JPS6243869B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin laminate body having a polycarbonate resin surface layer and a method for manufacturing the same, and more particularly to a thick synthetic resin laminate body having a polycarbonate resin surface layer that hardly transmits ultraviolet rays, and a method for manufacturing the same. be. Polycarbonate resin (hereinafter referred to as PC)
Synthetic resin laminates having a layer on the surface are known, for example, as disclosed in Jitsukasho, filed by one of the present applicants.
It is described in Publication No. 54-165573 and Japanese Patent Application Laid-Open No. 55-49261. Synthetic resin laminates having a PC surface layer have many uses as plates with high impact resistance. Regarding this synthetic resin laminate body having a PC surface layer, the present inventors have considered increasing the thickness of the PC layer, adding an uneven pattern to the surface, and obtaining a transparent synthetic resin laminate body. .
It is difficult to manufacture these by the method described in the above-mentioned Japanese Patent Application Laid-Open No. 55-49261. The first reason
The problem is that the method described in the above publication requires the use of a pre-laminated film using a thin PC film, so it is not possible to use a thick PC sheet, and even thinner PC films have uneven patterns. cannot be attached. The second reason is that heat and pressure are used to laminate the pre-laminated film and vinyl chloride resin sheet, so it is almost impossible to use a PC sheet with an uneven pattern on its surface. be. The third problem is that the hot melt type adhesives used do not have sufficient transparency. The inventor further investigated adhesives that can firmly bond PC and other synthetic resins. In general, PC has poor solvent resistance, and if adhesives containing solvents or highly soluble liquid monomers are used, the surface will be attacked in a short period of time, easily causing cracks and whitening. On the other hand, the so-called dope bonding method, which takes advantage of the solubility of PC and uses an adhesive dissolved in a solvent such as methylene chloride, is effective for bonding small-area PC boards together; It has poor adhesion with resin and is not practical. Additionally, when bonding a PC board with a large area, or a PC board and a different type of synthetic resin board, non-reactive solvents such as dove adhesive may be encapsulated in the adhesive layer, which may adversely affect adhesive strength and other properties. unfavorable to Further, as mentioned above, the use of hot melt adhesives is not suitable for the present purpose due to the necessity of heating and pressing. As a result of these studies on adhesives, an ultraviolet curing adhesive was found to be the most suitable adhesive. As will be described later, this ultraviolet curable adhesive does not contain a solvent, and it is preferable that it does not contain a highly soluble liquid monomer such as styrene, or even if it contains it, it contains only a small amount. It is also preferable to first apply the ultraviolet curable adhesive to the PC surface as a primer to protect the PC surface, and then use another adhesive to bond it to a synthetic resin sheet or the like. On the other hand, the use of ultraviolet curable adhesives poses a problem regarding their curing. The reason is that PC usually has low UV penetration. Good weather resistance
In order to make it a PC, UV absorbers are often added to the PC. Furthermore, since a PC board with an uneven pattern on its surface reflects light due to the unevenness, it is difficult for ultraviolet rays to pass through even if no ultraviolet absorber is added. Of course, opaque PC does not allow UV rays to pass through. Hereinafter, "UV-resistant" PC refers to PC that is transparent to visible light but difficult to transmit to UV rays due to the combination of UV absorbers, etc., and is essentially UV-transparent. Even if the surface is opaque, it is difficult to transmit UV rays due to the nature or shape of the surface, such as the presence of uneven patterns on the surface, or it is opaque or at least opaque to UV rays due to the coloring agent, filler, other formulations, and type of PC. what is,
etc. This ultraviolet rays are difficult to penetrate (hereinafter referred to as
Ultraviolet curing type (hereinafter referred to as UVC)
Even if you apply an adhesive and irradiate it with ultraviolet light from the UVC-PC surface, the adhesive will not harden. Therefore,
Even if you sandwich a synthetic resin board between two UVO-PC boards and try to cure it by placing a UVC-adhesive between them, the only way to cure it is to irradiate the UV rays from the UVO-PC surface, so there is almost no sufficient adhesion. It's impossible. As a result of further study to solve the above problem, the present inventor has developed a preliminary laminate in which UVO-PC and ultraviolet-transparent (hereinafter referred to as UVT) synthetic resin are bonded together using UVC-adhesive or a combination of it and other adhesives. is first manufactured, and the UVT of these two preliminary laminates is
We have discovered a method for manufacturing the desired laminate by bonding synthetic resin surfaces using various methods. UVT-synthetic resins are usually bonded together using an adhesive, but this adhesive is not a UVC-adhesive. Further, this bonding may be performed by fusion bonding, etc. Furthermore, one or more sheets of other synthetic resin (not necessarily UVT) may be interposed between these two surfaces, and the bonding may be performed by adhesion or fusion bonding. You can also do it. The present invention first relates to a synthetic resin laminate having at least a six-layer structure as described above, that is, a synthetic resin laminate having at least a six-layer structure in which both surfaces are polycarbonate resin layers that hardly transmit ultraviolet rays. , and a second layer inward from the first both surface layers A.
