JPS58213661A - Preparation of laminated safety glass - Google Patents

Abstract

PURPOSE:To obtain a two-layer glass having improved bonding and surface characteristics without using a thermosetting resin, by contact heat bonding an unmodified surface of a thermoplastic resin layer having one surface modified with light or moisture directly or indirectly to a rigid substrate. CONSTITUTION:A laminated safety glass has at least the two-layer structure of a thermoplastic resin layer and a rigid substrate layer and may consist of a multi-layered structure in both the thermoplastic resin layer and the rigid substrate layer. A thermoplastic resin 2 having a surface (A) modified with light or moisture and an unmodified surface (B) alone or in combination with the second thermoplastic resin 3 is contact heat bonded to a rigid substrate 4, e.g. glass, by using the surface (B) as a fusing surface with mold materials 1 having smooth surfaces. Thus, the aimed transparent or semitransparent safety glass having the thermoplastic exposed to the surface and another glass surface and improved bonding and surface characteristics is easily obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for manufacturing laminated safety glass having at least a two-layer structure of a thermoplastic resin layer with an exposed surface and a hard substrate layer, and is particularly suitable for manufacturing a laminated safety glass that is not modified by light or moisture. The present invention provides a method for manufacturing laminated safety glass with excellent surface characteristics by thermocompression bonding a thermoplastic resin having a textured surface and a glass sheet.

Laminated sheets of glass sheets and synthetic resin sheets are well known as laminated safety glass. For example, a laminated sheet h consisting of a three-layer structure of glass-polyvinyl butyral-glass
is widely used as safety glass for automobiles. Synthetic wood 111 laminated between such glass sheets
One layer is called an interlayer film, and polyvinyl butyral, polyurethane, and various other synthetic resins are used or proposed. On the other hand, in laminated safety glass made of glass and synthetic resin, the synthetic wood is exposed with a saw M.
Layer sheet, / so to speak, glass-synthetic resin or glass-synthetic resin-gas? The product, such as synthetic resin, which has one side of glass and the other side of synthetic resin, is attracting attention for use in safety glass for automobiles. This laminated safety glass is considered to be even safer than conventional laminated safety glass, which is glass on both sides. For example, if this laminated safety glass is used as a front/window glass for vehicles with the synthetic resin side facing the inside of the vehicle, there will be fewer lacerations and cuts if a driver etc. collide with the 710 glass. It is thought that this will reduce the chance of glass fragments being scattered inside the car even if the glass is broken. Laminated safety glass like this, where one side is glass and the other side is synthetic resin,
Hereinafter referred to as [Pielayer glass].

About pie layer glass (cutting, analogy 'i I'?
Kaisho Kaimei No. 41423, JP 48-25714
No. 49-34910, and Japanese Patent Application Publication No. 8-53-276'71. As shown in these prior art examples, the exposed synthetic resin layer (hereinafter referred to as a pie layer) is usually made of polyurethane. Polyurethanes are also well known as interlayers in laminated glass.Polyurethanes include so-called thermoplastic polyurethanes and thermoset polyurethanes, the former being linear polymers, usually containing high molecular weight diols, chain extensions and diisocyanate compounds. obtained by reacting
The latter are crosslinked polymers, such as high molecular weight diols, crosslinkers, and fM agents.

and a diisocyanate compound. The first layer of pie layer needs to be strongly adsorbed to the glass. When Totoro uses a single layer of heat-cured polyurethane, there is a problem that it does not adhere firmly to glass.

On the other hand, heat radiation II' (the polyurethane is strongly bonded to the glass J, but as a pie layer) as far as the citation is concerned.
- Since the tx plane is exposed, the properties of the surface change.

That is, thermal OTV and d-type polyurethanes have insufficient weather resistance and are easily attacked by solvents. These problems are explained in detail in JP-A-53-276714, particularly on pages 6 to 7 of 1g.

- In order to solve the problem of one-layer structure, in the invention described in JP-A No. 55-27671, two layers of polyurethane occupy one layer, the surface is made of thermosetting polyurethane, and glass is used. This problem has been solved by using thermoplastic polyurethane.Since both polyurethanes 1d strongly adhere to each other, this invention solves the problem of adhesion of the pie layer to glass and surface properties.

