JPH0578416B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to automobile windshields and laminated safety glass for vehicles and buildings. [Prior Art] Important requirements for a structure called laminated safety glass are impact resistance and penetration resistance. Conventionally,
In HPR laminated glass (High Penetration Resistance), known as automobile windshield glass, the adhesive strength between the glass plate and the plastic interlayer is lower than that of ordinary laminated glass in order to satisfy penetration resistance. This has been effective. That is, if the adhesive force between the glass plate and the plastic interlayer film is too high, the plastic interlayer film will be extremely susceptible to breakage because the elongation deformation of the plastic interlayer film will be restrained upon impact, leading to penetration. However, on the other hand, lowering the adhesive strength between the glass plate and the plastic interlayer film prevents mechanical vibrations acting through the mounting members (gaskets and sealing materials) at the periphery of the joint, and penetration through the end surfaces of the laminate. The current situation is that it is easily affected by moisture, etc., and in many cases this appears as defects such as peeling and foaming. These situations also apply to tear-resistant glass laminates made by bonding a glass plate and a plastic film together via an adhesive intermediate layer, or by bonding a glass plate and a plastic film. [Problems to be Solved by the Invention] The present invention provides a glass laminate in which a glass plate and a plastic film are bonded together via an adhesive intermediate layer;
Alternatively, the purpose is to improve the penetration resistance of a tear-resistant glass laminate made by bonding a glass plate and a plastic film, and to improve defects such as peeling and foaming in the peripheral area. [Means for Solving the Problems] The present invention was invented as a result of studies based on the above-mentioned objectives, and its gist is to bond a glass plate and a plastic film through an adhesive intermediate layer. In a glass laminate formed by bonding a glass plate and a plastic film, the adhesive force between the glass plate and the adhesive intermediate layer at the periphery of the glass laminate, or the adhesive force between the glass plate and the plastic film. The present invention relates to a glass laminate characterized in that the adhesive strength of the bonding surface with the glass laminate is higher than that of the inside of the surface excluding the periphery. Hereinafter, the present invention will be explained in detail with reference to the drawings. Figure 1 shows glass plate 1 and plastic film 2.
FIG. 2 shows a cross-sectional view of a glass laminate 4 formed by bonding a glass plate 1 and a plastic film 2 together via an adhesive intermediate layer 3. FIG. 3 is a plan view of a glass laminate 4 for a front window of an automobile, in which the adhesive strength of the peripheral portion 5 of the glass laminate 4 is higher than that of the inner surface 6 of the glass laminate 4. The figure is shown below. The glass plate 1 in the present invention may be a raw glass plate, or may be one that has been subjected to peripheral reinforcement processing, semi-reinforcement processing, partial reinforcement processing, or full reinforcement processing, or may be bent into various shapes. It may be a processed one. Alternatively, the glass plate may be partially or entirely coated with a transparent, translucent, or opaque surface coating such as a heat-reflecting coating, a conductive coating, or a colored coating. The thickness of the glass plate is about 1.0 to 20 mm, and preferably about 2.0 to 6.0 mm, especially for automobile window glass. The plastic film 2 may be a thermoplastic plastic film, a thermosetting plastic film, a plastic film made of multiple layers of thermoplastic plastic film and thermosetting plastic film, or an adhesive intermediate film on the laminated surface side of the glass plate. Various transparent plastic films can be used, such as a plastic film on which the layer 3 is formed, a plastic film on which various treatments have been applied, and the like. The plastic film may be partially coated with a colored coat, a heat ray reflective coat, a conductive coat, a surface hardening coat, or various other functional coats. More specifically, transparent plastic films such as polyethylene terephthalate film, nylon film, etc. have functions such as reducing skin damage caused by damage to glass plates during collisions, and also have functions such as penetration resistance and scratch resistance. Laminated plastic film of self-healing thermosetting polyurethane film with adhesive interlayer such as polyvinyl butyral or ethylene-vinyl acetate copolymer, or polyethylene terephthalate or nylon with an adhesive layer on the side that is laminated with the glass plate. film,
A plastic film such as a self-healing thermosetting urethane, or a single-layer or multi-layer film of polyurethane, such as a plastic that has a thermoplastic urethane side on the side laminated with a glass plate and a self-healing thermosetting urethane layer on the outside. Typical examples include film and plastic film made of thermoplastic urethane whose surface has been modified. In the present invention, the glass laminate 4 is constructed by bonding the glass plate 1 and the plastic film 2 described above together.
The adhesive force of the peripheral part 5 having a width of 150 mm is controlled to be higher than the adhesive force of the inner surface 6 inside the peripheral part 5. This adhesive force is the adhesive force of the bonding surface of the glass plate 1 with the plastic film, or when the adhesive intermediate layer 4 is interposed between the glass plate 1 and the plastic film 2 to bond them, It indicates the adhesive force between the glass plate 1 and the adhesive intermediate layer 4, and in the present invention, this adhesive force is expressed as 180° peel adhesive force (Kg/
cm). In the present invention, the adhesive force at the peripheral portion of the glass laminate is in the range of 3 to 6 kg/cm. If the adhesive strength is lower than 3 kg/cm, the adhesive strength will be insufficient, and moisture will enter through the end face of the glass laminate, causing peeling, foaming, etc., which is undesirable, and if it is higher than 6 kg/cm, the penetration resistance will be poor. decreases, which is not desirable. The adhesive force within the plane of the glass laminate is in the range of 0.5 to 2 kg/cm. This adhesive force
If it is less than 0.5, the adhesive force will be insufficient and peeling or foaming will occur on the mating surfaces, which is undesirable. If it is more than 2 kg/cm, it will greatly affect the decrease in penetration resistance, which is undesirable. The glass plate of the present invention is produced by stacking a plastic film on a glass plate that has been sufficiently washed, dried, and dust removed, and if necessary, stacking a cover glass plate as a pressing plate on top of the plastic film, and placing this laminate in a pressure bag. Typical examples include, but are not limited to, methods such as deaerating the material, pre-pressing it by heating if necessary, and then taking it out of the crimping bag or putting it in an autoclave as it is and heat-pressing it. It is also possible to use other methods for bonding various types of laminated glass. One way to make the adhesive strength of the peripheral part 5 higher than that of the inner surface 6 excluding the peripheral part 5 is to treat the glass plate side, the adhesive intermediate layer, or the plastic film side of the peripheral part with a silane coupling agent. It can be raised. Examples of silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, and vinyltriethoxysilane. , vinyl-tris(β-methoxyethoxy)silane, β-(3,
4-epoxycyclohexyl)ethyl-trimethoxysilane, vinyltriacetoxysilane, γ-
There are aminopropyltriethoxysilane and the like, and at least one of these may be used. Preferably, γ-glycidoxypropyltrimethoxysilane, which has good moisture resistance, is used. The silane coupling agent is diluted to 0.2 to 5 wt% with an organic solvent in which it can be stably dissolved, and applied to the glass plate side, adhesive intermediate layer, or plastic film side by brushing or dipping. Examples of organic solvents include methanol, ethanol, methylene chloride, and acetone. After treatment, air dry for 1 to 2 hours at room temperature. Thereafter, the glass plate and plastic film are laminated and uniformly thermocompressed, usually at 100 to 130°C, to obtain the desired adhesive strength distribution. Further, as a method for making the adhesive strength of the peripheral part 5 higher than the adhesive strength of the inside surface 6 excluding the peripheral part 5, there is a method of heat-treating only the peripheral part at a temperature 10 to 30 degrees Celsius higher than the inside of the surface. . In other words, crimping is performed at a relatively low temperature to satisfy penetration resistance on the inside of the surface except for the peripheral area.
A laminate that maintains durability can be obtained by increasing the compression temperature in the peripheral area. For example, the pressure bonding temperature is set to 100 to 130℃ on the inside of the surface except for the peripheral area, and the peripheral area is
Adhesive strength in the peripheral area can be increased by heat treatment at 130-150°C. In addition, when the above-mentioned method of applying a silane coupling agent to the glass plate side, adhesive intermediate layer, or plastic film side of the peripheral area and the above-mentioned heat treatment of the peripheral area are performed,
The higher the compression temperature of the silane coupling agent is, the more likely the condensation reaction will proceed, resulting in higher adhesion in the peripheral area. [Examples] Examples of the present invention will be described below. Example 1 In a laminate consisting of a glass plate 1 and a plastic film 2 having an adhesive intermediate layer 3 as shown in Fig. 1, the glass plate was a flat float glass plate (305 mm x 305 mm) with a thickness of 3 mm, and the plastic film was An example will be described using a glass laminate made of self-healing thermosetting polyurethane, the adhesive intermediate layer of which is based on thermoplastic polyurethane and containing 0.5% of a silane coupling agent. Methanol solutions with concentrations of 0.2 wt% and 1 wt% are prepared using A-187 (γ-glycidoxypropyltrimethoxysilane manufactured by UCC) as a silane coupling agent to strengthen the adhesive strength in the peripheral area. While washing the float glass in hot water and rinsing with distilled water, the bottom surface of the glass plate, which is the adhesive surface, is replaced with ethanol. The silane treatment was carried out by immersion, in which the glass plate side was treated and the plastic film side was treated, followed by air drying for 2 to 3 hours. This silane treatment was carried out over the entire circumference of the glass plate or plastic film in a width of 70 cm from the end thereof. Next, this was preliminarily crimped by a rubber bag crimping method, and then main crimping was carried out in an autoclave. Table 1 shows the state of adhesive strength depending on the thermocompression bonding conditions.
Shown as 180° peel adhesive strength (Kg/cm). The method of treating the glass side with a methanol solution with a silane concentration of 1% is stable, and preferably by thermocompression bonding conditions of 120° to 130°C, the untreated part can be heated to 2 kg/cm.
The silane-treated portion can exhibit an adhesive strength of 5 kg/cm. In other words, the untreated portion corresponds to the in-plane portion excluding the peripheral portion, and has an adhesive strength level that satisfies penetration resistance, and the peripheral portion has an adhesive strength that maintains durability due to the silane treatment.

