JPS59133049A - Laminated safety glass and its manufacture - 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 consisting of a synthetic resin layer and a hard substrate layer having a multilayer structure with exposed surfaces, and a method for manufacturing the same, and in particular to a laminated safety glass with excellent surface properties and a method for manufacturing the same. The present invention relates to a manufacturing method thereof.

A laminated sheet of an inorganic glass (hereinafter simply referred to as 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, and 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, a laminated sheet with an exposed synthetic resin layer is used, such as glass-synthetic resin or glass-synthetic resin-glass-synthetic resin, where one side is glass and the other side is synthetic resin. A certain laminated sheet is attracting attention for applications such as automotive safety glass. This laminated safety glass is considered to be even safer than conventional laminated safety glass, which has glass on both sides. 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 or other person collides with the windshield, and the glass will not break. It is thought that this will reduce the chance of glass shards flying into the interior of the car. Such laminated safety glass, in which one side is glass and the other side is synthetic resin, is hereinafter referred to as "pylayer glass."

Regarding pie layer glass, for example, Japanese Patent Application Laid-Open No. 1986-
41423, JP 48-25714, JP 49-34910, and JP 56-27
There is a description in Publication No. 671. As can be seen from these known examples, the exposed synthetic resin layer (hereinafter referred to as a pie 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. Coalescing agents, such as high molecular weight diols, crosslinking agents.

and a diincyanate compound.

The first layer of pie layer needs to be firmly bonded to the glass.

However, when a pie layer is made of thermosetting polyurethane, there is a problem that it does not adhere firmly to glass. On the other hand, thermoplastic polyurethane adheres strongly to glass, but when used as a single layer, the other side is exposed, so the properties of the surface become 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 pie layer consisting of two polyurethane layers, the surface of which is made of thermosetting polyurethane, and the adhesive surface with glass made of thermoplastic. The problem is solved by using polyurethane.Since both polyurethanes have strong adhesion, this invention solves the problems of adhesion and surface characteristics of the pie layer to glass.However, this invention solves all the problems. It is not considered that the problem could be completely solved.In other words, the laminated safety glass in this invention
Thermoplastic polyurethane is unique in that it takes advantage of the self-healing and tear-resistant properties of thermosetting polyurethane, and thermoplastic polyurethane is used as an adhesive to bond this thermosetting resin and glass. Therefore, one pie layer in this laminated safety glass consists of a thick thermosetting polyurethane and a thin thermoplastic polyurethane. However, as a pie layer of laminated safety glass, thermoplastic polyurethane is far superior to thermosetting polyurethane except for surface properties. For example, thermoplastic polyurethane is superior in terms of impact strength, penetration resistance, energy absorption properties, tear resistance properties, moldability (ease of forming sheets or films), and the above-mentioned adhesive properties. Regarding self-healing properties, it is possible to achieve performance equivalent to that of thermosetting polyurethane (by selecting the composition of thermoplastic polyurethane). Therefore, it is most preferable that the main part (i.e., the thickest part) of the pie layer is made of thermoplastic polyurethane.

On the other hand, when considering the manufacturing method of laminated safety glass, thermosetting polyurethane is not a particularly suitable material. Thermosetting polyurethane is suitable for molding.

Although there are limitations, casting uncured thermosetting polyurethane is almost the only way to make sheets or films. Moreover, after the price has been reduced, it is not possible to plastically process it.

Therefore, for example, in order to form a single pie layer as in the above-mentioned known example, it is necessary to use a method in which a preformed sheet containing thermosetting polyurethane molded by a casting method is laminated with glass.

If only a plastic material such as thermoplastic polyurethane is used, a sheet or film can be formed by various easy methods, and of course a casting method is also possible, giving a wide degree of freedom in the manufacturing method of laminated safety glass. In addition, there are various advantages of not using thermosetting polyurethane, such as the ability to compress the surface with a smooth mold material using a lamination method such as thermocompression bonding, thereby making the surface of the pie layer even smoother.