It cannot be considered that all the problems were completely solved by the invention of Shikijina-/Bara. First of all, the invention requires the production of two polyurethane notebooks (a preformed sheet and a polyurethane sheet).
Tore requires a relatively complicated process. Even if it's only 1,
As described, page 10, lower right column, line 13, 1] to page 11, upper right column, line 14, 1C, one sheet may be poured onto the other to integrate it, or one sheet may be dissolved in a solvent. For peace of mind, try applying it to the surface of the curved blade.

Second stage: The illumination point is a plane because thermosetting polyurethane loses its plasticity after curing. first,
The methods of forming thermosetting polyurethane sheets and films are limited (casting and curing is almost the only method), and there are extrusion molding, press molding, and other molding methods suitable for forming notebooks and films. For this reason, smooth sheets or films of uniform thickness are advantageous. If it has a flexible 17θ property, it can be compressed with a mold with a smooth surface to produce a smooth force surface of 1", but this is also difficult. Of course, this is also due to the lack of adhesive properties. Sixth, thermosetting polyurethane has a problem in that it does not have sufficient physical properties (for example, decoration 1 penetration and rigidity) that are required for pie layer glass, compared to thermal radiation polyurethane. be..

In the above invention, many problems such as /); have not yet been resolved, surface I! '￥Excluding 1 and 1 between sex, pa V,
Pilayer Glass's Pilayer 1 As the emperor, 1 is heat 1
It is believed that thermoplastic resins, especially polyurethane thermoplastic resins, are the most excellent.

The present inventor modified the surface of the layer of thermal 'oJ plastic 1 raw resin to obtain surface 11! It has been found that it is possible to improve the f properties and thereby produce a good pie layer glass without substantially using thermosetting polyurethane. The modified surface of the thermoplastic resin becomes an exposed surface, and the unmodified surface becomes a fusion surface and is fused to the hard substrate. Surface modification is carried out by crosslinking functional groups that are layered onto the surface and can be crosslinked with light or moisture. Even if it has these functional groups, if it is not crosslinked, it is not a modified surface. Under this definition, the present invention defines a modified surface (also referred to as a modified surface). A method for producing transparent or translucent laminated safety glass such as Pylayer glass by thermocompression bonding using a sheet or film of thermoplastic resin having two surfaces: a non-modified surface (also referred to as an unmodified surface). It is. That is, the present invention provides a method for producing transparent or translucent laminated safety glass having at least a two-layer structure of a thermal 5T plastic resin layer with an exposed surface and a hard W base layer, which is modified by light or moisture. A thermoplastic resin having a surface on one side and a hard substrate are bonded by thermocompression, using the unmodified surface of the thermoplastic resin as a fusion surface, either directly or via a second thermoplastic resin. This is a manufacturing method for laminated safety glass.

The ft i safety glass in the present invention has at least a two-layer structure. The thermal 5T plastic resin layer may have a multilayer structure, and the hard base layer may also have a multilayer structure like the laminated glass made of glass-synthetic resin-glass. Thermocompression bonding involves assembling at least one sheet or film of heat radiation + l'Q resin and a hard substrate (hereinafter referred to as a solid substrate), and then simultaneously or in the case of a multilayer structure of six or more layers. This is done by sequentially applying heat and pressure. ) Figures 1 to 4 are schematic cross-sectional views showing the gate configuration during thermocompression bonding. In FIGS. 1 to 4, the mold material (1) is made of a material with a smooth surface such as a glass sheet, and the surface is preferably treated to make it non-adhesive. The other mold material is normally not necessary since the hard base itself acts as a mold material, but it may of course be used if necessary. The thermoplastic resin (2) with a modified surface (G) and an unmodified surface (B) can be used not only alone (Figure 1), but also with a second thermoplastic resin (3). They can also be combined (Figure 2). Further, the thermoplastic resin (2) may be a multilayer structure that is laminated in advance (FIG. 3).

The hard substrate (4) such as a glass sheet may consist of one layer or may have a multilayer structure (Pl'l;
Figure 4). In the latter case, the production of a hard substrate with a multilayer structure may be carried out simultaneously with this thermocompression bonding. For example, as shown in FIG. 5, a synthetic resin such as butyral resin ( 7) can be placed and thermocompression bonded at the same time.

