JPS61177241A - Laminated safety glass and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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. The present invention relates to a laminated safety glass in which layers are laminated, 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. A laminated safety glass in which a layer of cross-linked polyurethane resin (also called thermosetting polyurethane resin or striated polyurethane resin) is provided on one side of a laminated glass sheet is disclosed, for example, in Japanese Patent Publication No. 59-4877.
It is described in Publication No. 5. The role of the cross-linked polyurethane resin layer of the laminated safety glass described on the publicly known side is to prevent the skin layer from being injured by broken glass pieces when a human body collides with the laminated safety glass (a property called tear resistance). It is in. 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 as described in the above publication, West German Patent No. 2
It is described in the specification of No. 058504 (see Japanese Patent Publication No. 55-61357). However, as described in these known examples, this crosslinked polyurethane resin has insufficient mechanical properties. Laminated safety glasses require mechanical properties such as energy absorption and penetration resistance in the event of a human body collision. Therefore, lb'i layer 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 a single sheet of glass.

In promoting the use of lighter automobiles, one glass sheet I
A laminated safety glass using -[- is more advantageous as an automobile window material than a laminated safety glass using a laminated glass sheet. 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 thick synthetic resin with high mechanical properties. Suitable synthetic resin materials include polyvinyl butyral resins and thermal n1 plastic polyurethane resins. However, these materials are prone to scratches on the surface, do not have sufficient properties such as solvent resistance (hereinafter referred to as surface properties), and require some kind of surface protection. 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 and Japanese Patent Application Laid-open No. 53-27 [i? Publication No. 1, Japanese Unexamined Patent Publication No. 57-1765
It is described in Publication No. 7, etc. In this known example,
In laminated safety glass using a single glass sheet, a relatively thick layer (approximately 0.5 mm or more) of thermoplastic polyurethane resin functions as four layers with mechanical properties. 2, the crosslinked polyurethane resin layer 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, the thermoplastic polyurethane resin layer functions as an adhesive layer, and it is clearly stated that it may be a thin layer.

In laminated safety glass using one glass sheet,
The need for thick mechanical properties imparting layers poses various difficulties. The sheet for constituting this layer must be C.I., which has an extremely smooth surface, a uniform thickness, and excellent optical properties. For example, extrusion molding of polyvinyl butyral resin and thermoplastic polyurethane resin can be used! The method of forming a sheet tends to cause fine surface irregularities and changes in sheet thickness, making it difficult to obtain a sheet that satisfies optical properties. Cross-linked 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 raw material mixture has a high viscosity. Forming into a sheet by cast molding refers to a method in which a raw material mixture is cast onto a smooth surface 1- and solidified to form a sheet. In order to lower the viscosity of the raw material mixture of thermoplastic polyurethane resin, it is possible to dilute it with a solvent and then perform cast molding, 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 composed of substantially one layer of synthetic resin material, then
1-1 Economy-1-It is expected to be extremely advantageous. 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) in which a thin adhesive layer is formed on one side of a sheet of cross-linked polyurethane resin is used. First, this pre-laminated sheet and one glass sheet are laminated to form 11
Laminated safety glass is manufactured.

] The present invention relates to a laminated safety glass having a layer of a crosslinked polyurethane resin having the characteristics mentioned above, and a method for manufacturing the same, and has the following two points.

In laminated safety glass that has a layer of one inorganic glass sheet, a sheet layer of cross-linked polyurethane resin provided on one side of the sheet, and a layer of adhesive material that adheres both sheet layers, cross-linked polyurethane resin The resin sheet has self-healing properties and has an elongation of about 25 oz or more and about 300 oz.
1. A laminated safety glass characterized by being a sheet of crosslinked polyurethane resin having a breaking strength of "kg/cm2 or more".