As a result of various research studies in consideration of these problems, the inventor of the present invention made the main part of the pie layer a thermoplastic resin such as a polyurethane thermoplastic resin, and in order to solve the problem of its surface characteristics, the main part of the pie layer was made of thermoplastic resin. By making the outer layer a thin crosslinked synthetic resin layer and using a crosslinked synthetic resin crosslinked by an action other than heat, we have discovered a laminated safety glass that has excellent performance and is easy to manufacture. . Crosslinked synthetic resin A synthetic resin that is crosslinked by an action other than heat, such as light or moisture. By using this material, the surface properties are improved, and it can be handled in the same way as thermoplastic resin before being exposed to light or moisture, making the method of manufacturing safety glass extremely easy. I can do it. The present invention relates to this laminated safety glass and its manufacturing method.The laminated safety glass of the present invention will be explained below, and then the manufacturing method will be explained.

The laminated safety glass of the present invention is a transparent or translucent laminated safety glass having at least a three-layer structure of at least a two-layered synthetic resin layer with an exposed surface and a hard base layer, which includes:
The synthetic resin layer is composed of a thin outermost layer having an exposed surface and at least one thick inner layer, the outermost layer is a crosslinked synthetic resin layer crosslinked by an action other than heat, and the main part of the inner layer is This is a laminated safety glass characterized by a thermoplastic resin layer. Schematic cross-sectional views of the laminated safety glass of the present invention are shown in FIGS. 1 to 3.

FIG. 1 is a cross-sectional view showing one example of the laminated safety glass of the present invention.
) has a two-layer structure including an outermost layer (3) made of a crosslinked synthetic resin and an inner layer (4) made of a thermoplastic resin. FIG. 2 is a sectional view showing another example of the laminated safety glass of the present invention, in which the synthetic resin layer (1) is the outermost layer (3) and the two inner layers (4).
) (5), the main part (4) of the inner layer is made of thermoplastic resin, and the inner layer (5) in contact with the hard substrate (1) is made of synthetic resin with high adhesiveness to the hard substrate. FIG. 6 is a sectional view showing another example of the laminated safety glass of the present invention, in which the hard substrate layer (1) is composed of two inorganic glasses (6) and (7) and an interlayer film such as butyral resin existing between them. It consists of a six-layer structure (8).

In the present invention, the synthetic resin layer is composed of an outermost layer made of a crosslinked synthetic resin and an inner layer made of at least one synthetic resin whose main portion is a thermoplastic resin. The crosslinked synthetic resin is a synthetic resin crosslinked by an action other than heat, particularly by light or moisture, and will be described later. The inner layer may consist of at least one thermoplastic resin layer only, or at least one thermoplastic resin layer and at least one thin layer of a synthetic resin other than a thermoplastic resin, such as cured by heat, light, moisture, etc. Alternatively, it is made of crosslinked synthetic resin. Synthetic resins other than thermoplastic resins for this inner layer are mainly used for the purpose of adhesion between multi-layered synthetic resin layers or between synthetic resin layers and hard substrate layers. The presence of the limiting layer is not essential, and it is preferable that it not exist. The main part of the inner layer, particularly preferably the entire inner layer, consists of at least one layer of thermoplastic resin.

It is preferable that this thermoplastic resin layer is dusty in the main portion of the entire synthetic resin layer. That is, at least %, preferably % or more of the total thickness of the synthetic resin layer is made of thermoplastic resin. The thickness of the outermost crosslinked synthetic resin layer is preferably less than 1/2, particularly less than 1/1, more preferably 1/100 to 115 of the total thickness of the synthetic resin layer. Although the thickness of the outermost layer is not particularly limited, it is preferably less than 0.5 layers, particularly less than 0.2 layers. Although the thickness of the entire synthetic resin layer is not particularly limited, it is preferably 0.2 layers or more, particularly 0.4 to 10 m. It is preferable that all or almost all of the synthetic resin layer be made of polyurethane-based synthetic resin. That is, it is preferable that the outermost layer is made of a crosslinked polyurethane synthetic resin crosslinked by an action other than heat, and that the main part of the inner layer, especially all of the inner layer, is made of a thermoplastic polyurethane synthetic resin.

These polyurethane-based synthetic resins will be described later.

In the present invention, the hard substrate layer is made of a sheet material harder than the synthetic resin of the synthetic resin layer, such as a sheet of glass (ie, inorganic glass), 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 space between the two hard substrates may consist of a soft material such as polyvinyl butyral. In the case of a glass sheet, it may be strengthened, such as by air tempering or chemical strengthening, and may have a thin film layer, such as an anti-reflection coating, on its exposed surface. In the case of an organic glass sheet, a treatment such as stretching may be performed, and the exposed surface thereof may have a thin film layer such as a hard coat layer. Furthermore, these rigid substrates may be colored in whole or in part, and may have patterned and partially opaque areas. The overall thickness of these hard substrates is preferably 0.5 knots or more, particularly about 1 to 50 knots, but is not limited to this.