Thermocompression bonding is a preliminary compression bonding process in which the snow layer is depressurized and degassed under heating at room temperature to 100℃ or less in order to remove air, etc. that exists between the hard substrate and the one-dimensional resin that is normally exposed to heat. This step and the main compression bonding step of thermocompression bonding the laminated assembly under heat and pressure are carried out seven times. For example, a thermoplastic resin may be layered on a hard substrate with the modified surface of the resin facing outward, or a thermo5T plastic resin having a modified surface may be placed on a hard substrate via a second thermoplastic resin. Then, on the modified surface of this thermoplastic resin, a mold material with a smooth surface, such as a mold-released glass sheet, rubber sheet, plastic sheet, metal sheet, etc., is placed on top of the modified surface. The laminate assembly is placed in a rubber pre-crimping device, the inside of the crimping bag is evacuated and pre-crimped, and then the pre-crimped laminate is placed in an autoclave with or without removing the shapes. Thermocompression bonding is performed by a method of performing main compression bonding with heat and pressure 1-. Such preliminary crimping is
Continuous pre-crimping equipment is approximately 700cm H7 or less, for example 20cm
After reducing the pressure to 0 to 650 mmHf, heat at approximately 100°C for 1 trial.
For example, heating is carried out at room temperature to 90°C. Mapuko,
The main crimping is usually carried out at a temperature ranging from about 60°C to melting of the thermoplastic resin, for example, if the thermoplastic resin is a polyurethane thermoplastic resin, the temperature is about 80 to 150°C.
The pressure is 2 K7/cJ or higher, for example, in the case of polyurethane thermoplastic resin, the pressure is about 7 to 20 Kg/-,
It is preferable that the process be carried out in These conditions can vary depending on the type of thermoplastic resin and hard substrate, the thickness and size of each constituent unit, and other factors.

The above-mentioned preliminary crimping is not limited to the method using the preliminary crimping device as described above. For example, a method for pre-crimping the laminated assembly by passing it between rolls and pressing it with a roll, a method for pre-pressing the laminated assembly by pressing it with a platen,
The laminated assembly is placed in the inner vacuum chamber of a decompression device having double vacuum chambers, and the outer vacuum chamber is evacuated first, then the inner vacuum chamber is evacuated, and then the outer vacuum chamber is released. It can also be carried out by a double vacuum crimping method in which crimping is performed at atmospheric pressure. Similarly, single crimping is not limited to thermocompression bonding in an autoclave; for example, the laminated assembly is placed in a heated oil tank and pressurized, or the laminated assembly is passed between rolls under heat and rolled. The bonding can also be carried out by a method of pressing, a method of pressing the laminated assembly under heat, a method of performing the above-mentioned double vacuum pressure bonding method under heat, and the like. In addition, during thermocompression bonding, especially in the pre-compression bonding process, it is preferable to place the above-mentioned mold material on top of the thermoplastic resin to ensure sufficient crimping and to obtain a smooth surface, but the crimping method Depending on the type and purpose, the use of such a mold material may be omitted. In addition, thermocompression bonding between a thermal radiation 1-1 resin and a hard substrate is most commonly carried out through a preliminary compression bonding process and a main compression bonding process. Depending on the conditions such as the type of material and the thickness and size of each component, thermocompression bonding may be performed in one step without going through the preliminary pressure bonding step and the seven pressure bonding steps.

The exposed surface of the thermoplastic resin is modified before the thermocompression bonding described above is performed. As will be described later, the modification is carried out by crosslinking functional groups that can be crosslinked with light or moisture introduced onto the surface of the thermoplastic resin with light or moisture.

That is, a thermoplastic resin having a photocrosslinkable group on its surface is irradiated with light, and a thermoplastic resin having a moisture crosslinkable group on its surface is immersed in water, a method of applying water,
Crosslinking is carried out by placing the material in an atmosphere containing moisture. The only surface that is modified is the exposed surface of the laminated safety glass. It is preferable that the other surface, that is, the welding surface, be substantially unmodified since modification may cause a decrease in adhesive strength. A functional group that can be crosslinked by light or moisture may be present on this 4tQ surface. However, when modifying one surface, the crosslinkable functional groups on the other surface are also easily crosslinked, so this functional group may be substantially absent on the surface that will become the fusion surface, or there may be less of this functional group than on the other surface. Less is preferable. This surface modification provides a surface with excellent surface properties such as weather resistance and solvent resistance.