A method for manufacturing laminated safety glass by laminating one inorganic glass sheet and one pre-laminated sheet, which has self-repairing properties, has an elongation of about 250z or more, and has an elongation of about 300kg/
A pre-laminated sheet consisting of a sheet of cross-linked polyurethane resin having a breaking strength of cm2 or more and a layer of an adhesive material on one side, and one inorganic glass sheet are laminated with the layer of the adhesive material on one side. A method for producing laminated safety glass, characterized by laminating the glass as a laminated glass.

The cross-linked polyurethane resin in the present invention is approximately the same level as or higher than known cross-linked polyurethane resins.
It has two self-repairing properties. In order to be self-healing, the measured value must be approximately 2.5g according to the test described below.
It is necessary that it is above. As described below, the measured value of the crosslinked polyurethane resin in the present invention is approximately 80 to 200 g.
within the range of The above-mentioned Japanese Patent Publication No. 59-48775 discloses that the crosslinked polyurethane resin used therein has a self-repairing 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 tip, etc. may be slightly different. According to other materials (Sangoyon Co., Ltd. technical data), it has been revealed that when the surface of inorganic glass is scratched using the method described in "-", scratches occur at 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 publication, the elongation (referring to the elongation at break) of the crosslinked polyurethane resin used there is approximately 10
0%, breaking strength is approximately 204 kg/cm2
(value converted to tl-position). In contrast, the crosslinked polyurethane resin of the present invention has an elongation of about 250 z 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 is generally used31).
0~1110(ll) elongation and approximately 500~800kg/c
It has a breaking strength of m2. 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. As is clear from Figure 1, the crosslinked polyurethane resin of the present invention exhibits behavior similar to thermoplastic polyurethane resins with excellent mechanical strength, and behaves completely differently from known crosslinked polyurethane resins. .

Polyurethane resins are polyvalent active hydrogen-containing compounds, especially polyols, and polyvalent incyane-1 group-containing compounds (
(hereinafter referred to as polyisocyanate-1 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 and has a molecular weight of about 450 ( hydroxyl radical 374)
It is limited to cross-linked polyurethane resins obtained by reacting approximately equal amounts of polyether triol and a polyisocyanate compound of 1,6-hexamethylene di incyanate in approximately equal amounts. 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.

(2) A relatively high molecular weight active hydrogen-containing compound, especially a polyol, and a low molecular weight active hydrogen-containing compound (hereinafter referred to as chain extender) must be used in combination. 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 polyol with a valence of 3 or higher, and their average hydroxyl value is about 7.
0 to 150, the equivalent ratio of (polyol)/(diol) should be in the range of about 0.1 to 0.6.

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 with a functionality of less than about 2.3, especially less than about 2.1, and the polyisocyanate compound must also have a functionality of less than about 2.3, especially about 2.1. It must be a subfunctional, substantially divalent polyisocyanate 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 0.4
~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.

Incidentally, as a natural premise for producing 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, 0.8 to 1.2 equivalents of the latter is suitable for 1 equivalent of the former. It is. 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 polyol (3) 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.

[OHV] = ([al)/[MW]) X 56. IX
103 [OHV]: Hydroxyl value (mgKOH/g)
[al: Number of functional groups [MW]: Molecular weight The above polyol has a hydroxyl group measurement of 40 to 250, particularly about 80
It is preferable to consist of a combination of a diol having a molecular weight of ~150 and a polyol having a valence of 50 to 300, particularly about 100 to 250, having a valence of 3 or higher. 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, as long as the average hydroxyl value falls within the above range, each polyol may fall 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 are a combination of a diol exceeding the upper limit and a diol below the upper limit, or a combination of a diol having a lower limit of 90 to 100 hydroxyl groups, or a combination of a diol having a lower limit of 90 to 100. The most preferred polyol is a combination of at least two diols having an average hydroxyl value of about 60 to 130 and at least one tri-polyol, especially a triol, having an average hydroxyl value of 150 to 250. Further, the average hydroxyl value in the combination of these diols and the polyol 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. 3 measuring tools for low molecular weight triols etc.”
Although a very small amount of a low molecular weight active hydrogen-containing compound may be used in combination, it usually consists of only divalent compounds. - The amount of chain extender per equivalent of polyol is about 0.7 to 1.
It is most preferable to be a 3rd enemy.