Although various methods can be considered for manufacturing the laminated safety glass of the present invention, the present inventor has found that the following three methods are particularly preferable. Of course, the method for manufacturing the laminated safety glass of the present invention is not limited to these three methods, but for reasons such as the performance of the laminated safety glass to be manufactured, ease of manufacture, or economic efficiency, these three methods may be used. It is preferable to adopt one of the following.

(2) A method in which an uncrosslinked synthetic resin and a thermoplastic resin are preliminarily laminated or simultaneously laminated on a hard substrate without prelaminating, and the uncrosslinked synthetic resin is crosslinked simultaneously with or after the lamination.

(2) A method of laminating a pre-laminated sheet having a crosslinked synthetic resin layer and a thermoplastic resin layer and a hard substrate, or laminating at least three of the crosslinked synthetic resin, the thermoplastic resin, and the hard substrate at the same time.

■ A method in which laminated safety glass is manufactured by laminating a hard substrate and a synthetic resin that does not have crosslinkable or crosslinked synthetic resin, and then a layer made of crosslinked synthetic resin is formed on the synthetic resin surface of the laminated safety glass.

When laminating synthetic resins together or laminating synthetic resins and hard substrates, heating and pressing is usually the most common and easiest method, and this lamination method is also adopted in the above method. is preferred. If the uncrosslinked synthetic resin has thermoplasticity and crosslinking is difficult to proceed under heat and pressure, this crosslinkable synthetic resin can be treated almost in the same way as a thermoplastic resin. This method of laminating multiple layers by heating and pressing (hereinafter also referred to as thermocompression bonding) can be used. In this sense, it is also possible to manufacture the laminated safety glass of the present invention using a crosslinked synthetic resin crosslinked by an action other than heat, while the crosslinkable synthetic resin is crosslinked by an action other than heat, especially light or moisture. However, thermocompression bonding in the presence of the above-mentioned uncrosslinked crosslinkable synthetic resin is not necessarily required in the method for manufacturing the laminated safety glass of the present invention.

For example, a pre-laminated sheet having a layer of cross-linkable synthetic resin and a layer of thermoplastic resin cross-linked by an action other than heat is manufactured by a method other than thermo-compression bonding, and this pre-laminated sheet and a rigid substrate are laminated by thermo-compression bonding. It is also possible to produce the laminated safety glass of the present invention by the method (an example of the method No. 1 above). However, in the case of method (2), it is usually advantageous to produce the pre-laminated sheet by thermo-compression bonding, and the pre-laminated sheet is produced by thermo-compression bonding using an uncrosslinked crosslinkable synthetic resin. It is preferable.

The first two of the above three manufacturing methods can be further divided into the following two types depending on whether preliminary lamination of synthetic resin is performed or not.

[First method] 1-a A pre-laminated sheet having an uncrosslinked crosslinkable synthetic resin layer that crosslinks by an action other than heat and a thermoplastic resin layer and a hard substrate are laminated by thermocompression bonding or the like. Laminated safety glass can be produced by crosslinking the crosslinkable synthetic resin simultaneously with lamination or after lamination. The pre-laminated sheet can be prepared by laminating at least two sheets or films of crosslinkable synthetic resin and thermoplastic resin by heating and pressing, or by laminating the crosslinkable synthetic resin and thermoplastic resin together. It can be manufactured by directly forming a pre-laminated sheet by extrusion molding or the like, but of course it can also be manufactured by casting one sheet or film onto the other.

Crosslinking of the crosslinkable synthetic resin is preferably carried out after laminating the pre-laminated sheet and the hard substrate, but a transparent mold material such as a glass sheet, which will be described later, is used as the mold material and is irradiated with light such as ultraviolet rays during lamination. It is possible to carry out crosslinking at the same time.

1-b A method can be used in which at least three of a crosslinkable synthetic resin sheet or film, a thermoplastic resin sheet or film, and a hard substrate are simultaneously laminated without using a pre-laminated sheet. After that, as in the case of a, the crosslinkable synthetic resin is crosslinked at the same time as this lamination or after this lamination.