In the present invention, the hard substrate is a sheet material harder than a thermoplastic resin, such as a sheet of inorganic glass (hereinafter simply referred to as glass), a sheet of polycarbonate, polymethyl methacrylate, or other organic glass. These hard substrates may have a single layer structure or may have a multilayer structure as described above. In the case of a multilayer structure, the thermoplastic resin is thermocompressed and the surface of the exposed outermost layer is made of a hard material, but the space between the two hard materials may be made of a soft material such as butyral resin. . In the case of a glass sheet, it may be strengthened by air-cooling strengthening or chemical strengthening, and the glass sheet may also be colored or have a thin layer such as a heat ray reflective film. In the case of an organic glass sheet, it may be subjected to a treatment such as a stretching treatment, and may have a thin layer such as a hard coat layer. Additionally, the organic glass notebook may be colored or patterned, and may even have partially opaque areas. These hard substrates 1-i are preferably transparent to semitransparent as a whole, and particularly preferably have excellent optical properties. The 1v value of the entire hard base layer is 0.
5 vn or more, especially about 1 to 50 ++ s is preferable.

This 11-cellulose substrate may be of course a flat plate, or may be molded into various shapes used for front windows or rear windows of automobiles. Furthermore, depending on the purpose, it may be something like a lens with variable thickness. Particularly preferred rigid substrates are transparent or colored transparent glass sheets having a single or multilayer structure.

In the present invention, the thermoplastic resin is made of a synthetic resin that is softer than the hard substrate. This thermoplastic resin is made of a transparent to translucent material, but the sheet or film itself may be opaque (for example, one with minute irregularities on the surface) that can eventually become transparent to translucent. . The thermoplastic resin may be colored or may have partially opaque areas. If the exposed surface? As described later, the most preferable thermoplastic resin is a polyurethane-based thermal i3J91 resin, but various thermoplastic resins can be used as the thermoplastic resin that does not form the exposed surface.

However, even if the thermoplastic resin does not have an exposed surface, if the physical properties of the pie layer mainly depend on that layer,
That is, when the layer is particularly thin compared to other thermoplastic resin layers, it is preferable that the thermal radiation plastic resin is a polyurethane thermoplastic resin. 11 layers of thermoplastic resin
If only, thermoplastic notes are used.

In the case of a multilayer structure of thermoplastic resin layers, sheets or films can be used. In the present invention, the sheet is 0.
21 or more, and the film refers to a film with a thickness less than 21. Therefore, for example, a thermoplastic resin layer can be constructed using a polyurethane thermoplastic resin film having a modified surface on one side and a single polyurethane thermoplastic resin sheet. The thickness of the entire thermoplastic resin layer is not particularly limited, but is 0.2 - or more, especially 0.
．． Preferably, the temperature is 4 to 10 degrees. In the present invention, the thermoplastic resin is preferably a polyurethane thermoplastic resin. Pond's heat oJvyii raw resins include polyester resin, butyral resin, polydiene resin, ethylene-
Vinyl acetate-based copolymers, polyolefin-based elastomers, and other relatively soft thermoplastic resins and thermoplastic elastomers can be used.

However, polyurethane-based thermoplastic resins are most preferred from the viewpoint of transparency, KI impact resistance, 4-pass resistance, and other physical properties. A polyurethane-based thermoplastic resin is a thermoplastic synthetic resin having a large number of urethane groups. In addition to urethane groups, this synthetic resin has urea groups, allophanate groups,
It may have a group formed by a reaction between a billet group or other active hydrogen-containing group and an isocyanate group. Also,
Isocyanurate group, carbodiimide group 1. It may also have groups derived from other isocyanate groups. Furthermore, the ester group that the polymer ridge polyol itself has,
It may of course contain an ether group, a carbonate group, or other groups, but it may also contain groups resulting from compounds such as chain extenders and crosslinking agents. In addition, as will be described later, the surface of the polyurethane base, which will be exposed, has a functional group that can be elevated by light or moisture. .

It is preferable to have an active di-, 1-, such as a carboxylic acid group or a tri-amino group, which can be packed with compounds having such functional groups.

