JP3135197B2 - Glass resin composite board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent glass-resin composite plate which is used for a window glass of an automobile or a viewing window of machinery and has an improved intermediate layer between a glass plate and a polycarbonate resin plate.

[0002]

2. Description of the Related Art Since glass plates generally have poor impact resistance, laminated glass in which two glass plates are bonded and reinforced with an intermediate layer of a polyvinyl butyral adhesive is used for window glass for automobiles. ing. The applicant has already proposed a transparent composite plate in which a glass plate and a polycarbonate resin plate are bonded with a hot-melt polyurethane adhesive and a method for producing the same (Japanese Patent Application No. 6-142596). Glass resin composite board has excellent transparency,
It is toughened by the impact resistance of the polycarbonate resin, and is characterized by being lighter than laminated glass of the same thickness.

[0003] A polyvinyl butyral adhesive used for bonding a glass plate is formed by adding a plasticizer to polyvinyl butyral and is spread in a film form. When bonding, the adhesive film is sandwiched between glass plates and heated. It was softened and pressed by a press or a roll. The intermediate layer had impact resistance, heat resistance and cold resistance, and had good adhesion to a glass plate.

When this polyvinyl butyral adhesive is used as an intermediate layer for bonding a glass plate and a polycarbonate resin plate, the plasticizer in the intermediate layer of the adhesive migrates and permeates into the polycarbonate resin plate to form an adhesive. There is a problem that the polycarbonate resin plate is whitened within a short period of time after molding, and the transparency of the composite plate is reduced.

On the other hand, the above-mentioned glass-resin composite board utilizes a hot-melt polyurethane adhesive for the intermediate layer in order to cope with whitening of the polycarbonate resin board. Although there was no problem of devitrification to the resin plate and the adhesion to the polycarbonate resin plate was good, it was considerably more expensive than the polyvinyl butyral adhesive. In particular, the intermediate layer of the composite plate absorbs the difference in thermal expansion and contraction between the glass plate and the polycarbonate resin plate to reduce distortion, and also increases the energy absorbed at the time of impact to reduce the impact. Therefore, it is necessary to make the intermediate layer thick, and in such a composite plate, there is a problem that the use of a hot-melt polyurethane adhesive increases the bonding cost.

Further, the hot-melt polyurethane-based adhesive has a property that its adhesive strength to glass is still insufficient as compared with the adhesive strength to a resin such as a polycarbonate resin plate, and the hot melt polyurethane adhesive has an impact on an intermediate layer of the glass plate. It was necessary to improve the peel strength.

In view of the above problems, the present invention provides a transparent composite plate of a polycarbonate resin plate and a glass plate which has high impact resistance and adhesive strength, maintains good transparency over a long period of time, and has a low bonding cost. It is something to offer.

[0008]

The transparent composite plate of the present invention is a glass resin composite plate in which a glass plate and a polycarbonate resin plate are bonded and integrated via an intermediate layer.
The intermediate layer is formed of two layers, a polyvinyl butyral adhesive layer on the glass plate side and a hot melt polyurethane adhesive layer on the resin plate side.

FIG. 1 schematically shows the basic structure of the transparent composite plate of the present invention. Since the polycarbonate resin plate 2 has a high impact resistance, it is bonded to the glass plate 1 with the intermediate layer 3 interposed. Thereby, the relatively low impact strength of the glass sheet is compensated for, and the composite sheet is given impact resistance.

In the present invention, the intermediate layer 3 has a two-layer structure, the polyvinyl butyral adhesive layer 31 adheres the glass plate 1, the hot melt polyurethane-based adhesive layer 32 adheres to the polycarbonate resin plate 2, and the polyvinyl butyral adhesive The layer 31 and the polycarbonate resin plate 2 are separated by a polyurethane adhesive layer 32. Here, the hot-melt polyurethane-based adhesive layer refers to an adhesive layer formed by heating and melting a hot-melt polyurethane-based adhesive, as described later, and this polyurethane-based adhesive layer is also used in the bonding step described below. Even after the adhesive molding, the plasticizer contained in the polyvinyl butyral adhesive layer is prevented from migrating to the polycarbonate resin plate, thereby preventing the polycarbonate resin plate from being whitened and devitrified. Since the polyurethane adhesive layer itself is transparent and does not have any adverse effect such as devitrification even when in contact with the polycarbonate resin plate, the composite plate can maintain good transparency over the long term as a whole.

