JP2001180265A - Conjuction structure of transparent resin plate with colored layer and metal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conjunction structure of a transparent resin plate with colored layer and a metal capable of easily forming the colored layer on a portion of the transparent resin plate being previously subjected to hard coat processing, highly exhibiting a conjunction force of the transparent resin plate with the metal on the above colored layer portion and imparting an effective shielding function. SOLUTION: In the conjunction structure of a transparent resin plate with colored layer and a metal, the transparent resin plate having a colored layer in which an urethane resin type colored layer is formed on one surface portion of a silicone type hard coat layer formed on a surface of the transparent resin plate; and a metal are adhered on the portion where the colored layer is formed through an elastic adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent resin plate having a coloring layer in a part of a window material for a vehicle, and more particularly, to a window glass, a sunroof, a light cover, a window for a vehicle, etc. The present invention relates to bonding of a transparent resin plate, which is hard-coated and has a colored layer on a peripheral portion, to be substituted, and a metal formed on a frame or the like.

[0002]

2. Description of the Related Art Generally, a transparent resin plate made of highly transparent acrylic resin or polycarbonate resin is used as a substitute for glass in a wide range of fields from the viewpoint of impact resistance, light weight, and easy workability. In addition, in many cases, these transparent resin plates are hard-coated with a silicone resin or the like for the purpose of compensating for the lack of the original surface hardness, and the scratch resistance is improved, Weatherability,
It is considered to be excellent in stain resistance and the like.

On the other hand, when the transparent resin plate subjected to the hard coating treatment as described above is used as an alternative material to glass, for example, for a window of an automobile, similarly to the glass material, the peripheral portion of the material is formed of metal of the window. In many cases, means for directly joining to a frame made of steel is used, and in order to hide the joined portion from the outside, the peripheral portion is mostly painted with black paint or the like.

[0004]

However, since the surface of the transparent resin plate which has been hard-coated as described above is poor in hydrophilicity and is chemically stable, it is directly attached to a metal frame with an adhesive. Joining was not easy.

[0005] In order to improve this point, for example, Japanese Patent Publication No. Hei 7-106613 proposes means for joining the transparent resin plate to the frame using a urethane-based adhesive as an adhesive. I have.

However, according to the above-mentioned joining means, it is possible to secure a certain degree of adhesive strength (4.0 to 4.5 MPa) between the transparent resin plate subjected to the hard coating treatment and the metal frame. However, it cannot be said that a sufficient adhesive strength has yet been reached in practical use. In particular, in recent years, it has been applied to a wider range of applications, the use form has been increased, and it has been used in harsh use environments (environments placed under sudden temperature changes, high loads, severe vibrations, repeated loads, etc.). Cases are increasing. By the way, JASO standard M338-
89 specifies that cohesive failure is 1.5 MPa or more, but in practice, it is actually required that the adhesive strength greatly exceed this standard.

On the other hand, in the above-mentioned proposal, on the other hand, prior to the hard coat treatment, screen printing is applied to a portion corresponding to the periphery of the window frame while keeping the transparent resin plate flat in accordance with the window frame of an automobile or the like to be applied. Although there is an advantage in the process that black ink can be printed on the surface, the primer treatment solution required for hard coat treatment is easily contaminated with black ink, and if this process is adopted, the transparent part of the product or the transparent part There is a drawback that dirt remains without being removed at the boundary portion between the ink and the black ink, which causes deterioration in appearance quality. The printing means of black ink in this proposal is already disclosed in Japanese Patent Publication No. 7-25910, and a vinyl-acrylic resin-based, vinyl-methacrylic resin-based, modified polyester A colored layer made of at least one kind of ink selected from a resin type is provided, and a polymethyl methacrylate-based primer layer is interposed between the colored layer and the hard coat layer.

On the other hand, Japanese Patent Application Laid-Open No. 9-47721 discloses a method of applying a black paint to a transparent resin plate which has been subjected to a hard coat treatment in advance. This coating means is a means for using a silicone-modified acrylic resin as a coloring layer and directly applying it to the hard coat layer. According to this coating means, since the coloring layer is directly provided on the transparent resin plate which has already been subjected to the hard coat treatment, a primer layer interposed between the transparent resin plate and the hard coat layer is formed. Since the treatment liquid does not come into direct contact with the black paint, it is not contaminated, and as a result, there is no danger that the appearance quality of the product is deteriorated due to dirt.