The second two layers are an ultraviolet curable adhesive layer or an adhesive layer B including that layer, and the third two layers are an ultraviolet-transparent synthetic resin layer C.
This is a synthetic resin laminate plate body characterized in that these are bonded together by adhesion, fusion, etc. either directly or via one or more synthetic resin layers. FIG. 1 is a cross-sectional view showing one example of the laminate body of the present invention. The first UVO-PC layer 1 and 2 are upper and lower 2
There are two surface layers A. The second two layers are UVC-
The adhesive layer B3, 4 includes an adhesive layer, and the third two layers are UVT-synthetic resin layers C, 5, 6.
The two UVT synthetic resin layers 5, 6 are bonded to each other by an adhesive layer 7 other than UVC adhesive.
Adhesive layers B, 3, and 4 may be composed only of a cured UVC adhesive, as shown in FIG.
It may consist of more than one layer. FIG. 2 is a partial cross-sectional view showing one example of the laminate body of the present invention,
This is an enlarged view of the adhesive layer 3. The adhesive layer B, 3 is composed of a UVC adhesive layer 8 adjacent to the UVO-PC layer and a second adhesive layer adjacent to the UVT synthetic resin layer 5, and this second adhesive layer 9 is preferably a UVC adhesive layer 8 adjacent to the UVO-PC layer. The adhesive layer 8 of No. 1 is a different type of ultraviolet curing adhesive, and both will be described later. The laminate of the present invention may also be one in which two UVT-synthetic resin layers C are bonded together by direct fusion, or by adhesive fusion or the like through one or more layers of synthetic resin or other material. It may be combined by FIG. 3 is a partial sectional view showing another example of the laminate body of the present invention, and is a
The bonding portions of UVT-synthetic resin layers C, 5, and 6 have been changed. Two UVT-synthetic resin layers 5, 6
A second synthetic resin layer 10 exists between them, and two adhesive layers 11 and 12 bond between them. The second synthetic resin layer 10 may not be transparent to ultraviolet light, and may be opaque to visible light. Further, this second synthetic resin layer 10 can be replaced with a layer made of other materials, such as metal, paper,
It may be FRP or other materials. It is preferable that at least one of the two adhesive layers 11 and 12 is a cured layer of an adhesive other than an ultraviolet curable adhesive, and that the UVT-synthetic resin layers 5 and 6 and the synthetic resin layer 10 are fused to each other. If adhesive layers 11 and 12 are present, these adhesive layers 11 and 12 may not be present. Two UVT-synthetic resin layers 5 and 6 similar to the one shown in Figure 3.
