JPS6336944B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates 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 particularly relates to a method for producing laminated safety glass that is not modified by light or moisture. The present invention relates to a method for producing laminated safety glass with excellent surface properties by thermocompression bonding a glass sheet with a thermoplastic resin having a transparent surface, and then modifying the modified surface.

A laminated sheet of a glass sheet and a synthetic resin sheet is well known as laminated safety glass. for example,
A laminated sheet having a three-layer structure of glass-polyvinyl butyral-glass is widely used as safety glass for automobiles. The synthetic resin layer laminated between such glass sheets is called an interlayer film, and various synthetic resins such as polyvinyl butyral, polyurethane, and others have been used or proposed. On the other hand, in laminated safety glass made of glass and synthetic resin, laminated sheets with exposed synthetic resin layers, such as glass-synthetic resin or glass-
Laminated sheets such as synthetic resin-glass-synthetic resin, in which one side is glass and the other side is synthetic resin, are attracting attention for use in automobile safety glasses and the like. This laminated safety glass is considered to be even safer than traditional double-sided glass laminated safety glass. For example, if this laminated safety glass is used as a car windshield with the synthetic resin side facing the inside of the car, there will be fewer lacerations and cuts when a driver etc. collides with the windshield, and even if the glass breaks. It is thought that this will reduce the chance of glass shards flying into the interior of the car. This kind of laminated safety glass, where one side is glass and the other side is synthetic resin,
Hereinafter referred to as "bilayer glass."

Bilayer glass is described, for example, in JP-A-48-41423, JP-A-48-25714, JP-A-49-34910, and JP-A-53-27671. As can be seen from these known examples, the exposed synthetic resin layer (hereinafter referred to as bilayer layer) is usually composed of polyurethane. Polyurethanes are also well known as interlayers in laminated glass. Polyurethanes include so-called thermoplastic polyurethanes and thermosetting polyurethanes; the former is a linear polymer, usually obtained by reacting a high molecular weight diol, a chain extender, and a diisocyanate compound, and the latter is a crosslinked polymer. For example, it can be obtained by reacting a high molecular weight diol, a crosslinking agent and a diisocyanate compound. The bilayer layer needs to be strongly bonded to the glass. However, when thermosetting polyurethane is used as a bilayer layer, there is a problem that it does not adhere firmly to glass. On the other hand, thermoplastic polyurethane adheres strongly to glass, but as long as it is used as a bilayer layer, the other side will be exposed, so the nature of its surface becomes a problem. That is, thermoplastic polyurethane has insufficient weather resistance and is easily attacked by solvents. These problems are explained in detail in the above-mentioned Japanese Patent Application Laid-Open No. 53-27671, particularly on pages 6 to 7.

In order to solve the above problems, the invention described in JP-A-53-27671 consists of a bilayer layer consisting of two polyurethane layers, the surface of which is made of thermosetting polyurethane, and the adhesive surface with glass made of thermoplastic. We are trying to solve this problem by using polyurethane. Since both polyurethanes adhere strongly, this invention solves the problems of adhesion and surface properties of the bilayer layer to the glass. However, it is not considered that all problems have been completely solved by this invention. First of all, the invention requires the production of sheets (called preformed sheets) of two different polyurethanes, which requires a relatively complicated process. For example, as explained in page 10, lower right column, line 13 to page 11, upper right column, line 14, one sheet may be poured onto the other to integrate it, or one sheet may be dissolved in a solvent. This requires a method such as applying it to the other surface.

The second problem is that thermosetting polyurethane loses its plasticity after curing. First, the methods for forming sheets and films of thermoset polyurethane are limited (cast molding and curing is almost the only method), making it difficult to form sheets or films by extrusion, press molding, or other methods. Therefore, it is difficult to obtain a smooth sheet or film of uniform thickness.
Furthermore, if it has plasticity, it can be compressed with a mold with a smooth surface to create a smooth surface, but this is also difficult. Of course, this is also due to the lack of adhesion. Third, thermosetting polyurethane has a problem in that, compared to thermoplastic polyurethane, it does not have sufficient physical properties required for bilayer glass, such as penetration resistance and impact resistance. Many of these problems have not yet been solved with the above invention, and apart from the problem of surface properties, thermoplastic resins, especially polyurethane-based thermoplastic resins, are considered to be the best for the bilayer layer of bilayer glass. Conceivable.