[Method of ■]

1 [-a Laminated safety glass can be manufactured by a method of laminating a hard substrate and a pre-laminated sheet having a crosslinked synthetic resin layer crosslinked by an action other than heat. This pre-laminated sheet is produced by the method of crosslinking a pre-laminated sheet having a cross-linkable synthetic resin layer as explained in I-a above, or by lamination or co-extrusion using a cross-linked synthetic resin, its sheet or film. be able to.

■-) Manufacture laminated safety glass by laminating at least 6 components at the same time: a crosslinked synthetic resin sheet or film, a thermoplastic resin sheet or film, and a rigid substrate without using a preformed sheet. I can do it.

Note that method (2) also includes a method of forming a crosslinkable synthetic resin layer on the thermoplastic resin surface of laminated safety glass and then crosslinking it, a method of directly forming a crosslinked crosslinking base-synthetic resin layer,
The outermost crosslinked synthetic resin layer is formed by laminating a preliminary laminate having an uncrosslinked or crosslinked synthetic resin layer and a thermoplastic resin and then crosslinking the uncrosslinked layers to form a crosslinked synthetic resin layer. can be formed.

As mentioned above, when laminating a rigid substrate and a pre-laminated sheet or a thermoplastic resin sheet or film, or simultaneously laminating other crosslinkable or crosslinked synthetic resin sheets or films. In this case, thermocompression bonding is the most preferred method. In the case of this thermocompression bonding, the surface in contact with the hard substrate needs to be made of thermoplastic resin. Thermocompression bonding in the lamination of at least two materials is usually carried out in order to remove air, etc. that exists between the thermoplastic resin and the hard substrate. This is carried out through a preliminary press-bonding step in which the pressure is reduced and degassed at room temperature to 100° C. or less, and a main press-bond step in which the laminated assembly is thermocompression bonded under heat and pressure. Specifically, for example, one or more thermoplastic resin sheets or films are layered on a hard substrate, and then a mold material with a smooth surface, such as a mold release-treated glass sheet, rubber sheet, or plastic sheet, is layered on top of that. , metal sheets, etc. are stacked, the laminated assembly is placed in a rubber pre-crimping device, the inside of the crimp bag is evacuated and preliminary crimping is performed, and then the pre-crimped laminate is placed with or without removing the form material. The thermocompression bonding is performed by placing it in an autoclave and applying heat and pressure to perform the main compression bonding. Such preliminary crimping is
Normally, after reducing the pressure inside the pre-crimping device to about 700 WIHg or less, for example 200 to 650 tmHg,
It is carried out by heating to a temperature below .degree. C., for example, room temperature to 90.degree.

In addition, the main crimping is usually performed at a temperature ranging from about 60°C at the lowest until the thermoplastic resin melts, for example, if the thermoplastic resin is a polyurethane thermoplastic resin, the temperature is about 80 to 150°C, and the pressure is 2Kf/crn2. For example, in the case of a polyurethane thermoplastic resin, it is preferable to carry out the reaction under a pressure of about 7 to 20 K17 cm2. These conditions may vary depending on the type of thermoplastic resin or 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 the laminated assembly against 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, the main crimping method is not limited to the method of thermo-compression bonding using an autoclave. It can also be carried out by a method of pressing with a roll, a method of pressing a laminated assembly under heating, a method of performing the above-mentioned double vacuum pressing method under heating, and the like. In addition, during thermocompression bonding, especially in the preliminary crimping step, it is preferable to place the above-mentioned mold material on top of the thermoplastic resin, excluding the crimping strip, so that sufficient crimping can be performed and a smooth surface can be obtained. Depending on the type and purpose of the method, the use of such a mold material may be omitted. In addition, thermocompression bonding between a thermoplastic resin and a hard substrate is most commonly carried out through a preliminary compression bonding process and a main compression bonding process. Depending on conditions such as the thickness and size of the unit, thermocompression bonding may be performed in one step without going through both the preliminary compression bonding process and the main compression bonding process.