There may be many more layers of synthetic resin or other materials between them, and as long as they are bonded to each other and to the UVT-synthetic resin layers 5 and 6 by adhesion or the like, the UVT-synthetic resin layer The configuration between 5 and 6 is not limited. As illustrated, the synthetic resin plate of the present invention is composed of at least six layers. That is, when the UVT-synthetic resin layers C, 5, and 6 are fused to each other, a six-layer structure is obtained. However, it is usually preferable to bond the UVT-synthetic resin layers C, 5, and 6 with an adhesive (that is, it may be difficult to fuse both layers by heating and pressing as described above). Preferably, it has at least a seven-layer structure with an adhesive layer 7 provided between both layers 5 and 6. Except for both surface layers A, 1 and 2, the adhesive layers 3 and 4 and the UVT-synthetic resin layer are transparent to visible light, but preferably have at least semi-transparency. It is preferable for the adhesive layer 7 between the UVT-synthetic resin layers 5 and 6 and other layers to be transparent to visible light, considering the commercial value of the synthetic resin plate of the present invention, but as mentioned above, they are not necessarily transparent. You don't have to. The present invention also relates to a method for producing the above-mentioned synthetic resin laminate, that is, in a method for producing a synthetic resin laminate in which both surfaces are polycarbonate resin layers that are hardly transparent to ultraviolet rays, A pre-laminated body is manufactured by bonding a UV-curable adhesive layer and an ultraviolet-transparent synthetic resin with an ultraviolet-curable adhesive layer or an adhesive layer containing the ultraviolet-curable adhesive layer, and then the ultraviolet-transparent This is a method for manufacturing a synthetic resin laminate, characterized in that synthetic resins are bonded to each other directly or through one or more synthetic resin layers by adhesion, fusion, or the like. First, the preliminary laminate will be explained. Preferably, the prelaminate is manufactured by the following two methods. The first method is to manufacture UVT synthetic resin by casting. first,
A UVC-adhesive is applied to one side of the UVO-PC sheet or film, and preferably this UVC-adhesive is partially cured by ultraviolet irradiation. UVC: Adhesives can be used in the next process without being even partially cured, but they become more easily dissolved in the curable synthetic resin raw materials used in the next process, especially those with high solubility such as styrene. When using a curable synthetic resin raw material, this UVC-adhesive will be eluted from the UVO-PC surface, resulting in decreased adhesion and the UVO-PC surface becoming more susceptible to attack by the curable synthetic resin raw material. on the other hand,
Although the UVC-adhesive applied to the UVO-PC surface may be almost completely cured, the adhesive strength is likely to decrease in this case as well. Therefore, it is preferred that the UVC-adhesive applied to the UVO-PC surface be partially cured by UV irradiation until some surface tack remains. Note that in this case, the UV irradiation is naturally performed from the surface coated with the UVC adhesive. Next, apply this UVC-adhesive UVO-on the PC.
UVT - Casting is performed to form a synthetic resin layer. UVT - usually liquid curable synthetic resin raw materials capable of forming synthetic resins, such as so-called acrylic syrups forming acrylic resins and uncured liquid unsaturated polyester resins.
The curable synthetic resin raw material is cured by casting on the UVO-PC surface coated with UVC-adhesive or by forming a casting mold and filling it inside. Cast molding will be explained as an example. FIG. 4 is a sectional view showing an example of a casting mold. UVO-PC sheet 21 is UVC-adhesive layer 2
2 is arranged as the inner surface of the casting mold, and the casting mold is constructed by combining a molding material 23 such as a glass plate, a sealing material 24 such as a gasket capable of sealing the periphery of the casting mold, and a holding material 25. The cavity 26 of this casting mold is filled with a curable synthetic resin raw material, and then this curable synthetic resin raw material is hardened. UVT-synthetic resin is formed by curing the curable synthetic resin raw material, and at the same time, UVO-PC and UVT-synthetic resin are
The mold material 23 and the holding material 25 on which the UVC-adhesive prelaminated body is formed are removed, and the sealing material 24 is further removed to take out the preliminary laminate. Curing of the curable synthetic resin raw material can be performed using light such as ultraviolet rays, other radiation, or heat, and room temperature curable synthetic resin raw materials can be used. Preferably, an ultraviolet ray curing type or room temperature curing type synthetic resin raw material is used. The reason for this is that in order to completely cure the UVC-adhesive, it is preferable to perform curing while irradiating ultraviolet rays. Therefore, if an ultraviolet curable synthetic resin raw material is used, the UVC adhesive can be cured at the same time by irradiating the mold material 23 with ultraviolet rays. Even in the case of a room temperature curing type or a thermosetting type synthetic resin raw material that can be cured at a relatively low temperature, curing can be performed at a relatively low temperature while irradiating ultraviolet rays. On the other hand, the use of thermosetting synthetic resin raw materials that require relatively high temperatures may be inconvenient in some cases. That is, the UVC-adhesive that has not been sufficiently cured is likely to be eluted into the synthetic resin raw material that is in the curing stage due to heat. Therefore, if the UVC-adhesive is sufficiently cured, or if the UVC-adhesive is difficult to dissolve into the thermosetting resin raw material even under heating, thermosetting synthesis that requires relatively high temperatures is required. The resin raw material can be used in the same way as the room temperature curable synthetic resin raw material. In addition, UVO-PC surface
UVC - UV irradiation is not necessarily required when curing synthetic resin raw materials, not only when the adhesive is almost completely cured, but also when it is partially cured. This is because UVC-adhesives often harden gradually under heating or at room temperature, and can also harden by contact with a hardening agent in synthetic resin raw materials. In addition, in the case of molding using a casting mold as described above, when ultraviolet ray irradiation is performed, the mold material 2
3 must be transparent to ultraviolet rays, and a material transparent to ultraviolet rays, such as a glass plate or a transparent synthetic resin, is used, and if necessary, a mold release agent or the like is applied to the surface on the cavity 25 side. A second method of producing prelaminates is UVT-
This is a method of manufacturing a preliminary laminate by bonding a synthetic resin sheet or film and a UVO-PC sheet or film. For example, when bonding a UVO-PC sheet and a UVT-synthetic resin sheet,
First, as in the first method, apply UVO to one side of the sheet.