The inventor has discovered that it is possible to modify the surface of a thermoplastic resin layer to improve its surface properties, thereby producing a good bilayer glass without substantially using thermosetting polyurethane. Ta. The modifiable surface of the thermoplastic is the exposed surface, the modification of which is effected by light or moisture. In the present invention, the surface that can be improved refers to a surface that has been introduced with a functional group that can be crosslinked by light or moisture, or a functional group that can be converted into such a functional group, and refers to a surface that has been introduced with a functional group that can be crosslinked by light or moisture, or a functional group that can be converted into the functional group. Alternatively, a surface that has not been introduced is not a surface that can be modified. That is, as will be described later, in order to facilitate the introduction of these functional groups, it is preferable to have active groups such as carboxylic acid groups present in the thermoplastic resin, but active groups such as carboxylic acid groups are crosslinked by direct light or moisture. Therefore, the surface with this active group is not a surface that can be modified. In addition, groups such as alkoxysilyl groups that are hydrolyzed by moisture to generate silanol groups and subsequently crosslinked by dehydration condensation are moisture crosslinkable functional groups, and the silanol groups generated during this process are also functional groups. Defined as a moisture crosslinkable functional group in the invention. Under this definition, the present invention describes a thermoplastic resin sheet or film having two surfaces: a surface that can be modified (also referred to as a modified surface) and a surface that cannot be modified (also referred to as a non-modified surface). The present invention relates to a method for manufacturing transparent or translucent laminated safety glass such as bilayer glass by thermocompression bonding using the present invention.

That is, the present invention provides an improvement that can be modified by light or moisture in a method for producing transparent or translucent laminated safety glass having at least a two-layer structure of a thermoplastic resin layer with an exposed surface and a hard substrate layer. A thermoplastic resin having a non-modified surface on one side and a hard substrate layer are bonded by thermocompression, using the non-modified surface of the thermoplastic resin as a fusion surface, either directly or via a second thermoplastic resin, and then or This method of manufacturing laminated safety glass is characterized in that the modifying surface is modified with light or moisture at the same time as pressure bonding.

The laminated safety glass in the present invention has at least a two-layer structure. The thermoplastic resin layer may have a multilayer structure, and the hard substrate layer may also have a multilayer structure, such as the laminated glass made of glass-synthetic resin-glass. Thermocompression bonding involves assembling at least one thermoplastic resin sheet or film and a hard substrate (hereinafter referred to as a laminate assembly), and heating and pressing them simultaneously or sequentially in the case of a multilayer structure of three or more. It is carried out by. 1 to 4 are schematic cross-sectional views showing the layer structure 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 A and a non-modified surface B can not only be used alone (FIG. 1) but also in combination with a second thermoplastic resin 3 ( 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 a single layer or may have a multilayer structure (FIG. 4). In the latter case, the production of a multilayer hard substrate may be carried out simultaneously with this thermocompression bonding, for example, as shown in FIG. 5, two glass sheets 5,
A synthetic resin 7 such as butyral resin can be placed between the holes 6 and 6, and thermocompression bonded at the same time.

Thermocompression bonding involves a pre-pressing process in which the laminated assembly is depressurized and degassed under heating at room temperature or below 100°C in order to remove the air that normally exists between the hard substrate and the thermoplastic resin layer; This is carried out through a main compression bonding step of thermocompression bonding under heating and pressure. For example, a thermoplastic resin may be stacked on a hard substrate with the modified surface of the resin facing outward, or a first thermoplastic resin may be placed on a hard substrate with a second thermoplastic resin interposed therebetween.
of thermoplastic resin is layered so that the modified surface of the resin faces outward, and then a molding material with a smooth surface, such as a glass sheet that has been subjected to mold release treatment, is placed on the modified surface of the thermoplastic resin. Layer rubber sheets, plastic sheets, etc., place this laminated assembly in a rubber pre-crimping bag, deaerate the inside of the crimping bag and perform preliminary crimping, then remove the pre-crimped laminate from the mold material, or Thermocompression bonding is performed by placing the components in an autoclave without separating them and applying heat and pressure to perform the main compression bonding. Such pre-crimping is usually carried out at a temperature of 700 mmHg within the pre-crimping bag, for example 200 mmHg to 650 mmHg.
After reducing the pressure to mmHg, below 100℃, e.g. room temperature to 90℃
This is done by heating to ℃. In addition, the main crimping is usually performed at a temperature ranging from about 60° to the point where the thermoplastic resin melts, for example, if the thermoplastic resin is a polyurethane thermoplastic resin, the temperature is about 80°C to 150°C, and the pressure is 2 kg/cm. As mentioned above, for example, in the case of polyurethane thermoplastic resin, it is preferable to carry out the reaction under a pressure of about 7 to 20 kg/cm ² . These conditions include the type of thermoplastic resin and hard substrate, the thickness and size of each constituent unit,
This may vary depending on other factors. In addition,
Preliminary crimping is not limited to the method of using a pre-crimping bag as described above, but also a method of passing the laminated assembly between rolls and pressing the rolls to pre-crimp, a method of pressing the laminated assembly with a platen and pre-crimping, Alternatively, the stacked assembly is placed in the inner vacuum chamber of a decompression device with 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 depressurized. This can also be done by a double vacuum crimping method in which the pressure is released and then crimped at atmospheric pressure. or,
This pressure bonding is not limited to the method of thermocompression bonding using an autoclave, but also a method of placing the laminated assembly in a heated oil tank and applying pressure, a method of pressing rolls between rolls under heat, a method of pressing under heat, It can also be carried out by a method of pressure bonding, such as a double vacuum pressure bonding method under heating.