Polyurethane thermoplastic resin is basically a polymer i! It is a linear polymer that is reacted with a diol, a chain extender, and a diisocyanate compound. However, a small number of branches may be present, for example, a large proportion with a small number of branches obtained by using a trifunctional or higher functional polyol, a crosslinking agent, or a polyisocyanate in combination with the above bifunctional compound. may be a linear polymer.

A thermoplastic polyurethane resin is obtained by using the three main raw materials of the polymer, a diol, a chain extender, and a diisocyanate compound, as well as various auxiliary raw materials if necessary. A catalyst is usually required as an auxiliary feedstock. Depending on the purpose, crosslinking agents, colorants, stabilizers, ultraviolet absorbers, anti-wrinkle agents, and other additives may be used as auxiliary raw materials.

As the polymer rigid diol, polyester diol, polyether diol, polyether ester diol, polycarbonate diol, and other polymer layer diols can be used, and in particular, 1) ester diol obtained from a dihydric alcohol and a dihydric carboxylic acid compound. Alternatively, polyester diol obtained by ring-opening polymerization of a cyclic ester compound is preferable, such as poly(1°4-butylene adipate), poly(ethylene adipate), poly(1
, 3-butylene azelate) poly((-caprolactone), etc.), water, dihydric alcohol, 2
Polyether diols and polycarbonate diols obtained by adding epoxides such as alkylene oxides, or other cyclic ethers having four or more members to hydric phenols and other initiators are also often suitable for polymerization. These polymer layer diols are suitably low 1tNk point compounds that are liquid at room temperature or VC liquid during reaction, and the molecular weight is not particularly limited, but 60
0-8000.

In particular, it is preferably 800 to 4000.

Chain extension 1, 4. The shavings are divalent compounds with relatively low molecular weight, such as diols, diamines, divalent alkanolamines, and other compounds having two hydroxyl groups or amine groups. Although it is not limited to the length of each molecule, it is preferably 300 or less, particularly 150 or less.

As the diol, dihydric alcohol 1. Mylyester diol, polyether diol, etc. can be used, and dihydric alcohols having 2 to 2 carbon atoms are particularly preferred. As the diamine, 1d aliphatic, alicyclic, aromatic, and other diamines can be used. As an alkanolamine, for example, N
- Divalent alkanolamines such as alkyl jetanolamines can be used. In the combination of these macromolecular diols and chain extenders, divalent compounds such as diols having a molecule M intermediate between the two may also be used in combination. Of course, two or more compounds of the polymer diol and the chain extender can be used in combination.

Diisocyanate-1 Compounds include aliphatic, alicyclic, aromatic, and other diisocyanates.

It is also possible to use two or more of these modified proboscises. Since an incyanate group directly bonded to an aromatic nucleus has the potential to cause a change in the resulting polyurethane, a diisocyanate without such an incyanate group, a diisocyanate that is usually called a non-deformed type, is preferred. For example, preferred diisocyanates include hexamethylene diisocyanate, notylene bis(ncrohexyl iso7anate), cycloheginylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and modified diisocyanates obtained by modifying these with various compounds or treatments.

In the present invention, a functional group that can be crosslinked by light or moisture is introduced into one side of the thermoplastic resin sheet or film constituting the exposed portion.

In order to introduce this functional group, it is necessary for the thermoplastic resin to have a highly reactive group (i), and it is particularly preferable to have a highly reactive group in advance.For example, polyurethane thermoplastic resin has carboxylic acid groups, It is preferable to have a class amine group or other highly reactive group.Of course, even if there is no such group, it is possible to use an active group that the substance itself has, such as a urethane group. However, considering the ease of introducing functional groups that can be crosslinked by light or moisture, it is preferable to use m groups with high reactivity during the production of boron-1-notane. Taking a carboxylic acid group as an example, a polymer layer diol having a carboxylic acid group and a chain extension chain having a carboxylic acid group 11 fi
Polyurethane having carboxylic acid groups can be produced using any of the main raw materials having carboxylic acid groups, auxiliary raw materials such as crosslinking agents having carboxylic acid groups, and other compounds having carboxylic acid groups. These compounds having a carboxylic acid group can be used in place of all of the above-mentioned polymer layer diols and Hanenbokuyaku, but they are usually used in combination with them. A carboxylic acid having a hydroxyl group such as dimethylolpropionic acid which can be used as a chain extender having a carboxylic acid group is preferably used in combination with a dihydric alcohol which is a usual chain extender. In addition, in cases where there is a risk that the carboxylic acid group may be converted into a carboxylic acid group in the reaction for producing polyurethane, or where there is a risk that the carboxylic acid group may react, a group that can be converted into a carboxylic acid group later may be used. It is also possible to adopt a method in which a polyurethane is produced using a compound having the following, and then the group is changed into a carboxylic acid group.