UVC-Adhesive is applied and partially cured, preferably by irradiation with ultraviolet light. Next, a method of applying a second adhesive on this UVC-adhesive coated surface and overlaying a UVT-synthetic resin sheet on top of it, UVC-
By stacking an adhesive-coated UVO-PC sheet and a UVT-synthetic resin sheet previously coated with a second adhesive with their adhesive-coated surfaces facing each other, or by other methods, UVC can be applied using the second adhesive. - Adhesive application: Adhere the UVO-PC sheet and UVT-synthetic resin sheet. The reason for using the second adhesive is that UVC adhesives, whether cured or uncured or partially cured, often have difficulty bonding firmly to UVT synthetic resins. It is from. This is presumed to be due to the essentially low adhesion between the two, but of course UVT-
Adhesion is possible depending on the type of synthetic resin. Second
By using this adhesive, it is possible to bond with a wider variety of UVT-synthetic resins. Second
As in the case of the curable synthetic resin raw material in the first method, it is preferable that the adhesive be an ultraviolet curable adhesive or a room temperature curable adhesive, and in some cases, a thermosetting adhesive, a hot melt adhesive, or another type of adhesive may be used. agents can be used. Similarly, UVC-adhesives and
The curing of the adhesive is preferably carried out while irradiating ultraviolet rays from the surface of the UVT-synthetic resin. In this method, the UVC-adhesive and the second UV-curable adhesive may be of the same type;
The second UV curable adhesive can be selected from a wider range of types. As mentioned above,
It is not preferable for UVC-adhesives to contain monomers or solvents that are highly soluble in PC, such as styrene, but the second UV-curable adhesive has UVC-
This is because since it is protected by an adhesive, there is no such restriction, and a material with higher adhesiveness can be selected relatively freely. The thus obtained prelaminated body, like the preliminary laminate obtained by the first method, is joined in the next step to form the synthetic resin laminate. In this method,
Since the main functions of the UVC-adhesive are to protect the surface of the UVO-PC and to improve adhesion with the second adhesive, this UVC-adhesive can be called a primer as described above. The prelaminated body is not limited to those manufactured by the above two methods. For example, there may be two or more UVT synthetic resin layers, and three or more adhesive layers containing UVC adhesives. As a specific example, in the first method of manufacturing a prelaminate shown in FIG. 4, a UVT synthetic resin sheet is used instead of the mold material 23, and if necessary, the cavity 25 side is By applying adhesive to the surface and filling the cavity 25 with curable synthetic resin raw material and curing, UVT
- A prelaminated body having two synthetic resin layers can be obtained. In addition, as another example, in the second method, a multilayer laminate of UVT-synthetic resin sheets is used, or two or more UVC-synthetic resin sheets are bonded at the same time when bonding to UVO-PC. By carrying out this process, a preliminary laminate consisting of two or more UVT-synthetic resin layers can be produced. The two prelaminates are then bonded together. The two prelaminates to be combined may be the same, or may be obtained by different methods or have different configurations. For example, different types of UVT synthetic resins can be used as long as they can be strongly bonded. The two preliminary laminates may be bonded together by applying heat and pressure to fuse the UVT-synthetic resin layers, as the case may be, but it is usually accomplished by bonding with an adhesive. Normally, room temperature curable, thermosetting, hot melt type adhesives, etc. are suitable for this adhesive, but ultraviolet ray curable adhesives are not so suitable. This is because it is difficult to cure the adhesive by irradiating ultraviolet rays from the sides of the laminate except when manufacturing a laminate with a small area. Of course, since both surface layers are UVO-PC layers, it is not possible to cure the adhesive by irradiating ultraviolet rays from above and below. Therefore, adhesives other than ultraviolet curable adhesives are preferable for adhering the prelaminates together, and in particular, adhesives that can be cured without producing volatile solvents or by-products, such as unsaturated polyester resin adhesives or epoxy resin adhesives, are preferred. Suitable adhesives include polyurethane resin adhesives, acrylic monomers and prepolymers, and other acrylic adhesives. The two prelaminates can also be bonded together as described above with one or more layers of synthetic resin or other material therebetween. Various materials can be interposed between the prelaminates depending on the purpose, as long as the layer and the two prelaminates or each of the layers can be firmly bonded by adhesive or the like. This synthetic resin layer does not have to be ultraviolet-transparent, or may be opaque, or may be made of a material other than synthetic resin or a composite material such as FRP. For bonding these layers to the UVT-synthetic resin layer or bonding these layers to each other, an ultraviolet curing adhesive may be used except for at least one bond.