In addition, when the chain extender is a low molecular weight polyol,
The average hydroxyl value of the relatively high molecular weight diol mentioned above, the polyol of 3 measuring tools -1-, and this low molecular weight polyol is not particularly limited, but is about 120 to 2
50, especially about 150 to 220, exhibits the best performance in both mechanical properties and self-healing properties, and is most preferable as a raw material for the crosslinked polyurethane resin in the present invention.

As the relatively high molecular weight diols and trivalent or higher polyols, polyester polyols, polycarbonate polyols, and poly(oxytetramethylene) polyols are selected as the main polyols (that is, as the majority of all polyols). It will be done. Polyoxypropylene polyols cannot be used in large quantities because of the mechanical properties of crosslinked polyurethane resins. 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, both are most preferably used in combination. However, polycarbonate polyols have the problems mentioned above because there are only a few commercially available products; 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. 3
There is currently no commercially available polycarbonate polyol for measuring tools, but of course it can be used if it is available. Therefore, at present, due to viscosity problems and problems in obtaining polycarbonate polyols, the best crosslinked polyurethane resin is a combination of trivalent or higher polyester polyols, polycarbonate diols, and polyester diols. bring. but,
If such restrictions are removed, the combination is not limited to this one. At present, the 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%.
Weight % is appropriate.

Examples of polycarbonate polyols include ethylene glycol, diethylene glycol, dipropylene glycol, and 1,4-butanediol.

Neopentyl glycol, 1,8-hexanediol,
Trihydric or higher polycarbonate polyols using cyclohexane dimetatool or other aliphatic or alicyclic dihydric or higher alcohols may also be used. It is known that polyurethane resins using polycarbonate-1 polyols are applied to laminated safety glass, for example, as disclosed in Japanese Patent Publication No. 55-19249 and Japanese Patent Application Publication No. 49-98818.
No. 1, JP-A-51-144492, JP-A-Sho! 1
It is described in L22197, 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 diol 1.) 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,
Residues such as diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl gelcol, l, θ-hexanediol, glycerin, trimethylolpropane, hexanetriol, and adipic acid, azelaic acid, and sebacic acid. Polyester polyols having residues such as , phthalic acid, etc. are suitable. The latter is preferably a polyester polyol obtained by adding a cyclic ester such as ε-caprolactone (hereinafter referred to as prolactone) or hydroxycaprolactone to a polyhydric alcohol, water, or other polyvalent compound. . In addition, the above-mentioned known examples, especially JP-A-53-
Polyester polyols described in JP-A No. 27871 and JP-A-57-178157 can be used. Furthermore, as general descriptions, the types described in pages 56 to 61 and pages 133 to 188 of [Plastic Comparison Course [2] Polyurethane Resins] published by Nikkan Kogyo Shimbun, etc. Examples include polyester polyols. The most preferred polyester polyols are poly(1,4-butylene adipate) polyol, poly(ethylene adipate) polyol, poly(1,4-butylene azele-1-) polyol, and poly(caprolactone) polyol. It is. As the polyol, particularly the triol, poly(caprolactone)-based polyol is particularly preferred.

In addition to the polycarbonate polyol and polyester polyol, a poly(oxytetramethylene) polyol 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. Polyols other than these (for example, polyoxypropylene polyols and polybutadiene polyols are not normally used, but even if they are used for some purpose, they are preferably not used as the main polyol.Of course, mechanical properties, If there is a polyol that is excellent in terms of weather resistance, water resistance, viscosity, etc., there is no hindrance to its use.