[Table] Example 2 Using the method shown in Example 1, a glass plate was treated with a silane coupling agent around the periphery and heat-pressed at 120°C, resulting in an adhesive force of 4.8 Kg/cm for the entire periphery of 50 mm.
Also, 1.5 mm or more inside the surface inside the above peripheral area.
Glass laminates for full-size automobile windshields with an adhesive strength of ~1.7 Kg/cm were produced by a conventional rubber bag crimping method and an autoclave crimping method. Using a thread launcher, the dummy was made to collide with the plastic film side of the glass laminate at a speed of 42 km/h and a glass temperature of 20°C. There was no penetration of the specimen, and the brain damage values of the dummy doll were almost the same as those of the specimen adjusted to a uniform adhesive force of 1.5 to 2.0 kg/cm over the entire surface, indicating that there was no adverse effect due to increasing the peripheral adhesive force. It wasn't recognized. Example 3 By the method shown in Example 1, the peripheral area 50mm was made 4.8
305mm
Two mm samples were exposed outdoors and aged using a Sunshine Weather-Ometer, and then subjected to an adhesion test. Outdoor exposure (in Yokohama, facing south, 45° from vertical)
After one year (tilt), the average adhesion strength of the two specimens at the periphery remained almost unchanged at 4.4 Kg/cm, and at the center remained unchanged at 1.6 Kg/cm. Also, 1000 on Sunshine Weather Ometer
The average adhesion force at the periphery after time exposure is 3.9Kg/cm
There was also a slight decline in the center area to 1.1Kg/cm.However, both in the case of outdoor exposure and Sunshine Weather-Ometer, peeling, foaming, and optical damage occurred in both the peripheral and central areas. There were no mechanical defects. As can be seen from the data of the sample without treatment with a silane coupling agent in Table 1, an adhesive strength of 4 to 5 kg/cm can be achieved by increasing the pressure bonding temperature even without silane treatment to strengthen the peripheral adhesive strength. In addition, a low level of adhesion that satisfies penetration resistance can be obtained on the inside of the surface. From this, the ambient temperature during thermocompression bonding using a full-sized automobile windshield was determined to be 10
A desired adhesive force distribution can be obtained by increasing the temperature by ~30°C. Similar to Example 2, no problems were found when a penetration resistance test was conducted on the glass laminate for automobile windshields produced by this method using a thread firing device. [Effects of the Invention] As described above, according to the present invention, in a glass laminate with improved safety in which a glass plate and a plastic film are bonded together, the glass plate in the peripheral portion and the adhesive interlayer film or the glass plate are bonded together. Since the adhesive force between the surface and the plastic film is stronger than that inside the surface, it is possible to satisfy both performance of penetration resistance and durability. Since the glass laminate of the present invention has such performance, it is particularly suitable for windshield glass for front windows, which requires high safety in the event of a collision for vehicle occupants.