Lamination by thermocompression bonding as described above is not the only method of manufacturing laminated safety glass. However, compared to other methods, it is possible to obtain higher adhesive strength between the thermoplastic resin and the hard substrate, and because the thermoplastic resin can be formed into a sheet or film in advance, it is smooth and has good optical properties. There are various advantages such as being able to obtain a smooth thermoplastic resin layer, and obtaining a smoother surface by pressing the thermoplastic resin layer or the crosslinkable synthetic resin layer thereon with a mold material during thermocompression bonding. .

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, from the viewpoint of transparency, impact resistance, penetration resistance, and other physical properties, polyurethane-based thermoplastic resins are most preferred.

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 incyanate group and an active hydrogen-containing group such as a urea group, an allophanate group, or a billet group. Further, it may have an incyanurate group, a carbodiimide group, or another group derived from an incyanate group. Furthermore, the high molecular weight polyol itself may contain ester groups, ether groups, carbonate groups, or other groups, but it may also contain groups resulting from compounds such as chain extenders and crosslinking agents. be.

Polyurethane thermoplastic resins are basically linear polymers obtained by reacting high molecular weight diols, chain extenders, and diisocyanate compounds. However, a small amount of branching may be present, for example a predominantly linear structure with a small amount of branching may be obtained by using trifunctional or higher functional polyols, cross-linking agents or polyisocyanates in combination with the above bifunctional compounds. It may also be a polymer. 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 agent,
Colorants, 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), and the like.

In addition, 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 often preferable. . 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 weight is not particularly limited, but is 600 to 8000, particularly 800 to 4000.
It is preferable that

The chain extender is a relatively low molecular weight divalent compound, such as a diol, diamine, divalent alkanolamine,
It is a compound having two other hydroxyl groups or two amino groups.

Although its molecular weight is not particularly limited, it is preferably 400 or less, particularly 200 or less. Diols such as dihydric alcohols, polyester diols, and polyether diols can be used as diols, especially diols having 2 to 6 carbon atoms.
Hydrolic alcohols are preferred. As the diamine, aliphatic, alicyclic, aromatic, and other diamines can be used. As the alkanolamine, divalent alkanolamines such as N-alkylgetanolamine 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 compounds of each of the high molecular weight diol and the chain extender 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 incyanate group directly bonded to an aromatic nucleus may cause yellowing of the obtained polyurethane, diisocyanate without such an incyanate group, a diisocyanate that is usually called a non-yellowing type, is preferable. For example, preferred diisocyanates include hexamethylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexylmethane diisocyanate, inholone diisocyanate, xylylene diisocyanate, and modified diincyanates obtained by modifying these with various compounds or treatments.

As the crosslinkable synthetic resin, polyurethane-based synthetic resins are preferred as mentioned above. Particularly preferred is a polyurethane-based synthetic resin obtained by introducing a crosslinkable group that can be crosslinked by an action other than heat into the polyurethane-based thermoplastic resin.

Some crosslinkable polyurethane synthetic resins that can be crosslinked by effects other than heat are known, for example, polyurethane synthetic resins that can be photocrosslinked are known. This photocrosslinkable polyurethane synthetic resin is made of a liquid resin such as acrylic modified polyurethane or an acrylic monomer in which polyurethane is dissolved (for example, see Japanese Patent Application Laid-open No. 149348/1983), and is crosslinked by curing with light irradiation. Polyurethane is obtained. This cross-linkable synthetic resin, which becomes a cross-linked synthetic resin from this liquid resin without passing through an uncross-linked solid resin having thermoplastic properties, may be applicable to the above-mentioned method (1), method (2), etc. It can also be used in the present invention. However, as mentioned above, it is preferable to use an uncrosslinked solid resin having thermoplastic properties.
This crosslinkable synthetic resin will be mainly explained below.