However, for at least the last step of bonding to finally form the laminate of the present invention, a bonding method other than bonding using an ultraviolet curable adhesive is suitable. As mentioned above, the UVO-PC layer in the present invention is preferably one that is difficult to transmit ultraviolet rays due to the combination of an ultraviolet absorber, various molding shapes such as surface irregularities, or opacity through a processed surface. These are preferably made of PC that is substantially transparent to visible light, for example, those that are transparent unless there are surface irregularities. Its thickness is 0.5mm or more,
In particular, it is preferably 0.8 mm to 10 mm, but is not limited thereto. The reason for this preference is
This is because a laminate body having a thick PC layer, which is difficult to obtain by the method using film-like PC described in the above-mentioned known example, can be obtained. Of course, the present invention can also be applied to the case where a PC sheet or film having a thickness of less than 0.5 mm is used to obtain a laminate with excellent transparency and high interlayer adhesion. In addition, in the present invention,
"Sheet" refers to something with a thickness of 0.2 mm or more, and "film" refers to something with a thickness less than 0.2 mm. Therefore, the material forming the UVO-PC layer is preferably a PC sheet, particularly a PC sheet with a thickness of 0.5 mm or more, and a more suitable one is a PC sheet with a thickness of 0.8 to 10 nm.
This is a PC sheet. As PC, ordinary polyphenol residues (e.g. bisphenol A residue) and

[Formula] Not limited to polycarbonate resins having groups, but also resins consisting of polycarbonate copolymers such as polycarbonate resins and polyester carbonate resins having polyhydric alcohol residues, and blend resins of these polycarbonate resins and other synthetic resins. It may be. PC can contain UV absorbers, flame retardants, stabilizers, colorants, fillers, and other additives. As mentioned above, the PC is preferably substantially transparent or at least translucent to visible light. As the UVC adhesive in contact with the UVO-PC layer, various UV-curable adhesives can be used. However, it is preferable that it does not contain solvents or highly soluble monomers that may attack the PC surface, or even if it does, it contains only a small amount. There are few such UVC-adhesives on the market, but examples include the UV-curable "Spiratsuk" (trade name) adhesive manufactured by Showa Kobunshi Co., Ltd. and the UV-cured adhesive manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd. Curing type “Goserac”
(Product name) Adhesives, etc. For example, the former is presumed to be a compound containing a cycloacetal compound having a polymerizable unsaturated group as a main component with a photosensitizer added (JP-A-56-2312, JP-A-53 -7796, JP-A-52-154884, etc.). In addition, epoxy acrylate-based, polyester acrylate-based, and other UVC adhesives may also be used. A preferred UVC-adhesive is one that does not contain a PC-soluble solvent, a more preferred UVC-adhesive is one that does not contain a PC-soluble monomer, and a highly transparent one is further preferred. The method of applying UVC-adhesive to the surface of UVO-PC is not particularly limited. For example UVO
- If the PC coating surface is flat, it is appropriate to apply it with a wire coater or bar coater, etc.