The adhesion between the polyvinyl butyral adhesive layer 31 and the glass plate 1 is sufficiently large as demonstrated with conventional laminated glass, and the peel strength of the glass plate 1 can be increased. On the other hand, the hot-melt polyurethane adhesive layer 32 adheres to the polycarbonate resin plate 2 and has a large adhesive strength, and the polyvinyl butyral adhesive layer 31 and the hot-melt polyurethane adhesive layer 32 are firmly adhered to each other. The board is tightly integrated as a whole. As a result, it is possible to eliminate the shortage of the adhesive force in the case where the single-layered hot-melt polyurethane-based adhesive layer is bonded to the glass plate side as in the related art.

The intermediate layer 3 is used to reduce the impact caused by the collision of a flying object with the composite plate together with the polycarbonate resin plate. In applications such as windshields, the glass plate or the resin plate is subjected to the impact. To prevent the debris from being scattered even when the vehicle is damaged, and to prevent penetration of flying objects into the composite board and penetration of the occupant's head in the event of a vehicle collision. 0.3 to 2.
It is good to make it as large as 0 mm.

[0013] Of the total thickness, the thickness of the polyurethane-based adhesive layer 32 is 0.1 to 0.8 mm, and the remainder is the thickness of the polyvinyl butyral adhesive layer 31. The lower limit of the thickness of the polyurethane-based adhesive layer 32 is set to 0.1 mm in order to completely prevent the plasticizer in the polyvinyl butyral adhesive layer from migrating to the polycarbonate resin plate over the entire area of the composite plate. , Preferably 0.3 to 0.6 mm
The reason why the thickness is good and the upper limit is set to 0.8 mm is that this resin is expensive. By making the inexpensive polyvinyl butyral adhesive layer 31 relatively thicker than the polyurethane-based adhesive layer 32 in the range of the entire thickness of the intermediate layer 3, the cost of forming the intermediate layer is reduced, and The impact resistance and penetration resistance of the layer can be ensured.

The adhesive for forming the polyurethane-based adhesive layer 32 is a film-shaped solid hot-melt polyurethane resin adhesive, which softens at a temperature of 80 to 150 ° C. and adheres. , Morton's product name "Crystal Flex PE-192, PE-1
93 (softening temperature 110-115 ° C) and PE-199 (softening temperature 100 ° C or less) can be used. On the other hand, the adhesive for forming the polyvinyl butyral adhesive layer 31 has 80 to 1
A material that is softened at a heating temperature of 50 ° C. and pressed against glass is selected. For this purpose, an ordinary polyvinyl butyral adhesive film for laminated glass can be used as it is.

The glass plate used in the transparent composite plate of the present invention can be widely used depending on the use of the composite plate, such as a plate glass for automobiles, a plate glass for buildings, and a tempered glass having a surface strengthening treatment. In addition, polycarbonate resin plate,
A weather-resistant plate or a surface hardened plate can be used.

The thicknesses of the glass plate and the polycarbonate resin plate are appropriately determined according to the use and required performance of the composite plate.
As an example, the thickness of the glass plate is about 1 to 5 mm, and the thickness of the polycarbonate resin plate is about 1 to 20 mm. Further, in order to increase the impact resistance of a composite plate having the same thickness, the thickness of the polycarbonate resin plate is relatively increased with respect to the glass plate 1. In particular, in order to have penetration resistance, the thickness of the polycarbonate resin plate is desirably 8 mm or more.

In the bonding step, a glass plate, a polyvinyl butyral adhesive film, a hot-melt polyurethane adhesive film and a polycarbonate resin plate are laminated in this order and heated to press the outer surfaces of the glass plate and the polycarbonate resin plate. The other pressing means uniformly presses and joins. At the heating temperature of 80 to 150 ° C., the polyvinyl butyral adhesive film is softened and pressed and bonded to the glass plate, and the hot-melt polyurethane adhesive film is in a softened state and the polyvinyl butyral adhesive film and the polycarbonate resin plate The space is filled and joined, and after cooling, it solidifies to form an integral intermediate layer.

In the present invention, 80 to 150 at the time of bonding is used.
At a heating temperature of ℃, the hot melt polyurethane adhesive film is in a softened state, so even if the molding pressure is low,
The hot-melt polyurethane adhesive has the advantage that the polyvinyl butyral adhesive layer and the polycarbonate resin plate are satisfactorily filled and adhered to each other, and there is no outflow of the adhesive from the gap and the thickness of the intermediate layer can be made uniform. is there. further,
Since the heating temperature range of 80 to 150 ° C. is lower than the glass transition temperature (about 150 ° C.) of the polycarbonate resin plate and the molding pressure is low, the heat distortion of the polycarbonate resin plate can be extremely reduced.