As the chain extender, diols are preferred as mentioned above, such as ethylene glycol, diethylene glycol,
, 3-propanediol, diethylene glycol, 1.
4-butanediol, neopentyl glycol, 1,5
-bentanediol, 1,6-hexanediol, dimethylolcyclohexane, etc. can be used. In place of or in addition to these, dimethylolacetic acid,
Dihydroxycarboxylic acids and diamines such as dimethylolpropionic acid, diaminodicyclohexylmethane, and inphorondiamine can be used. Preferred chain extenders are aliphatic diols having 2 to 6 carbon atoms, especially 1.
4-Butanediol and ethylene gelcol are preferred.

As the polyincyanate compound, divalent non-yellowing diincyanate-1 is used as described above. Specifically, for example, methylene bis(cyclohexyl isocyanate), inholodiisocyanate, 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(cyclohexyl isocyanate) and isophorodiisocyanate. Although the non-yellowing polyisocyanate described in "3 Measurement Tools" in the hanging part can be used in combination, usually only the 211Ti polyisocyanate compound is 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, a hinted phenol compound, a hindered amine compound, a phosphobutyric ester compound, a benzophenone compound, a benzotriazole compound, etc. can be used. In addition, depending on the purpose, colorants, flame retardants,
Use a small amount of mold release agent, adhesive agent, etc. In some cases, small amounts of diluents such as solvents may be used, but are usually unnecessary.

The crosslinked polyurethane resin is manufactured 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, forming a sheet by the casting method is disclosed in Japanese Patent Application Laid-open No. 5
Publication No. 5-105534, Japanese Unexamined Patent Publication No. 513-162618
It is stated in the No. 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 preliminary laminated sheet is preferably selected from thermoplastic polyurethane resins, polyvinyl butyral resins, or EVA resins. EVA resin refers to a resin consisting of a co-electrical resin of ethylene and vinyl acetate or a partial hydrolyzate thereof.

These adhesives have thermoplastic properties and are
When it is suppressed by a surface, it can deform to follow that surface. Therefore, the adhesive layer may have irregularities on its surface and may have a non-uniform thickness to some extent. In order to prevent the formation of bubbles due to residual air on the laminated surface with the 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 pre-laminated sheet and one glass sheet. In the case of flat glass sheets, you can first apply adhesive to the glass surface and then laminate sheets of cross-linked polyurethane resin! However, in the case of bent glass sheets such as those used in automobiles, it is difficult to apply this method. It is also possible to simultaneously laminate a sheet of cross-linked polyurethane resin and a sheet of adhesive onto a glass sheet, but handling the thin adhesive sheet and removing air from the laminated surface is complicated, and the lamination process is complicated. Make it complicated. Therefore, it is most preferable to use the pre-laminated sheet described in -. 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 suppress both sheets. It is also possible to suppress both sheets with just decompression,
Lamination can also be performed only by applying pressure. Specific lamination methods are described, for example, in Japanese Patent Publication No. 12140/1982 and Japanese Patent Publication No. 14074/1982. It is preferable that the adhesive surface of the glass sheet be pretreated in advance to improve its adhesion properties, and a suitable pretreatment agent may be a silane compound such as an alkoxysilane containing an amine group or a glycide group. be.

The thickness of the glass sheet layer in the laminated safety glass of the present invention is suitably about 1 to 10 mm, particularly about 2 to 6+ am. 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 about 0.2 to 2.0+am, especially about 0.000m.
4 to I', 5m++s is suitable. In the case of laminated safety glass used as a window material for automobiles, the thickness is particularly preferably 0.6 to 12 mm. The thickness of the adhesive layer is less than about 0.2 mm, 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 part m is appropriate.

The laminated safety glass of the present invention is most suitable as a window material for automobiles, especially as a windshield. However, 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, but the present invention is not limited 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: Scratch the surface of the cross-linked polyurethane resin with a diamond tip of Ogmφ under a load, and
It is expressed as the maximum load at which scratches caused by C can disappear within 10 minutes. Disappearance of scratches was visually observed. 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 KB301.

Light transmittance, taper wear: According to JIS K8301.