In addition, in thermocompression bonding, especially in the pre-compression bonding process,
In order to ensure sufficient preliminary crimping and to obtain a smooth surface, it is preferable to place a molding material on top of the thermoplastic resin that is to be removed after crimping, but depending on the type of crimping method, such a molding material may be placed. can be omitted.

In addition, crimping between a hard substrate and a thermoplastic resin is most commonly carried out through a preliminary crimping process and a main crimping process. Depending on the size etc., thermocompression bonding may be performed in one step without going through both the preliminary pressure bonding step and the main pressure bonding step.

One feature of the present invention is that after thermocompression bonding of a thermoplastic resin and a hard substrate, the modifying surface of the thermoplastic resin is treated with light or moisture to modify the surface. This includes both after preliminary crimping and after main crimping. Therefore, the modification treatment may be performed after the preliminary crimping and before the main crimping, or the modification treatment may be performed after the main crimping, or the step may be performed both after the preliminary crimping and after the main crimping. Alternatively, a modification treatment may be performed.

Further, the modification of the modifyable surface can be carried out almost simultaneously with this thermocompression bonding. For example, when a transparent mold material such as a glass sheet is used as described above, light such as ultraviolet rays is irradiated from above the mold material to modify the modifying surface, that is, crosslink the photocrosslinkable groups present on the surface. Thermocompression bonding can be performed while the process is being carried out. However, the surface is usually modified after the thermocompression bonding is completed. Surface modification is carried out for photo-crosslinkable groups by irradiation with light, and for moisture-crosslinkable groups by immersion in water, application of water, or under a moist atmosphere. This is done by placing the Functional groups that can be crosslinked by light or moisture;
Alternatively, the functional group convertible into the functional group is introduced onto the surface of the thermoplastic resin before thermocompression bonding, but the conversion of the functional group may be performed before or after thermocompression bonding. Further, the hydrolysis of the alkoxysilyl group, which will be described later, may be carried out before or after thermocompression bonding. In the case of a functional group that easily causes crosslinking, the latter case is considered to be suitable because crosslinking may occur before thermocompression bonding. 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 thermoplastic resin, such as a sheet of inorganic glass (hereinafter simply referred to as glass), polycarbonate,
Sheets of polymethyl methacrylate and other organic glasses. These hard substrates may have a single layer structure or a multilayer structure as described above. In the case of a multilayer structure, the surface to which the thermoplastic resin is thermocompressed and the surface of the exposed outermost layer are 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, such as by air tempering or chemical strengthening. Further, the glass sheet may be colored or may have a thin layer such as a heat ray reflective film. For organic glass sheets,
It may be subjected to a treatment such as a stretching treatment, and may have a thin layer such as a hard coat layer. Furthermore, the organic glass sheet may be colored or patterned, and may also have partially opaque portions. These hard substrates are preferably transparent to semitransparent as a whole, and particularly preferably have excellent optical properties. This hard substrate may not only be a flat plate but may also be formed 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 fine irregularities on the surface) that can eventually become transparent to translucent. . This thermoplastic resin may be colored or may have partially opaque areas. The thermoplastic resin constituting the exposed surface is most preferably a polyurethane thermoplastic resin, as described below, but various thermoplastic resins can be used as the thermoplastic resin not constituting the exposed surface. However, even if the bilayer layer is a thermoplastic resin that does not constitute an exposed surface, if the physical properties of the bilayer layer mainly depend on that layer, that is, if the layer is particularly thick compared to other thermoplastic resin layers,
The thermoplastic resin is preferably a polyurethane thermoplastic resin. 1 layer of thermoplastic resin
If it is only a layer, a sheet of thermoplastic resin is used. In the case of a multilayered thermoplastic resin layer, a sheet or film can be used. In the present invention, a sheet refers to a sheet with a thickness of 0.2 mm or more,
Film is anything with a thickness less than that. Therefore, the thermoplastic resin layer can be constructed using, for example, a polyurethane thermoplastic resin film having a modifying surface on one side and a polyurethane thermoplastic resin sheet. The thickness of the entire thermoplastic resin layer is not particularly limited, but is 0.2 mm or more,
In particular, it is preferably 0.4 to 10 mm.