However, the formation of a silicone-modified acrylic resin-based colored layer involves a curing reaction between a main agent and a curing agent, and can ensure sufficient durability especially under severe use environments in the application field of the present invention. In this case, it is usually necessary to perform a baking and drying process for about 30 to 60 minutes. In industrial production, not only a drying furnace is indispensable, but also a work process becomes longer and production costs increase. There is a problem.

The present invention has been made under the above-mentioned technical background, and utilizes a known technique of providing a resin-based colored layer on a transparent resin plate which has been subjected to a hard coat treatment in advance. With a colored layer, a colored layer can be easily formed on a part of the colored layer, and a high bonding strength between the transparent resin plate and the metal can be expressed in the colored layer part, and an effective concealing function can be imparted. An object is to provide a joint structure between a transparent resin plate and a metal.

[0011]

According to the present invention, in order to achieve the above object, if a colored paint made of a urethane-based resin is used as the colored layer, the baking of the colored layer on the surface of the transparent resin plate is achieved. No process is required, reaction can be cured in a short time at room temperature, the formation of the colored layer becomes easy, and the adhesion between the colored layer and the silicone-based hard coat layer formed on the surface of the transparent resin plate is improved. The present inventors have found that it is possible to form a colored layer with improved weather resistance and abrasion resistance, and to secure a desired high bonding strength between a transparent resin plate and a metal.

That is, the present invention provides a transparent resin plate having a colored layer in which a silicone-based hard coat layer is formed on the surface and a urethane resin-based colored layer is formed on a part of the surface of the hard coat layer. The present invention provides a joint structure between a transparent resin plate with a colored layer and a metal, wherein the transparent resin plate with the colored layer is bonded to the metal via an elastic adhesive at a portion where the colored layer is formed.

That is, the main points of the constitution of the present invention are: first, use of a transparent resin plate having a silicone-based hard coat layer formed on the surface thereof in advance; second, the surface of the transparent resin plate having the hard coat layer Thirdly, the transparent resin plate and the metal are bonded via an elastic adhesive at a portion where the colored layer is formed, wherein the colored layer formed on a part of the colored layer is made of a urethane resin-based colored paint. This is a bonding structure between a transparent resin plate with a colored layer and a metal, which is summarized in the following.

The transparent resin plate used in the present invention is a plate formed of a single resin selected from an acrylic resin, a polycarbonate resin, a polyarylate resin, and a polysulfone resin.

The silicone-based hard coat layer formed on the surface of the transparent resin plate is made of RSi (OH) ₃ (R
Is a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, a vinyl group, a 3.3-trifluoropropyl group, a γ-aminopropyl group, a γ-methacryloxypropyl group, and a γ-glycidoxypropyl group. ) And a coat layer containing colloidal silica.

Further, in the transparent resin plate on which the hard coat layer is formed, the thickness of the urethane resin-based colored layer formed on a part of the surface of the hard coat layer is 10 μm to 10 μm.
The preferred range is 0 μm.

Further, when a primer layer is interposed between the transparent resin plate and the hard coat layer, the primer layer is suitably made of, for example, an acrylic solvent type primer treatment solution.

The elastic adhesive is an adhesive generally used for joining a metal frame of a vehicle window material to a transparent resin plate. In addition to a urethane-based adhesive, a polysulfide-based adhesive is also applicable. It is possible.

In the present invention, the metal bonded to the transparent resin plate is, for example, a window glass of an automobile or a construction machine, a sunroof, a light cover, or a metal material formed on a frame such as a window for a vehicle. Is meant.

As described above, in the present invention, as in the conventional joining structure, a black paint is applied before the transparent resin plate is subjected to the hard coat treatment, and then the hard coat treatment liquid is applied to the transparent resin plate including the painted surface. Unlike the method in which a hard coat treatment is performed so as to seal the colored layer inside the hard coat layer by coating, the hard coat treatment is performed on the upper surface of a silicone-based hard coat layer of a transparent resin plate that has been subjected to a hard coat treatment in advance. Since the black paint made of urethane resin is applied with high adhesiveness to the coat layer and adhesiveness to the elastic adhesive, it does not involve baking and drying work, and it is a simple operation of drying at room temperature. The black paint can be formed on the upper surface of the hard coat layer with high bonding strength and high strength, and the bonding strength between the black paint and the elastic adhesive is increased. It can be be made rigid structure bonding between genera. Further, with such a structure, there is no danger of contaminating the hard coat treatment liquid.