As a method for producing a composite plate, a conventional adhesive molding method such as a press method or a roll method can be used. The method for producing a composite plate of the present invention is described in Japanese Patent Application No. Hei 6-142596 described above. Are preferred. In this method, the inside of the container is airtightly partitioned by a soft and flexible pressing sheet, the lower side from the pressing sheet inside the container is set as a decompression chamber, and the upper side inside the container is set as a pressurizable chamber capable of pressure control,
In the decompression chamber, a heatable platen is fixed directly below the lower surface of the press sheet. While heating the laminated material to be molded placed on the platen, pressure is applied by the pressure difference between the decompression chamber and the pressurized chamber. The sheet presses the surface of the laminated material.

This method will be described in more detail.
As shown in (A), a laminated material A in which a glass plate 1, a polycarbonate resin plate 2 and the adhesive films 31 and 32 between them are stacked is placed on a surface plate 8 fixed in a lower container 6. As shown in FIG. 3B, the lower container 6 is connected to the upper container 5.
When the flanges 51 and 61 are attached with face to face,
The interior 6a of the lower container 6 is hermetically sealed by a pressing sheet 52 to form a decompression chamber. In this state, the upper container 5
5a (ie, pressurized chamber) and the inside 6a of the lower container 6
(Decompression chamber) is simultaneously depressurized by the vacuum pump 7,
Air contained in each layer gap of the laminated material A is removed, and the laminated material A is preheated while supplying heated air to the inside of the surface plate 8. When the air pressure in the interior 5a (pressurized chamber) of the upper container 5 is increased from the pressure in the interior 6a of the lower container 6 while finally heating to a predetermined temperature of 80 to 150 ° C., the flexible pressing sheet 52 becomes The laminated material A on the surface plate 8 is pressed over the entire surface. According to this method, the inside 5a of the upper container 5 and the inside 6a of the lower container 6
The molding pressure of the laminated material A can be increased by simply adjusting the pressure difference from
For example, there is an advantage that a required pressure as low as about 1.5 kg / cm ² can be easily and accurately adjusted. The adhesive film is softened and melted in a state of pressurization and heating, held for a predetermined time, and then cooled by flowing normal-temperature air into the surface plate 8 to form a composite plate. And take out the composite board.

The transparent composite plate of the present invention can be used as a window glass for vehicles such as automobiles, particularly a windshield (windshield), a sight glass for monitoring the inside of machinery, a window glass for architecture, and others for highways. As a soundproof wall plate or a plate material for an aquarium tank.

[0022]

【Example】

Example 1 A specific example of the transparent composite plate of the present invention is shown below. First, a composite plate of the glass plate 1 and the polycarbonate resin plate 2 shown in FIG. 1 was formed. Glass plate (length 182c)
mx 92 cm in width, thickness 3.0 mm) and a polycarbonate resin plate (same dimensions, thickness 5.0 mm), and a polyvinyl butyral adhesive film (thickness 0.4) on the glass plate side.
mm) and a hot-melt polyurethane adhesive film (0.4 mm thick) sandwiched on the resin plate side to form a laminate A. The hot melt type polyurethane-based adhesive film uses the above-mentioned product name “Crystal Flex PE-199” manufactured by Morton, and the polyvinyl butyral adhesive film uses a product name manufactured by Sekisui Chemical Co., Ltd. "Eslec film" was used.

In the bonding step, the laminated material A is sandwiched between the surface plate 8 and the pressing sheet 52 by applying the above-mentioned manufacturing method, and the heating temperature is 150 ° C., the molding pressure is 1.3 kg / cm.
^{In 2} , the adhesive film was softened and melted and bonded under a condition of a holding time of 1.0 h (hour) to form a flat composite plate. The intermediate layer of the composite plate had a total thickness of 0.8 mm, and the polyurethane-based adhesive layer had a thickness of 0.4 mm.

In the molded composite plate, no whitening was observed in the polycarbonate resin plate, the transparency was high, and the polycarbonate resin plate had good flatness without any deformation or edge flow.

As a comparative example, Example 1 was obtained from a laminated material C laminated only with a hot-melt polyurethane adhesive film (0.8 mm thick) as an intermediate layer between a glass plate and a polycarbonate resin plate. In the same manner as in the bonding step, a transparent composite plate was formed. Except that the transparent composite plate of this comparative example does not have a polyvinyl butyral adhesive layer,
This is the same as that of the first embodiment.

With respect to the transparent composite plates of Example 1 and Comparative Example,
In order to examine the adhesive strength, a heat shock test was performed using a thermal shock tester (manufactured by Tabai Espec Corp.). That is, the process of cooling and holding at −20 ° C. × 1 h and heating and holding at 70 ° C. × 1 h were defined as one cycle, and heating and cooling were repeated for 100 to 200 cycles, and the peeling state of the intermediate layer was examined.