Penetration resistance: Based on JIS R3212. 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: Poly(1,6-hexane carbonate) diol 4' having a hydroxyl value of about 122, 3.86 parts [parts by weight, the same applies hereinafter], a hydroxyl value of about 90.5 Poly(caprolactone) diol 88
．． After heating and melting 93 parts of poly(caprolactone) triol having a measured hydroxyl group of 185.2 at 100° C., the mixture was stirred and mixed while being dehydrated and degassed under reduced pressure. After cooling this polyol mixture to 80°C, diptyltin diurarate [hereinafter referred to as catalyst] fl, o'X
10-3 parts, 1,4-butanediol 1o, 'c+2
and 4,4'-methylenebis(cyclohexyl isocyanate) [hereinafter referred to as HI2 MDI] 84
．． 5 parts were sequentially added and mixed with stirring. An exotherm was observed at the beginning of the reaction. 80° when the system becomes homogeneous
Degassing was carried out under reduced pressure while stirring at C for 3 minutes. A glass sheet (500 x 500
15mm cast in a 120”C nitrogen purged furnace.
The reaction was carried out for a period of time to obtain a transparent sheet having a thickness of 0.7 mm+ and 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. This cross-linked polyurethane resin sheet has an elongation of 374z and a breaking strength of 771k.
g/c+a, and tear strength was 30 kg/am. A crosslinked polyurethane resin sheet was produced in the same manner as described in Section 2, except that the raw materials were changed. Name of each sheet (A
-2 to A-4), its raw materials, sheet thickness, and average hydroxyl value of polyol (not including button extension agent) are shown below.

43.53 parts of poly(1,6-hexanecarbon-1.) diol with a hydroxyl value of approximately 54.5'2 Poly(caprolactone) diol with a hydroxyl value of approximately 70.79
[18,41 parts Poly(caprolactone) triol with a hydroxyl value of about 195.2
12.44 parts catalyst
6. OXl0-3 part 1,4-butanediol
12.44 part HI2MDI
63.18 parts Average hydroxyl value of polyol
88.5 Sheet thickness 0
．． 7mm elongation
415% breaking strength 8
55kg/cm2 tear strength 3
8kg/cm poly(1,Ei-11 xane carbonate) diol with a hydroxyl value of approximately 57 [13,07 parts poly(caprolactone) diol with a hydroxyl value of approximately 80.5
99.12 parts Poly(caprolactone) triol with a hydroxyl value of about 195.2 1
8.02 parts catalyst
8.25X 10-3 parts 1,4-butanediol
14.42 parts H12MDI
80.37 parts Average hydroxyl value of polyol
89.25 Sheet thickness 1 m
m elongation
474z breaking strength 8
55kg/cm2 tear strength 3
Poly(1,6-hexane carbonate) diol with 3 kg/am hydroxyl value of 54.52 35. Bl1
Part Suichu Poly(caprolactone) diol with 90.79 hydroxyl groups 124.87 parts Hydroxyl value approx. 1
95.2 poly(caprolactone) triol
17.84 parts catalyst
8.25X 10 3 parts 1,4-butanediol 14.27 parts H17MDI
82.34 parts Average hydroxyl value of polyol 84.0 Sheet thickness
1.1mm elongation
495χ breaking strength
[190kg/cm2 tear strength
35kg/cm [Comparison sheet] Poly(1,6-hexane carbonate 1.) diol with a hydroxyl value of 122 52.86 parts Hydroxyl value approx. 8
0.5 poly(caprolactone) diol
79.30 parts catalyst
e, o 3 parts of XIO 1,4-butanediol 10.57 parts H+2Ml]I
83.8? Part A-1 using the above raw materials
A sheet with a thickness of 1 mm was manufactured by the same casting method as the crosslinked polyurethane resin sheet. The obtained thermoplastic polyurethane resin sheet had a dish-like surface, and could not be optically applied to laminated safety glass at all. The elongation of this cross-linked polyurethane resin sheet is 69 oz.
Breaking strength L1400kg/cm2, tearing strength 41kg
/c+a.