For non-flat surfaces such as curved surfaces, it is appropriate to apply by spraying or brushing. The coating thickness of the UVC-adhesive is not particularly limited, but from a cost perspective it is preferable to be thin, and for practical purposes it is
200μ is appropriate. It is preferred to use a light source with a high amount of UV radiation, such as a mercury vapor lamp, to irradiate the applied UVC adhesive to at least partially cure it. UVC adhesives in terms of curing properties depend on the light source wavelength range, output, irradiation time, etc. of the irradiation device, but for example, a high-pressure mercury lamp for photochemistry, wavelength range 245-577nm, output 80W/cm
When irradiated with UVC from a height of 50 cm above the surface on which the adhesive is applied, it is appropriate that the adhesive cures within 30 seconds, especially within 2 to 10 seconds, leaving some tackiness. Of course, these conditions may vary depending on the type of UVC adhesive, the type and amount of photosensitizer added, and so on. Although the irradiation time may become longer if the intensity of the ultraviolet rays is changed, it is not preferable to make the irradiation time extremely long. This is UVC - the adhesive may have some UVO
- This is because it tends to attack the PC surface and cause it to turn white. Therefore, even when using UVC-adhesive without curing, it is not preferable to allow too much time for final curing. Conversely, significantly shortening the curing time tends to reduce adhesive strength. Therefore, it is preferable that the at least partial curing time is from 30 seconds to 45 minutes, particularly from 2 minutes to 30 minutes, while leaving some tackiness. As the UVT synthetic resin, various synthetic resins can be used as long as they have UV transmittance. These synthetic resins are usually transparent to semitransparent to visible light. For example, acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS, polyester resins such as polyethylene terephthalate, unsaturated polyester resins, vinyl ester resins, epoxy resins, UV-transparent PC (with UV absorbers) (not included) There are other items. Particularly preferred are acrylic resins, unsaturated polyester resins, and styrene resins. Among these, acrylic resin and styrene resin are used as sheets in advance.
It is preferable to apply it to the method of manufacturing a preliminary laminate using the first method, and acrylic resins and unsaturated polyester resins are preferably applied to the method of manufacturing a preliminary laminate using the first method from uncured liquid synthetic resin raw materials. It is preferable to apply. In these cases, the curing time of the second adhesive or synthetic resin raw material in contact with the UVC-adhesive layer is preferably within 3 hours, particularly within 2 hours, for the reasons described above. As described above, various kinds of adhesives can be used as the second adhesive. Preferred are ordinary UV-curable adhesives and curable synthetic resins, such as acrylic syrup, epoxy-acrylate, acrylic urethane, acrylic ester, other acrylic resins, unsaturated polyester resins, and liquid polybutadiene rubber. . Particularly preferred are the above-mentioned acrylic resins and unsaturated polyester resins having an acrylic group or methacrylic group at the end. The thickness of the synthetic resin laminate of the present invention is not particularly limited. However, the preferred thickness is 2 mm or more, especially 5 mm or more. The method of the present invention is characterized in that particularly thick laminates can be produced, and those with a thickness of 10 mm or more can be produced. The laminate of the present invention may be of various shapes such as a flat plate or a curved plate or a bent plate. Since it is difficult to process anything other than a flat plate after forming a flat laminate, it is preferable to manufacture it using a UVO-PC sheet or UVT-synthetic resin sheet that has been previously processed into the desired shape. The laminate of the present invention can be subjected to surface treatment such as surface painting or physical processing such as surface cutting after its manufacture. These processes are used to create the above-mentioned uneven pattern.
It may also be done before lamination, such as with UVO-PC. The laminate of the present invention can be used for various purposes.
Since the laminate of the present invention has high strength, excellent weather resistance, and excellent transparency, it is suitable for use as, for example, door materials and window materials for buildings. For example, in the case of doors, tempered glass doors and acrylic resin doors have traditionally been used as doors with excellent transparency. However, tempered glass doors are heavy and it is not possible to add textured patterns to the surface. On the other hand, doors made of acrylic resin are lightweight and can be patterned with irregularities, but even if they contain UV absorbers, they have poor weather resistance and are prone to minute cracks on the surface. The door made of a laminated plate of the present invention has a PC layer on its surface that hardly transmits ultraviolet rays, so its weather resistance is much higher than that of an acrylic resin door. On the other hand, PC
Not only are manufactured doors extremely expensive compared to the material they are made of, but thicker ones must be manufactured by laminating multiple PC sheets, which is difficult due to the nature of PC. The laminate of the present invention not only has an inexpensive intermediate layer and has excellent adhesive strength with the surface UVO-PC layer, but also has high transparency to visible light and the formation of uneven patterns on the surface. is also possible.