Polyurethane thermal 0T plastic resin can be produced using the above-mentioned raw materials by one-shot method, prepolymer method, quasi-prepolymer method,
It is manufactured by various other methods. Not only can sheets or films be formed directly by these methods, but also sheets or films can be formed from the resulting polyurethane solution or powder to granular polyurethane. For example, it can be made into a sheet or film by a casting method, an extrusion molding method, an injection molding method, a press method, or other methods. Next, a functional group capable of crosslinking with light or moisture, or a functional group capable of crosslinking with 14A, is introduced onto one side of the sheet or film.

For example, in the case of polyurethane having the above-mentioned carvone stage, an alkoxysilane having an epoxy group on its surface,
For example, alkoxysilyl groups are introduced by coating and reacting γ-glycidquinprobyltrimethoxysilane or a coating solution containing it. Alkoxysilyl groups do not quickly crosslink in a short time when exposed to moisture in the air, but when actively hydrolyzed by heating in water, silanol groups are generated, and these silanol easily undergo a dehydration reaction. crosslink. Moisture crosslinking of alkoxysilyl groups 1 is thought to occur through two reactions: this hydrolysis reaction and a crosslinking reaction due to dehydration of the silanol groups produced. Therefore, in the case of an alkoxysilyl group which is a moisture crosslinkable group,
For example, as described above, an alkoxysilyl group is hydrolyzed by immersing a polyurethane thermoplastic resin sheet or film having this group in water, applying water, or placing it in the presence of moisture, Crosslinking is achieved by carrying out a dehydration reaction with the ash by heating under normal pressure or reduced pressure, or at room temperature. This crosslinked surface is the modified surface in the present invention, which is heated to 1 f
ui: This is substantially one side of a sheet or film made of a polyurethane resin, and is an exposed surface. The above-mentioned crosslinkable functional group can be introduced into one or both sides of the thermoplastic resin sheet or film, but is preferably introduced into only the piece 11M as described above. Even if this crosslinkable group is introduced on both sides, by crosslinking only one side, it is possible to obtain a thermoplastic resin having a modified surface on one side.

As shown in FIG. 5 1 above, when the thermoplastic resin has a multilayer structure, a layer of thermoplastic resin having a modified surface (b) is added to the crosslinkable resin as described above. An example of how to easily introduce functional groups? It is possible to use a polyurethane thermoplastic resin having more carboxylic acid groups, and the layer having the other surface to be a normal polyurethane thermoplastic resin having no active group. This multilayer structure can be produced by crosslinking the surface and then laminating it, or by introducing a crosslinking group on the surface, then laminating and then crosslinking, but usually these two types of polyurethane-based After laminating the plastic resin, crosslinking is performed by introducing a crosslinkable group.

The second thermoplastic resin is preferably a polyurethane thermoplastic resin as described above, but if it is thin and does not primarily affect the physical properties of the pie layer, it may be a butyral resin, polyester resin, or other resin. It may also be a hard-wearing resin other than polyurethane. This second thermal 0T plastic resin may be a multilayer structure, and a plurality of notebooks or films thereof may be used and thermocompression bonded simultaneously at the time of thermocompression bonding. In addition, sheets and films of thermoplastic resins with a multi-story structure, including thermoplastic resins having a modified surface and a non-modified surface, are bonded with thermosetting resin between each layer. It may also have a thin layer of thermosetting resin such as an agent.

The transparent to translucent laminated safety glass obtained by the present invention can be used as a window material for automobiles, 7-10 vehicles, or 1R.
, +3 Suitable as a window material for H'Wk. but,
Its uses are not limited to these, but it can also be used in various uses that require transparency and physical strength, such as eyeglass lenses.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples 1a only.

Reference example [A] Bolib'tyrene adipate 15002 with hydroxyl group Tsukuda 15
was dehydrated at 110° C. for 2 hours under vacuum at 3wnH9, -ff.