Preferably, the uncrosslinked solid synthetic resin has thermoplasticity. This is because sheets and films can be easily manufactured by extrusion molding etc. due to their thermoplasticity. Still, a sheet or film having at least a two-layer structure can be obtained by coextruding the thermoplastic resin and this uncrosslinked thermoplastic crosslinkable synthetic resin. The crosslinkable synthetic resin is particularly preferably a polyurethane-based synthetic resin, which can be obtained by introducing a functional group that can be crosslinked by light, moisture, etc., ie, a crosslinkable group, into the polyurethane thermoplastic resin. The polyurethane thermoplastic resin has a reactive functional group such as a urethane group, and a crosslinking group can be introduced into it, but preferably a more active group, that is, a crosslinking group is introduced. It is preferable to use a synthetic resin having a kanji group, which is easy to use. For example, a polyurethane thermoplastic resin can be produced using a diol having a carboxylic acid group, and the carboxylic acid group facilitates the introduction of a crosslinking group. Dimethylolpropionic acid is particularly preferred as the diol having a carboxylic acid group, and is used as part of the chain extender. Furthermore, a polyurethane thermoplastic resin having a crosslinkable group can be produced using a compound having a group having active hydrogen such as 1 or 2 hydroxyl groups or amine groups and a crosslinkable group. For example, a polyurethane-based thermoplastic resin is created using mono- or di(meth)acrylic acid ester of trimethylolpropane as a chain extender, and a sensitizer is added to this to create a thermoplastic polyurethane-based resin that has photocrosslinkability. Synthetic resins can be produced. In the case of the above polyurethane thermoplastic resin having carboxylic acid groups,
Thermoplastics that can be crosslinked by light, moisture, etc. by reacting a compound that has a functional group that easily reacts with carboxylic acid groups such as an epoxy group or a glycidyl group and a crosslinkable group such as a cinnamic acid group or an alkoxysilyl group. Polyurethane-based synthetic resin can be used.

The laminated safety glass of the present invention is suitable for use as an automobile windshield, but is not limited to this.
Suitable as a window material for automobiles and other vehicles, and for buildings. EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples.

Reference Example CAJ moisture crosslinkable polyurethane production side hydroxyl value 54.
3■Hg of polybutylene adipate 15001F
Dehydration was performed under vacuum at 110° C. for 2 hours. To this, 4,4' methylene-bis(cyclohexyl isocyanate) ts42
1F and di-n-butyltin dilaurate 0.33
f was added and reacted for 15 minutes at 80°C under a nitrogen stream. Next, 1,4-butanediol 1211,
Dimethylolpropionic acid 451 was added and mixed quickly with stirring. 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 resulting polymer was kneaded with 799% of γ-glycidoxychlorotrimethoxysilane and 0.72% of N,N'-dimethylaniline in a double-arm kneader at 180° C. under a nitrogen atmosphere. The mixed material was then crushed and granulated using a crusher. Hereinafter, this moisture-crosslinkable polyurethane will be referred to as polyurethane (A).

[B] Production side of photocrosslinkable polyurethane Polybutylene adipate 1500S' with a hydroxyl value of 56,
A polyurethane was prepared in the same manner as in Reference Example A using Inphoron diisocyanate 9081, 1,4-butanediol 2441, dimethylolpropionic acid 75f, and 0.16 t of di-n-butyltin dilaure.

This was mixed with glycidyl cinnamate 1101, triethylamine 301.2.2, dimethoxy 2-7 enylacetophenone 451 in a double-arm kneader in the same manner as in the reference example to obtain a granulated product.

Hereinafter, this photocrosslinkable polyurethane will be referred to as polyurethane (B).
That's what it means.

[C] Production of photocrosslinkable polyurethane Polybutylene adipate 15001F having a hydroxyl value of 73 was dehydrated under vacuum at 110° C. for 2 hours under 3 g of Hg. To this, '4.4'-methylenebis(cyclohexyl isocyanate) 9505F and 0.16r of di-n-butyl tin dilaure were added and reacted for 15 minutes at 80°C under a nitrogen stream.

This reaction mixture [203 g of 1,4-butanediol, 75 g of acrylic acid monoester of trimethylolpropane
, benzoin methyl ether 30f were added, and after reacting for several minutes, the liquid reaction mixture was poured into a Teflon-coated vat, and the urethane reaction was completed at 100°C. The product was ground and granulated in a grinder. Hereinafter, this photocrosslinkable polyurethane will be referred to as polyurethane (0).