In the present invention, the thermoplastic resin is preferably a polyurethane thermoplastic resin. As other thermoplastic resins, polyester resins, butyral resins, polydiene resins, ethylene-vinyl acetate copolymers, polyolefin 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, impact resistance, penetration resistance, and other object aspects.
A polyurethane-based thermoplastic resin is a thermoplastic synthetic resin having a large number of urethane groups.
In addition to the urethane group, this synthetic resin may have a group formed by a reaction between an isocyanate group and an active hydrogen-containing group such as a urea group, an allophanate group, or a biuret group. Further, it may have an isocyanurate group, a carbodiimide group, or another group derived from an isocyanate group. Furthermore, the ester group that the high molecular weight 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 the case of exposed polyurethane, in order to introduce functional groups that can be crosslinked by light or moisture, as will be described later, active groups that can bond with compounds having those functional groups, such as carboxylic acid groups and
It is preferable to have a grade amino group.

Polyurethane thermoplastic resins are basically linear polymers obtained by reacting high molecular weight diols, chain extenders, and diisocyanate compounds.
However, small amounts of branching may be present;
For example, it may be a mostly linear polymer with a small amount of branched parts obtained by using a trifunctional or higher functional polyol, a crosslinking agent, or a polyisocyanate in combination with the above bifunctional compound. In addition to the three main raw materials of a high molecular weight diol, a chain extender, and a diisocyanate compound, a polyurethane thermoplastic resin can be obtained using various auxiliary raw materials as necessary. A catalyst is usually required as an auxiliary feedstock.
Depending on the purpose, crosslinking agents, coloring agents, stabilizers,
UV absorbers, flame retardants and other additives can be used as auxiliary raw materials.

As high molecular weight diols, polyester diols, polyether diols, polyether ester diols, polycarbonate diols, and other high molecular weight diols can be used, especially polyester diols obtained from dihydric alcohols and dihydric carboxylic acid compounds, or cyclic ester compounds. Polyester diols obtained by ring-opening polymerization are preferred, such as poly(1,4-butylene adipate), poly(ethylene adipate), poly(1,3-butylene azelate), poly(ε-caprolactone), etc. Can be used. Polyether diols and polycarbonate diols obtained by adding epoxides such as alkylene oxides or other cyclic ethers with four or more members to water, dihydric alcohols, dihydric phenols, or other initiators are also rarely preferred. do not have. These high molecular weight diols are suitably low melting point compounds that are liquid at room temperature or can become liquid during reaction, and their molecular weights are not particularly limited, but are preferably from 600 to 8,000, particularly from 800 to 4,000. The chain extender is a relatively low molecular weight divalent compound, such as a diol, diamine, divalent alkanolamine, or other compound having two hydroxyl groups or two amino groups. Although its molecular weight is not particularly limited, it is preferably 300 or less, particularly 150 or less. As the diol, dihydric alcohols, polyester diols, polyether diols, etc. can be used, and dihydric alcohols having 2 to 6 carbon atoms are particularly preferred. As the diamine, aliphatic, alicyclic, aromatic, and other diamines can be used. Examples of alkanolamines include N-
Dihydric alkanolamines such as alkyldiethanolamines can be used. In the combination of these high molecular weight diols and chain extenders, other divalent compounds, such as diols having a molecular weight intermediate between the two, may be used in combination. Of course,
Two or more types of high molecular weight diols and chain extenders can be used in combination.

