pre-laminated sheet was laminated on the surface of the glass plate which had been surface-treated, with the surface of the adhesive layer serving as the lamination surface. Put this stuff in a rubber bag, reduce the pressure inside the bag to about 1mmHg, and keep it at 120℃.
Keep in the oven for 10 minutes. Next, the laminate was taken out from the rubber bag, and then hot-pressed in an autoclave at 130° C. and 10 kg/cm ² for 30 minutes, and allowed to cool.
The obtained laminated safety glass is hereinafter referred to as B-1. In the same way, from sheet A-2 to B-2. From sheet A-3 to B-3, from sheet A-4 to B-4, A.
-5 sheet to B-5, A-6 sheet to B
-6, B-7 sheets to B-7 and A-8
A laminated safety glass called B-8 was manufactured from the sheet. [Physical Properties of Laminated Safety Glass] Table 1 shows the performance and penetration resistance of the crosslinked polyurethane resin surface of the laminated safety glasses B-1 to B-8 above. 【table】

[Brief explanation of the drawing]

FIG. 1 is a graph showing stress strain curves of the crosslinked polyurethane resin sheet used in Examples, a known crosslinked polyurethane resin sheet, and a thermoplastic polyurethane resin sheet.

Claims (1)

[Claims] 1. One inorganic glass sheet layer, a crosslinked polyurethane resin sheet layer provided on one side of the inorganic glass sheet layer,
In laminated safety glass having a layer of an adhesive material that adheres both sheet layers, the sheet of crosslinked polyurethane resin has an average hydroxyl value of 70 to 150, (3
The equivalent ratio of (polyol)/(diol)
A cross-linked polyurethane obtained by reacting a relatively high molecular weight diol consisting of a combination of 0.1 to 0.6, a trivalent or higher valence polyol, a substantially divalent chain extender, and a substantially divalent polyisocyanate compound. A laminated safety sheet comprising a cross-linked polyurethane resin that has self-healing properties, an elongation of about 250% or more, and a breaking strength of about 300 kg/cm ² or more. glass. 2 In a method for manufacturing laminated safety glass by laminating one sheet of inorganic glass and one pre-laminated sheet, the average hydroxyl value of the diol and polyol with a valence of 3 or more is 70 to 150, A relatively high molecular weight diol and a trivalent or higher valent polyol consisting of a combination in which the equivalent ratio of polyol)/(diol) is 0.1 to 0.6, a substantially divalent chain extender, and a substantially divalent polyol. A cross-linked polyurethane resin obtained by reacting isocyanate compounds, which also has self-healing properties and has approximately
A pre-laminated sheet consisting of a sheet made of a cross-linked polyurethane resin having an elongation of 250% or more and a breaking strength of about 300 kg/cm ² or more and a layer of adhesive material on one side, and one inorganic glass sheet. A method for manufacturing laminated safety glass, comprising laminating the adhesive material layer as a lamination surface.