(mahydric acid), (poly(butylene adipate) with a measurement of 90.5)
Diol 87.09 parts Hydroxyl value approx. 90
．． 5 poly(caprolactone) triol
87.09 parts catalyst
8.25X 10-3 parts 1,4-butanediol 1[1,45 parts H+2MDI
93.37 parts A sheet having a mirror surface and having a thickness of 1.1 mm+ sheet was obtained in the same manner as the A-1 sheet. In addition, the average hydroxyl value of the polyol is 142.9
(However, the contact ratio of triol/diol is 1.44
). This cross-linked polyurethane resin sheet had an elongation of 23 oz, a breaking strength of 380 kg/cm2, and a tear strength of 27 g/cm.It is a known cross-linked polyurethane/tan resin sheet with self-healing properties. (thickness 0.13+n+*') was input. This cross-linked polyurethane resin sheet]
It is recognized that it is a cross-linked polyurethane resin sheet described in Publication No. 75 (for the composition, refer to the examples of the Japanese Patent Publication No. 55-Et65) (according to the results of physical property measurements, chemical analysis, etc.). Butylene Adipe-1.) Diol 3B, poly(caprolactone) triol with a hydroxyl value of about 54 in the OO part
36.00 parts catalyst
? , 2 Xl0-3 parts 1,4-butanediol 9.71 parts H+2MDI
A block of thermal t+7 Qj polyurethane resin was produced by a prepolymer method using the raw materials listed in "38.29 parts". 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 48o
z, breaking strength f (45 kg/cm2, tear strength 98k
g/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 of A-1 to A-4 and the sheets of X-3 and X-4 are shown in FIG.

Example [Manufacture of laminated safety glass 1 A preliminary laminated sheet having an adhesive layer with a thickness of about 0.20 m+a is obtained by applying an ethanol solution of polyvinyl butyral resin to one side of the crosslinked polyurethane resin sheet of A-1 and drying it. 17 were manufactured. A glass plate (3 x 5
00 x 500 mm) 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 and the bag will contain about 1 mm and 1 g.
Depressurize to.

It was kept in an oven at 120°C for 10 minutes.

The laminate was then removed from the rubber bag and heated to 130°C.
, Heat-compression bonding was carried out for 30 minutes in an autoclave at 110 kg/cm 2 and allowed to cool. The obtained laminated safety glass is shown below as B.
Call it -1. Using the same method, a laminated safety glass called 8-2 was manufactured from the sheet of A-2, a laminated safety glass called B-3 was manufactured from the sheet of Al1, and a laminated safety glass called B-4 was manufactured from the sheet of A-4. did.

[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-] to B-4.

Table 1

[Brief explanation of drawings]

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. Koto 1 Zushinhi (24) Procedural amendment written in 1986 > Date

Claims (1)

[Claims] 1. A laminated safety device comprising one inorganic glass sheet layer, a crosslinked polyurethane resin sheet layer provided on one side of the inorganic glass sheet layer, and an adhesive material layer that adheres both sheet layers. In glass, sheets of cross-linked polyurethane resin have self-repairing properties, elongation of approximately 250% or more, and approximately 30% elongation.
A laminated safety glass characterized by being a sheet of cross-linked polyurethane resin having a breaking strength of 0 kg/cm^2 or more. 2. A method for manufacturing laminated safety glass by laminating one sheet of inorganic glass and one pre-laminated sheet layer, which has self-healing properties, has an elongation of about 250% or more, and has an elongation of about 30%.
A pre-laminated sheet consisting of a sheet of cross-linked polyurethane resin having a breaking strength of 0 kg/cm^2 or more and a layer of an adhesive material provided on one side, and one inorganic glass sheet are combined with the layer of the adhesive material. A method for manufacturing laminated safety glass characterized by laminating it as a laminated surface.