As the diisocyanate compound, aliphatic, alicyclic, aromatic, and other diisocyanates and modified products thereof can be used, and it is also possible to use two or more of them in combination. Since an isocyanate group directly bonded to an aromatic nucleus may cause yellowing of the resulting polyurethane, diisocyanates that do not have such isocyanate groups, usually called non-yellowing diisocyanates, are preferred. For example, preferred diisocyanates include hexamethylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexylmethane 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 surface. In order to introduce this functional group, the thermoplastic resin needs an active group, and it is particularly preferable that the thermoplastic resin already has a highly reactive group. For example, polyurethane thermoplastic resins have carboxylic acid groups, tertiary amino groups,
It is preferable to have other highly reactive groups. Of course, even if there is no such group, it is also possible to utilize an active group that it itself has, such as a urethane group. However, considering the ease of introducing a functional group that can be crosslinked by light or moisture, it is preferable to introduce a group that is highly reactive in polyurethane production. Taking carboxylic acid groups as an example of highly reactive groups, main raw materials with carboxylic acid groups such as high molecular weight diols with carboxylic acid groups and chain extenders with carboxylic acid groups, or crosslinking agents with carboxylic acid groups A polyurethane having a carboxylic acid group can be produced using auxiliary raw materials such as and other compounds having a carboxylic acid group. Although these compounds having a carboxylic acid group can be used in place of the entire amount of the above-mentioned high molecular weight diol and chain extender, they are usually used in combination with them. For example, 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 common chain extender. In addition, in cases where there is a risk that the carboxylic acid group may affect the reaction in the production of polyurethane or where there is a risk that the carboxylic acid group may react, use a compound that has a group that can be converted into a carboxylic acid group later. It is also possible to adopt a method in which polyurethane is produced using a polyurethane, and then the groups are changed to carboxylic acid groups.

Polyurethane thermoplastic resins are manufactured using the above-mentioned raw materials by a one-shot method, a prepolymer method, a quasi-prepolymer method, and 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 that can be crosslinked by light or moisture, or a functional group that can be converted thereto, is introduced onto one side of this sheet or film. For example, in the case of the above polyurethane having carboxylic acid groups, alkoxysilanes having epoxy groups on the surface, such as γ
- Glycidoxypropyltrimethoxysilane or a coating solution containing it is applied and reacted to introduce an alkoxysilyl group. 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 and crosslink. do. Moisture crosslinking of alkoxylyl groups 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 present invention, surface modification refers to this crosslinking reaction, and therefore, as defined above, the silanol groups generated during moisture crosslinking of alkoxysilyl groups do not crosslink due to moisture. No, but
In the present invention, it is a type of functional group that can be crosslinked by moisture. In the present invention, since crosslinking is performed after thermocompression bonding, this hydrolysis may be performed before or after thermocompression bonding.

The crosslinkable functional group is introduced into one surface of the thermoplastic resin sheet or film. The surface into which this functional group is introduced is a modified surface, and the other surface is a non-modified surface. It is not preferable to introduce a crosslinkable group into the unmodified surface because it may reduce the adhesive strength of the fused surface. However, as long as there are no such inconveniences, a crosslinkable group may be introduced into the unmodified surface. For example, introducing crosslinking groups onto only one side of a thermoplastic resin sheet or film may complicate the manufacturing process; in such cases, the presence of crosslinking groups on the unmodified surface may is allowed as long as it does not cause any inconvenience. In particular, even if the moisture crosslinkable group is present on the fusion surface, it will not be crosslinked later, so there is little inconvenience. However, unless there is a positive meaning of introducing a crosslinkable group into the unmodified surface, the crosslinkable group is substantially introduced only into the modified surface.

The second thermoplastic resin is preferably a polyurethane thermoplastic resin as described above, but if it is thin and does not mainly affect the physical properties of the bilayer layer, it may be a butyral resin, a polyester resin, etc. Thermoplastic resins other than polyurethane may also be used. This second thermoplastic resin may be a multilayer structure, or a plurality of sheets or films thereof may be used and thermocompression bonded simultaneously during thermocompression bonding. Note that sheets and films of thermoplastic resins with a multilayer structure, including thermoplastic resins having a modified surface and a non-modified surface, may be coated with a thermosetting resin such as a thermosetting resin adhesive between each layer. It may also have a thin layer of resin.