This was added to 6-isocyanatomethyl, 35'5'-trinotylcyclohexyl isocyanate 9082 and di-
n-Butyltin dilaurate 0162 was added and reacted for 15 minutes at 80°C under a nitrogen stream. Next, 2442 of 1.4-butanediol and 759 of dimethylolpropionic acid were added to this reaction mixture, and the mixture was rapidly stirred and mixed. An exotherm was observed with the onset of the reaction and a substantially homogeneous mixture was obtained. This liquid reaction mixture was poured into a Teflon-coated vat and reacted at 110° C. for 12 hours. The produced polymer was pulverized and granulated using a pulverizer, and then formed into a film using an extruder. Next, on one side of this film, glycidyl cinnamate 502 triethylamine 15f
, 2.2 dimethoxy72-phenylacetophenone 5t,
A solution consisting of 500 g of benzene was uniformly applied, and the mixture was directly transferred to a nitrogen purge oven at 110° C. and reacted for 1 hour.

BI Polyethylene adipate 1500 with hydroxyl value 56.7?
, 4.4'-methylene-bis(cyclohexyl isocyanate) 781, di-n-butyltin dilaurate 0
．． A film was prepared by reacting in the same manner as in Reference Example A using 45r, 1,4 butanediol 144f, and dimethylolpropionic acid 751. A solution made from glycy-gamma-dyl methacrylate 502, N-N' dimethylaniline 151, benzoin methyl ether 57, and benzene 500ii' was uniformly applied to one side of the film, and the film was transferred to a nitrogen-purged oven at 110°C and reacted for 30 minutes. Ta.

[C]

Polybutylene adipate 1500 with a hydroxyl value of 543? ,
4.41-methylene-bis(cyclohexyl isocyanate) 642S', di-n-butyltin dilaurate 0
35? , 1.4-butanediol 1212, and dimethylolpropionic acid 457 were reacted in the same manner as in Reference Example A to prepare a film. One side of this film was coated with 1% N of γ-grid
, N-dimethylaniline was applied very thinly and uniformly, and the mixture was directly transferred to a crab purge furnace and reacted at a temperature of 110° C. for 30 minutes.

CD) Polyethylene adipate 1500f, 4 with a hydroxyl value of 56
．． 4-methylenebis(cyclohexyl isocyanate)
11737.1.4 Butanediol 327 f, di-n
A film was prepared by reacting in the same manner as in Reference Example A using 0.18 f of -butyltin dilaurate. On one side of this film, γ-isoanate propyltrimethoxysilane 507 lead octylate o, 5v, benzene 5
Uniformly apply a solution consisting of 002 at -1 to 110℃
The mixture was transferred to a nitrogen purged furnace and reacted for 1 hour.

Example 1 Using the film having a thickness of 06flIII+ produced in Reference Example A, glycidyl cinnamate was treated.

Light was irradiated from a distance of 5 rrn for 5 minutes using a 100 W high mercury lamp from the treated surface. After this, the film was placed between two glass plates. At this time, polydinotylsiloxane was uniformly coated in advance on a piece of glass that was in contact with the light-treated surface of the film, and heat-treated at 350°C. This non-adhesive glass laminate was placed in a rubber bag, and the rubber bag was placed in an autoclave. First, both the rubber bag and the autoclave were emptied to remove the air between the glass and the film. Next, the autoclave was heated to 100°C, and the inside of the autoclave was returned to atmospheric pressure while keeping the inside of the rubber bag 1° empty, thereby applying a pressure of I kg/J. After keeping this state for 15 minutes, autoclave 14
The conditions were set to 0°C and 13 Kq/J and held for 20 minutes. After removing the glass layer from the autoclave, the glass treated with polydimethylsiloxane is rinsed, resulting in a layer with a glass-like smooth surface and good adhesion to the glass. Glass was obtained. For the film surface of this bilayer glass,
Artificial ethanol/methanol = 1 o/1 (v/v) Dye each of felt with moxibustion tetrachloride, kerosene, and gasoline,
A rubbing test was conducted, but no change was observed even after rubbing 1000 times. In addition, in the Taber test based on JISR3212, the increase in haze after 100 times was 25
%Met. In addition, in a falling ball test based on the same < JISR3212, one ball did not lose layer weight and showed sufficient gastric permeability.