Example 1 Polyethylene adipate 1500f, 4 with a hydroxyl value of 56
．． A polyurethane was produced in the same manner as in Reference Example A using 4'-methylene bis(cyclohexyl isocyanate) 1731F, 1.4butanediol 327f, 18F, and 18F. was granulated to produce thermoplastic polyurethane. This thermoplastic polyurethane and the polyurethane obtained in Reference Example A (A
), a laminate sheet with a thickness of (16111111) having a moisture crosslinkable layer of α05 on one side was produced by coextrusion.Next, using this sheet,
A two-layer laminate of Gansu plastic sheets was made in the following manner. First, place the sheet between two glass plates. At this time, the surface of the glass in contact with the moisture-crosslinkable surface of the sheet is coated uniformly with polydimethylsiloxane in advance.
Heat treatment was performed at 0°C. This non-adhesive glass laminate was placed in a rubber bag, and the bag was placed in an autoclave. Initially, both the rubber bag and the autoclave were evacuated to remove the air between the glass and the sheet. Next, autoclave 1
By heating to 00℃ and returning only the inside of the autoclave to atmospheric pressure while keeping the inside of the rubber bag vacuum, 1Kg/I:
A pressure of rn2 was applied. After this state was maintained for 15 minutes, the autoclave was set to 140° C. and 13K47 cm 2 and maintained for 20 minutes. After taking out the glass laminate from the autoclave, by removing the polydimethylsiloxane-treated glass, the exposed surface of the polyurethane sheet is as smooth as glass, creating a pie layer that has good adhesion to the glass. I made it.

Next, this Pylayer glass was immersed in hot water at 90°C for 30 minutes, then transferred to a dryer at 120°C and dried under a nitrogen atmosphere for 15 minutes.

Ethanol/methanol-1o/1 (v/v) carbon tetrachloride on the polyurethane sheet surface of this Pylayer glass.
When a rubbing test was carried out by dyeing each of kerosene and gasoline with 7 elt, no change was observed even after rubbing 1000 times, and no increase in haze was observed.

Further, when a taper test was conducted based on J Engineering EIR 3212, the increase in haze after 100 cycles was 2.6%. Also, in a falling ball test based on J-K5R3212, the steel balls did not penetrate and showed sufficient penetration resistance.

Comparative Example In Example 1, pie layer glass was prepared using only the thermoplastic polyurethane prepared in Example 1 without using polyurethane (4), and the same heat treatment as in Example 1 was performed. Ethanol/methanol-10/1 (V/V
) When an iC rubbing test was conducted, the film was damaged and a 35% increase in haze was observed after 1000 times.

Example 2 Thermoplastic polyurethane made in Example 1 and Reference Example B
Using the granulated polyurethane (B) obtained in Example 1, a 0.6-mist polyurethane sheet having a 0.0!5 m+ photocrosslinkable layer on the exposed surface of the polyurethane sheet was prepared. A pie layer glass containing a layer of .

Next, the surface of the polyurethane sheet of the Pylayer glass was irradiated with light from a high-pressure mercury lamp from a distance of 5 m for 20 minutes. This Pylayer glass showed the same performance as Example 1 in the other tests, except that the haze increase in the taper test was 28%.

Example 3 Using the thermoplastic polyurethane produced in Example 1 and the granulated polyurethane (C) obtained in Reference Example C, the same coextrusion method as in Example 1 was used to obtain a photocrosslinking property of 0.05+o+ on one side. A 0.6 wn polyurethane sheet with a layer of 0.6 wn was produced. Using this polyurethane sheet, Example 1
Pylayer glass was produced in the same manner as in Example 2, and then irradiated with light in the same manner as in Example 2. A pie layer glass having the same performance as Example 1 was obtained, except that the increase in haze in the taper test was 3.0 inches.

Example 4 A 0.6 M thick polyurethane sheet having a moisture-crosslinkable layer on one side obtained in Example 1 was immersed in hot water at 90°C for 60 minutes and then dried at 120°C for 15 minutes.

The obtained polyurethane sheet having a crosslinked layer on one side was laminated with a sheet of glass using the same lamination method as in Example 1 to produce pie layer glass. The same test as Example 1 for this Pylayer glass showed that the haze increase due to the taper test was 2.
It had the same performance as the Pylayer glass of Example 1, except for the 7th layer.

Example 5 The photocrosslinkable layer of the polyurethane sheet having a photocrosslinkable layer on one side and having a photocrosslinkable layer on one side obtained in Example 2 was irradiated with light for 95 minutes from above the photocrosslinkable layer. Using this polyurethane sheet, pie layer glass was manufactured using the same lamination method as in Example 1. This Pylayer glass had the same properties as the Pylayer glass of Example 1, except that the haze increase in the taper test was 2.8%.