The transparent to translucent laminated safety glass obtained by the present invention is suitable as a window material for automobiles and other vehicles, or as a window material for architecture. However, its uses are not limited to these, and 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 using Examples, but the present invention is not limited to these Examples.

Reference Example Production example of a polyurethane film having a photomodifiable surface on one side [A] 1500 g of polybutylene adipate with a hydroxyl value of 56
was dehydrated at 110° C. for 2 hours under a vacuum of 3 mmHg. To this was added 908 g of isophorone diisocyanate [3-isocyanate methyl 3,5,5-trimethylcyclohexyl isocyanate] and di-n-
0.16 g of butyl tin dilaurate was added and reacted for 15 minutes at 80°C under a nitrogen stream. Next, 244 g of 1,4-butanediol and 75 g 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. Pour this liquid reaction mixture into a Teflon-coated vat 110
℃ for 12 hours. The produced polymer was pulverized and granulated using a pulverizer, and then formed into a film using an extruder. Next, a solution consisting of 50 g of glycidyl cinnamate, 15 g of triethylamine, 5 g of 2,2 dimethoxy-2-phenylacetophenone, and 500 g of benzene was uniformly applied to one side of the film, and the film was transferred as it was into a nitrogen-purged oven at 110°C. Allowed time to react.

[B]

Polyethylene adipate 1500 with hydroxyl value 56.7
g, 4,4'-methylene-bis(cyclohexyl isocyanate) 781 g di-n-butyltin dilaurate 0.45 g, 1,4-butanediol
A film was prepared by reacting in the same manner as in Reference Example A using 144 g of dimethylolpropionic acid and 75 g of dimethylolpropionic acid. A solution made from 50 g of glycidyl methacrylate, 15 g of N,N' dimethylaniline, 5 g of benzoin methyl ether, and 500 g of benzene was applied uniformly onto one side of this film, and the film was transferred as it was into a nitrogen purge oven at 110° C. and reacted for 30 minutes.

Production example of a polyurethane film with a moisture-modifying surface on one side [C] Polybutylene adipate 1500 with a hydroxyl value of 54.3
g, 4,4'-methylene-bis(cyclohexyl isocyanate) 642 g, di-n-butyltin dilaurate 0.33 g, 1,4 butanediol
121g of dimethylolpropionic acid and 45g of dimethylolpropionic acid were used to react in the same manner as in Reference Example A to produce a film. A mixture of γ-glycidoxypropyltrimethoxysilane and a trace amount of N,N dimethylaniline was applied very thinly and uniformly to one side of this film, and the film was transferred as it was to a nitrogen purge furnace.
The reaction was carried out at a temperature of 110°C for 30 minutes.

[D]

Polyethylene adipate 1500 with hydroxyl value 56
g, 4,4-methylenebis(cyclohexyl isocyanate) 1173g, 1,4butanediol
327g, di-n-butyltin dilaurate 0.18
A film was produced by reacting in the same manner as in Reference Example A using g. A solution consisting of 50 g of γ-isocyanatepropyltrimethoxysilane, 0.5 g of lead octylate, and 500 g of benzene was uniformly coated on one side of this film, and the film was transferred as it was into a nitrogen purge oven at 110° C. and reacted for 1 hour.

Example 1 The 0.6 mm thick film produced in Reference Example A was placed between two glass plates. At this time,
Polydimethylsiloxane was uniformly coated in advance on the surface of one piece of glass that was in contact with the modifying 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, a vacuum was applied to both the garbage bag and the autoclave to remove the air between the glass and film. Next, heat the autoclave to 100℃ and return only the inside of the autoclave to atmospheric pressure while keeping the inside of the rubber bag in a vacuum to produce 1Kg/cm ²
pressure was applied. After keeping it in this state for 15 minutes, set the autoclave to 140℃ and 13Kg/ ^cm2.
Hold for 20 minutes. After removing the glass laminate from the autoclave, the glass treated with polydimethylsiloxane was removed, resulting in a bilayer glass in which the exposed surface of the film was glass-like and smooth and had good adhesion to the glass. .
Next, a 100W high-pressure mercury lamp was applied to this bilayer glass from a distance of 5 cm from the film surface.
Light was irradiated for a minute. On this film surface, ethanol/methanol = 10/1 (V/V), carbon tetrachloride,
A rubbing test was conducted by dyeing felt with kerosene and gasoline, but no change was observed even after 1000 rubbings. Also, JIS R
The Taber test based on 3213 showed a 2.5% increase in haze after 100 cycles. Also JIS R 3212
In a falling ball test based on the above, the steel ball did not penetrate and showed sufficient penetration resistance.