Further, as a preferred embodiment of the present invention,
As described in claim 2, since the urethane resin-based colored layer has a bonding structure of a transparent resin plate with a colored layer containing a silane-based coupling agent and a metal, the silicone-based colored layer of the transparent resin plate is used. The bonding strength between the hard coat layer and the elastic adhesive is further enhanced, and the bonding structure between the transparent resin plate with the colored layer and the metal can be made stronger as a whole.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a basic embodiment of a joint structure between a transparent resin plate with a colored layer and a metal according to the present invention will be described with reference to the drawings. In FIG. 1, (1) is a transparent resin plate, on both sides of which silicone-based hard coat layers (2) and (2) are formed, and a part of the surface of the hard coat layer (2) on one side. A urethane resin-based coloring layer (3) is formed. (4) is a metal, and at a position facing the urethane resin colored layer (3) formed on one upper surface of the transparent resin plate (1), the transparent resin plate is interposed via a urethane adhesive (5). The structure is joined to (1).

The basic embodiment shown in FIG. 1 will be described with reference to a specific example. For example, when applied to a front window or a rear window of an automobile, as shown in FIG. A black urethane resin-based coloring layer (3) having a fixed width is applied along the periphery of the transparent resin plate (1) having the hard coat layers (2) and (2) on both surfaces. (4) is a metal frame for integrally joining the windows, which is coated with a resin paint such as melamine alkyd, melamine acrylic, polyester melamine or the like. Transparent resin plate (1)
A urethane-based adhesive (5) is interposed between the colored layer (3) and the colored layer (3) formed at the periphery of the colored layer (3), and the adhesive (5) is hidden without protruding from the colored layer (3). Thus, the structure is joined by being interposed between them.

In an actual joining structure of an automobile window or the like, in addition to the above-described basic embodiment, a structure in which a dam rubber or a molding is arranged so as to cover the side surface of the elastic adhesive (not shown). ).

Here, as the resin material of the transparent resin plate (1), a single resin selected from acrylic resin, polycarbonate resin, polyarylate resin and polysulfone resin was formed into a plate shape as described above. Things,
The thickness is arbitrarily determined depending on the application, but is generally 2
It is about 8 mm to 8 mm.

In the present invention, the transparent resin plate (1) and the hard coat layers (2) formed on both surfaces thereof are provided.
Usually, a primer layer is interposed between (2) and
There is no particular limitation on the type, and any type may be used as long as it is compatible with the resin material (1) and the silicone-based hard coat layer (2). For example, when the transparent resin plate (1) is made of a polycarbonate resin, an acrylic solvent-type primer is suitable. In addition, additives such as a cross-linking agent and an ultraviolet absorber may be appropriately compounded in the primer as needed.

Further, the hard coat layers (2) and (2)
Is preferably about 1 μm to 5 μm,
If it is too thin, the effect of scratch resistance cannot be obtained, and if it is too thick, no further effect can be obtained, which is uneconomical.

Next, as the urethane resin-based colored layer (3), for example, "Primer 35" (trade name, manufactured by Sunrise MSI) as a suitable commercial product of the resin-based paint can be used.

As the silane coupling agent blended in the urethane resin colored layer (3), those having dispersibility with the urethane resin can be used, and the blending amount is based on 100 parts by weight of the urethane resin. The amount is preferably about 5 to 100 parts by weight.

As the coloring agent to be mixed in the urethane resin-based coloring layer (3), it is possible to use carbon black, other inorganic pigments and organic pigments which are dispersible and wettable with the urethane resin. The mixing amount is about 5 to 200 parts by weight based on 100 parts by weight of the urethane resin.

The thickness of the urethane resin-based coloring layer (3) is about 5 μm to 100 μm, and depends on the amount of the coloring agent. In practice, it is desirable to set the thickness in the range of 10 μm to 30 μm because it is uneconomical.