[Brief explanation of drawings]

1 and 2 show a cross-sectional view of a glass laminate according to a specific example of the present invention, and FIG. 3 shows a plan view of the glass laminate for a front window of an automobile of the present invention. 1: Glass plate, 2: Plastic film,
3: Adhesive interlayer film, 4: Glass laminate, 5: Periphery of glass laminate, 6: Inside surface of glass laminate.

Claims (1)

[Scope of Claims] 1. A glass laminate in which a glass plate and a plastic film are bonded together via an adhesive intermediate layer, or a glass laminate in which a glass plate and a plastic film are bonded together. 180° peel adhesion of the adhesive force between the glass plate and the adhesive intermediate layer, or the adhesive force of the bonding surface between the glass plate and the plastic film, in the peripheral area with a width of 20 to 150 mm from the edge of the glass plate. 3-6 by force
Kg/cm ² , and the adhesive strength within the surface excluding the periphery is 0.5 to 2 Kg/cm ² in terms of 180° peel adhesive strength. 2. The glass laminate according to claim 1, wherein the plastic film is a thermosetting urethane film having self-repairing properties. 3. The glass laminate according to claim 1, wherein the plastic film is composed of a two-layered film of thermosetting urethane and thermoplastic urethane having self-healing properties. 4. The glass laminate according to claim 1, wherein the adhesive intermediate layer is made of at least one member selected from the group of thermoplastic urethane, polyvinyl butyral, and ethylene vinyl acetate copolymer. 5. The glass laminate according to claim 1, wherein the plastic film is a polyethylene terephthalate film.