Therefore, it has far more suitable performance as a door material than conventional door materials. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 2.2 mm thick containing about 0.2% by weight of ultraviolet absorber,
Wire UVC-adhesive “Spiratsuk U-3253-1X” (product name, sold by Showa Kobunshi Co., Ltd.) on one side of a 1000 x 2000 mm UVO-PC sheet (sold by Asahi Glass Co., Ltd., product name “Lexan”). It was applied to a thickness of 50μ using a coater. Fluorescent light for immediate copying FL40BA-37φ-35mm
(Sold by Matsushita Electric Industrial Co., Ltd.) were irradiated with UVC-adhesive from a distance of 150mm above the coated surface using an ultraviolet irradiation device arranged in parallel at a spacing of 30mm. Approx. 25℃, approx. 15
In minutes, the UVC-adhesive cured to the point where the surface remained slightly tacky to the touch. Next, apply acrylic syrup (commercially available methyl methacrylate and acrylic powder (manufactured by Kyowa Gas Chemical Co., Ltd.) to 0.2% by weight of photosensitizer on the UVC-adhesive).
% by weight], and then overlay a 6 mm thick polymethyl methacrylate sheet (trade name: "Paraglass", manufactured by Kyowa Gas Chemical Co., Ltd.) with no added UV absorber on top of it, and squeeze it to remove it. It bubbled. Furthermore, a glass plate with a thickness of 8 mm was placed on top of the glass plate, the periphery was clamped, and the glass plate was irradiated with ultraviolet rays for 60 minutes using the same irradiation equipment and conditions as above to cure the acrylic syrup. The resulting UVO-PC-acrylic resin prelaminate was completely transparent to visible light. Two of the above preliminary laminates were prepared, their acrylic resin surfaces facing each other, and an adhesive was filled between them. This adhesive is a room temperature curing adhesive obtained by adding 0.2% by weight of Acrybond BC-415 (sold by Mitsubishi Rayon Co., Ltd.) as a room temperature curing accelerator to the above acrylic syrup and thoroughly dissolving the mixture. After filling with adhesive, it was squeezed to remove air bubbles, and then it was clamped and placed in a heating furnace at 60 to 80°C, heated for about 60 minutes, and then taken out and allowed to cool. The resulting laminate had a thickness of 18 mm and was completely transparent to visible light. UVO-PC of laminate sample obtained to examine adhesive strength
When a sharp wedge was driven into the adhesive layer between the layer and the UVT-acrylic resin layer, the UVO-PC layer broke.
It was found that the adhesive strength was extremely high. similarly
The adhesive strength between the UVT and acrylic resin layers was also extremely high. In addition, a sample of the laminate was exposed for 1200 hours in a Sunshine Weather-Ometer, but there was no peeling of the UVO-PC layer or deterioration of its surface, and no discoloration was observed throughout the laminate. Example 2 UVO-PC of the same size and type as Example 1
One side of the sheet is coated with UVC adhesive
CKS400” (Product name: Sold by Nippon Gosei Kagaku Kogyo Co., Ltd.)
was applied to a thickness of 50μ using a wire coater. Immediately turn off the high-pressure mercury lamp H02-L-21 (eye graphics).
Co., Ltd.) and irradiate it with ultraviolet light for 4 seconds from a height of 50 mm.
UVC—After curing a portion of the adhesive, Example 1
The UVC-adhesive was cured to the extent that the surface became somewhat sticky by irradiating it with ultraviolet light for about 15 minutes using the same irradiation device. Using this UVO-PC sheet, a preliminary laminate was produced using the same materials and methods as in Example 1, and three of the sheets were subsequently bonded together to produce a laminate with a thickness of 18 mm. The obtained laminate was transparent, and its adhesion and weather resistance were as good as those produced in Example 1. Example 3 A UVO-PC sheet with a partially cured UVC-adhesive layer on one side was produced using the same materials and methods as in Example 1. UVC-
Face each other with the adhesive-applied surfaces inside, and insert a soft polyvinyl chloride resin tube (diameter 10
mm) was used as a gasket, and the resulting cavity was cast and filled with unsaturated polyester resin.
This unsaturated polyester resin is
2004WM-2” 100 parts (parts by weight, same below),
1 part of "Accelerator E", 1 part of "Accelerator K" (all three product names, sold by Showa Kobunshi Co., Ltd.), and 2 parts of "Permec N" (trade name, sold by NOF Corporation). It is well mixed. The gelation of the filled unsaturated polyester was completed in about 60 minutes at about 25°C. The glass plate was left as it was for 16 hours, then heated at 80℃ for 60 minutes, left to cool, and after the unsaturated polyester had completely cured, the glass plate was released from the mold and made into a UVO with a thickness of about 11 mm.