In order to manufacture the transparent resin plate (1) having the silicone-based hard coat layers (2) and (2) of the present invention, if necessary, a primer treatment liquid is applied to both surfaces of the transparent resin plate (1). After drying to form a primer layer, a silicone-based hard coat liquid is applied and cured by hot-air drying or the like to form the hard coat layer (2).
Form (2).

Then, a urethane resin colored layer (3) is formed on the surface of the silicone hard coat layer (2) on one side of the transparent resin plate (1). As the forming means, the transparent resin plate (1) is trimmed in advance into a predetermined shape, or the uncolored portion on the surface of the silicone-based hard coat layer (2) is masked without trimming, and then the coloring is performed. It is possible to adopt means for applying the paint, mainly by spray coating, brush coating, roller coating, flow coater coating, etc., and to leave it at room temperature or heat treatment to cure it, but if necessary, screen printing can also be applied. is there.

[0034]

Next, examples of the present invention will be described together with comparative examples. In addition, the following Examples 1-4 and Comparative Examples 1-2
The joint structure between the transparent resin plate with the colored layer and the metal, which is the target, is a joint structure between the transparent resin plate with the colored layer and the metal such as a rear window or a sunroof of an automobile whose structure is generally shown in FIG. The bonding strength was evaluated by measuring the adhesive strength using a test sample prepared on the assumption of the above, and the appearance quality was evaluated by observing the presence or absence of contamination by visual inspection. The materials used as each measurement sample will be described below. <Transparent Resin Plate> S1: A black urethane resin-based coloring layer (“Primer 35” manufactured by Sunrise MSI, thickness: 15 μm) was formed on one surface of a 5 mm-thick polycarbonate resin plate having a silicone-based hard coat layer formed on both surfaces. S2: Polyurethane methacrylic resin plate with a thickness of 15 mm having a black urethane resin colored layer (Sunrise MSI, "Primer 35") on one surface of a polymethyl methacrylic resin plate having a thickness of 5 mm and a silicone hard coat layer formed on both surfaces. ) Is partially formed. S3: A black silicone-modified acrylic resin-based colored layer ("Silicon Wide # 500" manufactured by Toupe Co., Ltd.) is coated on one side of a 5 mm thick polycarbonate resin plate having a silicone hard coat layer formed on both sides. ", A resin plate partially having a thickness of 20 µm) S4: A silicone-based hard coat layer is formed on both surfaces. A polycarbonate resin plate having a thickness of 5 mm. However, this transparent resin plate assumes that a colored layer is formed between the resin plate-shaped molded body of the conventional structure and the hard coat layer, but the colored layer is used as the material for measuring the adhesive strength. The material which was not formed, and the material for the visual inspection, which had actually formed a colored layer (“SS8-Conc 991 Black”, manufactured by Toyo Ink Mfg. Co., Ltd., polyvinyl chloride / acrylic resin-based, 10 μm thick) was used. . <Metal> M1: 1 mm thick steel plate having a 35 μm thick melamine alkyd coating film formed on the surface (SS41) M2: 1 mm thick steel plate having a 20 μm thick acryl melamine coating film formed on the surface (SS41) <Adhesive> Urethane-based adhesive [SR Seal U90 manufactured by Sunrise MSI]

[Adhesion Strength Test] The preparation of a test sample will be described. As shown in FIG. 3, a transparent resin plate (1) and a metal plate (4) are formed into rectangular sections each having a size of 120 mm × 25 mm. From 15 mm inside from the short side end of the section to 2
5m thickness parallel to the short side in 10mm width part up to 5mm
This was prepared by joining both sections with an adhesive (5) layer of m.

The materials used for each of the above measurement samples were as follows:
Table 1 shows examples and comparative examples.

[0037]

[Table 1]

The test method and test conditions were as follows. <Test Method> The bond strength of the test sample was measured by measuring the shear strength, and a constant crosshead speed short axis tensile tester (Autograph AG-5, manufactured by Shimadzu Corporation) was used.
000C) under a measuring condition of a tensile speed of 200 mm / min, and an average value of measured values of five samples was adopted. <Test conditions> The test samples were subjected to the following four levels of state adjustment and measured for each state.