Example 6 Using the polyurethane sheet obtained in Example 3 and having a photocrosslinkable layer on one side and having a thickness of α6, the sheet was photocrosslinked in the same manner as in Example 5, and then laminated with glass to form a pie layer glass. was manufactured. This Pylayer glass had properties similar to the Pylayer glass of Example 1, except that the haze increase in the taper test was 40%.

Example 7 A 0.05 tan film was produced by extrusion molding from polyurethane A obtained in Reference Example [A).

A film of A and a sheet of thermoplastic polyurethane produced in Example 1 were laminated by thermocompression bonding, and using this laminated sheet, the same method as in Example 1 was carried out so that the polyurethane A film was the exposed surface. Then, a pie layer glass was attached, hot water treatment, and drying were performed. The pie layer glass exhibited similar performance to that of Example 1.

Example 8 A 9Q, 05m+ film was produced from polyurethane B obtained in Reference Example CB'J by extrusion molding.

This film and the thermoplastic polyurethane sheet produced in Example 1 were laminated by thermocompression bonding, and using this laminated sheet, the same method as in Example 1 was carried out so that the polyurethane B film was the exposed surface. I made pie layer glass. Next, the surface of the polyurethane sheet of the Pylayer glass was irradiated with light from a high-pressure mercury lamp for 20 minutes from a distance of 5 crn. This pie layer glass exhibited the same performance as the pie layer glass in Example 2.

[Brief explanation of the drawing]

Figures 1 to 3 are cross-sectional views showing schematic cross-sections of the laminated safety glass of the present invention. FIG. 3 shows a laminated safety glass having a two-layered synthetic resin layer and a three-layered hard base layer. 1...Synthetic resin layer 2...Hard base layer 5...
Crosslinked synthetic resin layer 4... thermoplastic resin layer agent 1
) Ming

Claims (1)

[Claims] 1. A transparent or translucent laminated safety glass having at least a three-layer structure consisting of at least a two-layer synthetic resin layer with an exposed surface and a hard substrate layer, wherein the synthetic resin layer is on the exposed surface. and at least one thick inner layer, the outermost layer being a crosslinked synthetic resin layer crosslinked by an action other than heat, and the main part of the inner layer being a thermoplastic resin layer. Laminated safety glass featuring: Z. The laminated safety glass according to claim 1, wherein the synthetic resin crosslinked by an action other than heat is a synthetic resin crosslinked by light or moisture. 3. The laminated safety glass according to claim 1, wherein the thickness of the outermost layer is less than or equal to the thickness of the entire synthetic resin layer. 4. The laminated safety glass according to claim 1, wherein the crosslinked synthetic resin is a polyurethane-based crosslinked synthetic resin. 5. The laminated safety glass according to claim 1, wherein the thermoplastic resin is a polyurethane thermoplastic resin. 6. The laminated safety glass according to claim 1, wherein the hard substrate layer is composed of at least one inorganic glass layer. Z: Crosslinking property that can be crosslinked by an action other than heat in a method for producing transparent or translucent laminated safety glass having at least a three-layer structure consisting of at least a two-layer synthetic resin layer with an exposed surface and a hard substrate layer. A laminated synthetic resin having at least a two-layer structure having a thin layer of synthetic resin on one surface, the main part of which is a thermoplastic resin, and a hard substrate; 1. A method for manufacturing laminated safety glass, which comprises laminating the glass directly or via a second synthetic resin, using the surface that does not have a lamination surface as a lamination surface, and crosslinking the crosslinkable synthetic resin during or after the lamination. The method according to claim 7, wherein the laminated synthetic resin having at least a two-layer structure is obtained by laminating a thermoplastic crosslinkable synthetic resin and a thermoplastic synthetic resin. 9. The method according to claim 8, wherein the λ lamination is a lamination by coextrusion. 10. In the method for producing transparent or semi-transparent laminated safety glass having at least a three-layer structure of at least a two-layer synthetic resin layer with an exposed surface and a hard substrate layer, cross-linked synthetic resin cross-linked by an action other than heat. A laminated synthetic resin having at least a two-layer structure having a thin layer of resin on one surface, the main part of which is a thermoplastic resin, and a rigid substrate, the laminated synthetic resin not having a thin layer of the crosslinked synthetic resin. A method for manufacturing laminated safety glass, which comprises laminating the glass directly or via a second synthetic resin, using the surface as the lamination surface.