Example 2 Using the film made in Reference Example B with a thickness of 0.6 mm, a pie layer glass was made by the same method as in Example 1 after being irradiated with light. Increase in haze after rotation is 2.3%
Other than that, the same performance as in Example 1 was shown in the rubbing test and falling ball test shown in Example 1.

Example 3 The film with a thickness of 0.6 mm produced in Reference Example C was
It was immersed in hot water at 0° C. for 30 minutes, then transferred to a dryer at 120° C. and dried for 15 minutes. Thereafter, pie layer glass was prepared by the same method as in Example 1. The film surface of this Pylayer glass was glass-like and smooth, and no optical distortion was observed. In addition, adhesion to glass was also good. For this pie layer glass,
When the same trial run as in Example 1 was conducted,
In the rubbing test, no change was observed even after 1000 times. Further, in the taper test, the increase in haze after 100 rotations was 2.0%, and in the falling ball test, the ball could not be seen through, indicating good anti-haze performance.

Example 4 Using the film with a thickness of 0.6 mm produced in the second example, it was subjected to hot water treatment and drying in the same manner as in Example 5, and then a pie layer glass was produced. This Pylayer glass showed a 24% increase in haze after 100 rotations in the taper test.
In the falling ball test, the same performance as in Example 6 was exhibited.

Actual Ijm Example 5 Polybutylene adipate with 56 hydroxyl groups 15002.4
．． 4'methylene-bis(cyclohexyl isocyanate) 6422, di-n-butyltin dilaurate 0429
．． Using 1,4-butanediol 1217 and dimethylolpropionic acid 457, the reaction was carried out in the same manner as in Reference Example A) to produce a film having a speed of 0.6 + nm. The solution of glycidyl cinnamate prepared in Reference Example A was uniformly applied to one side of this film and allowed to react for 1 hour. After that, the pie layer glass was irradiated with light in the same manner as in Example 1. In the taper test, this Pylayer glass showed an increase in haze of 1.0 after 100 rotations.
Example 6 Polycaprolactone diol 15009.4.4'-methylene bis(15009.4'-methylene bis(hydroxyl value) 15009.4'-methylene bis(hydroxyl value 55.8) showed the same performance as that of Example 1. 6
A film with a thickness of +-rn was "')". One side of this film was subjected to the same treatment as in Reference Example C, and then a pie layer glass was made by the same method as in Example 6. In the taper test, the increase in haze after 100 rotations was 2.9%.Other performances were the same as in Example 5.

Example 7 In Reference Example C, the same method as Reference Example C was used except that β-(3-4 evogycyclohexyl)ethyltrimethoxysilane was used instead of γ-glycidoxypropyltrimethoxysilane. I made a film with the name 06-.

Using this film, by the same method as in Example 16,
I made pie layer glass. With this Pylayer glass, the haze increase after 100 rotations was 2.
Except that the performance was 6%, it showed the same performance as the real 1ii+lB'lI3.

[Brief explanation of the drawing]

Figures 2 and n1 to 4 are schematic cross-sectional views showing the formation of each layer when manufacturing the laminated safety glass according to the present invention. Figure 1 1d: Two-layer structure, Figure 2 and Figure 6 are 2
5-layer structure with a resin layer; FIGS. 4 and 5 show a 4-layer structure with 6 hard substrate layers. 1. Mold material 2. Heat Plastic resin 4...
・Hard substrate A...Modified surface B'...Unmodified surface, 3 buds, 2 fan buds, 4 lice buds

Claims (1)

[Claims] 1. A method for producing transparent or translucent laminated safety glass having at least a two-layer structure of a thermoplastic resin 1:li7 layer with an exposed surface and a hard substrate layer, in which the glass is modified by light or moisture. A thermoplastic resin hard substrate having a textured surface on one side and the modified thermoplastic resin surface of the thermoplastic resin on one side are used as a fusion surface either directly or through a No. 20 thermoplastic resin. A method for producing laminated safety glass characterized by thermocompression bonding. 2. The modified surface is a surface obtained by crosslinking functional groups that can be crosslinked with light or moisture introduced into the surface of a thermoplastic resin with light or moisture. Method of scope 1. '6. 2. The method of claim 1, wherein the thermoplastic resin having a modified surface is a polyurethane thermoplastic resin. 4. The method according to claim 1, +Q, characterized in that the hard substrate layer is made of an inorganic glass layer.