Condition 1 = Normal strength: 1 at room temperature after sample preparation
Measured after standing for 68 hours.

Condition 2 = heat resistance: 1 at room temperature after sample preparation
Left for 68 hours, then 336 hours at 90 ° C.
Measure after standing for 1 hour at room temperature.

Condition 3 = water-resistant strength: 1 at room temperature after sample preparation
After immersion in water at 40 ° C. for 336 hours, and then left at room temperature for 1 hour, measurement was performed.

Condition 4 = Accelerated weathering strength: After the sample was prepared, it was left at room temperature for 168 hours, and then subjected to a 2000-hour weathering deterioration acceleration test using a sunshine weather meter, and then left at room temperature for 1 hour and measured.

The measured values of the shear strength of each test piece are as shown in Table 2, and the evaluation criterion based on each measured value was 5.5M.
When Pa or more was evaluated as good, and less than 5.5 MPa was evaluated as poor. Examples 1 to 4 were all good, and Comparative Examples 1 and 2 were all poor.

[0044]

[Table 2]

[Visual Inspection] Mainly, a sample according to the embodiment of the present invention having the same material composition as the test sample of the embodiment 1, a polyvinyl acetate / acrylic resin-based coloring layer provided on a transparent resin plate, A sample of the comparative example having the same material composition as the test material of the comparative example 2 except that a transparent resin plate obtained by interposing a polymethyl methacrylate-based primer layer between the hard coat layer and the colored layer was used. Was formed in the automotive window shown in FIG. 2, and a visual inspection was performed to determine whether or not contamination due to the paint of the colored layer was present near the boundary between the colored layer and the non-colored layer of the transparent resin plate.

As a result, according to Example 1 of the present invention, the hard coat layer did not contain any contamination and had good appearance quality, whereas according to Comparative Example 2, the hard coat layer was colored. Slight contamination was observed in the hard coat layer near the boundary between the layer and the non-colored layer, and the appearance quality was poor.

[0047]

As described above, the bonding structure of the transparent resin plate with the colored layer and the metal according to the present invention has a silicon-based hard coat layer formed on the surface thereof, Because a transparent resin plate having a colored layer in which a urethane resin-based colored layer is formed in part and a metal are bonded to each other via an elastic adhesive in a portion where the colored layer is formed, since a bonding structure is used. The colored layer, on the upper surface of the silicone-based hard coat layer, by a simple operation of only drying at room temperature without baking and drying operation, it is possible to form a strong and strong adhesive strength, and between the colored layer and the elastic adhesive By increasing the bonding strength, the shear strength at the interface between the transparent resin plate with the colored layer and the elastic adhesive can also be improved, and the effect that the overall bonding between the transparent resin plate with the colored layer and the metal can be firmly achieved. is there.

Further, according to the present invention, in the transparent portion of the transparent resin plate, in particular, in the hard coat layer near the boundary between the colored layer and the non-colored layer, there is no contamination and the transparent resin with the colored layer excellent in appearance quality. There is an advantage that a joint structure between the plate and the metal can be obtained.

Further, in the present invention, as described in claim 2, the colored layer contains a silane-based coupling agent, so that the silicone-based hard coat layer and the elastic adhesive can be used. Has the advantage that the bonding strength between the transparent resin plate with the colored layer and the metal can be further strengthened as a whole.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view showing an embodiment of a basic bonding structure of a transparent resin plate with a colored layer and a metal according to the present invention.

FIG. 2 is a partial sectional perspective view showing a specific example of the embodiment of the present invention.

FIG. 3 is a perspective view showing a test sample for measuring a shear test in an example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Transparent resin plate 2 ... Hard coat layer 3 ... Urethane resin coloring layer 4 ... Metal 5 ... Urethane adhesive

Claims (2)

[Claims] 1. A transparent resin plate having a colored layer in which a silicone-based hard coat layer is formed on the surface and a urethane resin-based colored layer is formed on a part of the surface of the hard coat layer, and a metal A bonding structure between a transparent resin plate with a colored layer and a metal, wherein the transparent resin plate with the colored layer is bonded via an elastic adhesive at a portion where the colored layer is formed. 2. The structure according to claim 1, wherein the urethane resin-based colored layer contains a silane-based coupling agent.