Example 2 Using the 0.6 mm thick film produced in Reference Example B, a bilayer glass was made in the same manner as in Example 1, and irradiated with light. After the light treatment, the bilayer glass showed a 2.3% increase in haze after 100 rotations in the taper test, and in the rubbing test and falling ball test shown in Example 1, it showed the same results as in Example 1. showed the same performance.

Example 3 A bilayer glass was made in the same manner as in Example 1 using the 0.6 mm thick film made in Reference Example C. This bilayer glass
It was immersed in hot water at 90°C for 30 minutes, then transferred to a dryer at 120°C and dried for 15 minutes. The film surface of this bilayer glass was glass-like and smooth, and the adhesion between the film and the glass was also good. When this bilayer glass was subjected to the same test as in Example 1, it was found that the rubbing test
No changes were observed even after the treatment. In addition, in the taper test, the haze increased by 2.0% after 100 rotations.
In the falling ball test, the ball did not penetrate and showed good penetration resistance.

Example 4 Using the 0.6 mm thick film produced in Reference Example D, a bilayer glass was made in the same manner as in Example 3, followed by hot water treatment and drying. In the Taber test, this bilayer glass showed the same performance as Example 3 in other tests, except that the increase in haze after 100 rotations was 2.4%.

Example 5 1500 g of polybutylene adipate with a hydroxyl value of 56,
642 g of 4,4-methylenebis(cyclohexyl isocyanate), 0.42 g of di-n-butyltin dilaurate, 121 g of 1,4-butanediol, and 45 g of dimethylpropionic acid were reacted in the same manner as in Reference Example A to give a thickness of 0.6 mm. I made a film. The solution of glucidyl cinnamate prepared in Reference Example A was uniformly applied to one side of this film and allowed to react for 1 hour. Using this film,
A bilayer glass was made in the same manner as in Example 1. This bilayer glass is
Haze increase by 1.9% after 100 rotations in taper test
In other respects, the performance was similar to that of Example 1.

Example 6 1500 g of poly(caprolactone) diol with a hydroxyl value of 55.8, 1003 g of 4,4-methylene-bis(cyclohexyl isocyanate), di-
A 0.6 mm thick film was made using 0.33 g of n-butyltin dilaurate, 150 g of 1,4-butanediol, and 75 g of dimethylolpropionic acid.
After subjecting one side of this film to the same treatment as in Reference Example C, a bilayer glass was produced. This product showed a 2.9% increase in haze after 100 rotations in the taper test. Other performances were the same as in Example 3.

Example 7 The thickness was determined by the same method as in Reference Example C except that β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was used instead of γ-glycidoxypropyltrimethoxysilane. I made a 0.6mm film. A bilayer glass was made using this film in the same manner as in Example 3. This bilayer glass has a haze increase of 2.6 after 100 rotations in a taper test.
The performance was the same as in Example 3 except for the percentage.

[Brief explanation of the drawing]

FIGS. 1 to 4 are schematic cross-sectional views showing the layer structure when manufacturing the laminated safety glass according to the present invention. Fig. 1 shows a two-layer structure, Figs. 2 and 3 show a three-layer structure with two thermoplastic resin layers, and Figs. 4 and 5 show a four-layer structure with three hard substrate layers.
A layered structure is shown. 1... Shape material, 2... Thermoplastic resin, 4... Hard substrate, A... Modified surface, B... Non-modified surface.

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 layer with an exposed surface and a hard substrate layer, which can be modified by light or moisture. A thermoplastic resin having a modified surface on one side and a hard substrate are bonded by thermocompression, using the non-modified surface of the thermoplastic resin as a fusion surface, either directly or via a second thermoplastic resin, and then or A method for manufacturing laminated safety glass, which comprises modifying the modifying surface with light or moisture at the same time as thermocompression bonding. 2. The method according to claim 1, wherein the modifying surface is a surface having a functional group that can be crosslinked by light or moisture introduced into the surface of the thermoplastic resin. 3. The method according to claim 1, wherein the thermoplastic resin having a modifying surface is a polyurethane thermoplastic resin. 4. The method according to claim 1, wherein the hard substrate layer comprises an inorganic glass layer.