[0027]

[Table 1]

The results of the heat shock test are shown in Table 1. In the case of 200 cycles, the transparent composite plate of the comparative example peeled off between the glass and the polyurethane-based adhesive layer. No change in the transparent composite plate. Thus, even if the thickness of the intermediate layer is the same, the polyvinyl butyral adhesive layer is interposed on the glass plate side of the intermediate layer, as in the present embodiment, as compared with the case where the hot-melt polyurethane adhesive layer alone is used. It can be seen that the composite plate was excellent in thermal shock resistance.

Embodiment 2 As another example, as shown in FIG. 2, a composite plate in which a polycarbonate resin plate 2 is disposed and sandwiched between two glass plates 1 and 1 was formed. The composite plate comprises a polyvinyl butyral adhesive layer 31 on the glass plate 1 side and a hot melt polyurethane adhesive layer 3 on the resin plate side 2 between each glass plate 1 and the polycarbonate resin plate 2.
2 and two intermediate layers 3 in an integrally joined state.

The laminate B is made of two glass plates (length 182c).
mx 92 cm wide, 3.0 mm thick) on the bonding surface with a polyvinyl butyral adhesive film (0.8 m thick)
m), and a hot-melt polyurethane adhesive film (0.4 mm thick) on both sides of a polycarbonate resin plate (same dimensions, thickness 4.0 mm) so that the adhesive films come into contact with each other. Intussusception. The used polyvinyl butyral adhesive film and the hot melt type polyurethane adhesive film are the same as those used in Example 1.

In the bonding step, the laminated material B is heated under pressure under the conditions of a heating temperature of 150 ° C., a molding pressure of 1.3 kg / cm ² , and a holding time of 1.5 h using the above-described apparatus. Thus, a transparent composite plate having excellent transparency and flatness could be formed. A heat shock test was performed under the same conditions as in Example 1 with the transparent composite plate. The results are shown in Table 1. No peeling was observed even with heat shock of 200 cycles.

Such a transparent composite plate in which a polycarbonate resin plate is disposed and sandwiched between two glass plates is particularly excellent in terms of impact resistance, penetration resistance and optical distortion, and is a front window for automobiles and high-speed trains. It is suitable for use as a dough glass or windshield, or a viewing window for machinery.

Further, it is also possible to form a multilayered ultra-thick transparent composite plate alternately stacked with a glass plate, a polycarbonate resin plate and the above-mentioned intermediate layer via the above-mentioned intermediate layer, and to constitute a transparent water-resistant container such as an aquarium tank. Can be used for

[0034]

According to the transparent composite plate of the present invention, the intermediate layer has
Since it is composed of two layers, a polyvinyl butyral adhesive layer on the glass plate side and a hot melt polyurethane adhesive layer on the polycarbonate resin plate side, the adhesive strength between the intermediate layer, the glass plate and the polycarbonate resin plate is large, and the transparent composite The peel strength and impact resistance of the whole board can be increased, and the whitening of the polycarbonate resin board caused by the polyvinyl butyral adhesive can be completely prevented, and the transparency of the whole composite board is guaranteed even after long-term use can do.

In the transparent composite plate of the present invention, the inexpensive polyvinyl butyral adhesive layer can be made thicker than the polyurethane-based adhesive layer. At the same time, it is possible to reduce the bonding cost.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a transparent composite plate in which a glass plate and a polycarbonate resin plate are laminated.

FIG. 2 is a schematic cross-sectional view of a transparent composite plate in which a polycarbonate resin plate is disposed between two glass plates and laminated.

FIGS. 3A and 3B are cross-sectional views of a vacuum forming apparatus for forming a transparent composite plate, wherein FIG. 3A shows a state in which a laminate is loaded and unloaded in the apparatus, and FIG. The state which forms a transparent composite board by pressurizing is shown.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass plate 2 Polycarbonate resin plate 3 Intermediate layer 31 Polyvinyl butyral adhesive layer 32 Hot melt type polyurethane adhesive layer 5 Upper container 52 Press sheet 6 Lower container 8 Surface plate

Continuation of the front page (56) References JP-A-63-57228 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 17/10 B32B 27/30 102 B32B 27/36 102

Claims (2)

(57) [Claims] 1. A transparent composite plate in which a glass plate and a polycarbonate resin plate are bonded and integrated via an intermediate layer, wherein the intermediate layer comprises a polyvinyl butyral adhesive layer on the glass plate side and a hot melt on the resin plate side. CLAIMS 1. A transparent composite plate formed of two layers of a polyurethane-based adhesive layer. 2. The intermediate layer has a total thickness of 0.3 to 2.0 m.
m, and the thickness of the polyurethane-based adhesive layer is 0.1
The transparent composite plate according to claim 1, which has a thickness of from 0.8 to 0.8 mm.