- A prelaminate of PC layer and unsaturated polyester resin was obtained. The resulting UVO-PC unsaturated polyester resin prelaminate was completely transparent to visible light. Two of the above preliminary laminates were prepared and filled with an adhesive with their unsaturated polyester resin surfaces facing each other. As this adhesive, polyester-based, epoxy-based, or polyurethane-based adhesives known as adhesives for unsaturated polyester resins can be used. For example, after filling unsaturated polyester with a room-temperature curing accelerator added, it is squeezed, degassed, and then clamped.
It was placed in a heating oven at 80°C and heated for about 60 minutes, then taken out and left to cool. The thickness of the obtained laminate was approximately 22 mm, and it was completely transparent to visible light. When the unsaturated polyester resin surface was sanded before filling with adhesive, the adhesive strength between the preliminary laminates became stronger.
The obtained laminate was transparent and had good adhesion and weather resistance not much different from that produced in Example 1. Example 4 The primer-applied surface of UVO-PC needs to be smooth, but there is no problem in manufacturing even if the other surfaces have an uneven pattern. For example, Example 1 is applied to a smooth surface using a UVO-PC board with an uneven pattern on one side.
Primer treatment was performed in the same manner as above, and the same operations were carried out thereafter to obtain a laminate that was translucent but had little transparency. It goes without saying that the adhesiveness and weather resistance of this laminate are the same as in Example 1. Example 5 When manufacturing a laminate board in Example 1, a decorative cloth is encapsulated in the adhesive layer 7 shown in FIG. A laminated board with a high decorative value and a variety of patterns was obtained. The adhesiveness and weather resistance of this laminate were the same as in Example-1. Example 6 When producing a laminate in Example 3, when filling unsaturated polyester between the UVO-PC sheet coated with UVC adhesive and the glass plate, a decorative encapsulant made of glass fiber mat was placed in advance. After gelation, curing was completed in the same manner as in Example 3, resulting in a laminate that was translucent but had little transparency and had high decorative value due to the patterns of the various inclusions. . The adhesion and weather resistance of this UVO-PC and unsaturated polyester resin laminate were good, with no significant difference from Example 3.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing one example of the laminated plate body of the present invention, and FIGS. 2 and 3 are partial cross-sectional views showing other examples of the laminated plate body of the present invention, respectively. FIG. 4 is a partial sectional view showing an example of a casting mold for manufacturing a prelaminated body according to the present invention. 1, 2... Surface layer, 3, 4... Adhesive layer, 5, 6... Synthetic resin layer, 7... Adhesive layer, 8... UVC-adhesive layer, 9... Second adhesive layer, 21... UVO-PC Sheet, 22...UVC-adhesive layer, 23...Glass plate,
24...Sealing material.

Claims (1)

[Scope of Claims] 1. A synthetic resin laminate having at least a 6-layer structure in which both surfaces are polycarbonate resin layers that hardly transmit ultraviolet rays, and inward from the first both surface layers A. The second two layers are an ultraviolet curable adhesive layer or an adhesive layer B including the layer, and the third two layers are an ultraviolet-transparent synthetic resin layer C,
A synthetic resin laminate body characterized in that the synthetic resin layers C are bonded together by adhesion, fusion, etc. directly or via one or more synthetic resin layers. 2. The plate according to claim 1, wherein the adhesive layer B is an adhesive layer cured by ultraviolet rays and has an ultraviolet curable adhesive layer adjacent to the surface layer A. 3. The plate according to claim 2, wherein the ultraviolet curable adhesive does not contain a solvent that is highly soluble in polycarbonate resin. 4 Two synthetic resin layers C are bonded via at least one adhesive layer, and at least one of the adhesive layers
2. The plate according to claim 1, wherein the first part is made of an adhesive that is not an ultraviolet curable adhesive. 5. In a method for manufacturing a synthetic resin laminate in which both surfaces are polycarbonate resin layers that hardly transmit ultraviolet rays, a polycarbonate resin that hardly transmits ultraviolet rays and a synthetic resin that transmits ultraviolet rays are bonded to an ultraviolet curable adhesive layer or A prelaminate bonded with an adhesive layer containing layers is produced, and then the ultraviolet-transparent synthetic resin of the two prelaminates is bonded directly or directly to each other.
A method for manufacturing a synthetic resin laminate, characterized by bonding by adhesion, fusion, etc. through more than one synthetic resin layer. 6 Apply an ultraviolet curable adhesive to one side of a polycarbonate resin that is difficult to transmit, and partially cure it by irradiating it with ultraviolet rays, and then bond it with an ultraviolet ray transparent synthetic resin and a second adhesive to form a prelaminate. 6. A method according to claim 5, characterized in that: