JP2013226719A - Resin product, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin product in which degradation of tight adhesiveness between an undercoat layer and a topcoat layer due to UV irradiation and occurrence of cracks on the topcoat layer can be advantageously prevented.SOLUTION: A resin product is configured by lamination-forming an undercoat layer 14 including a base layer part 18 constituted of a UV-curing acrylic resin layer and a surface layer part 20 constituted of a fluororesin layer, on a surface of a resin substrate 12 made of polycarbonate, meanwhile, performing argon plasma treatment on the surface layer part 20 of the undercoat layer 14 and, further, lamination-forming a topcoat layer 16 constituted of plasma CVD layers 22, 24 of silicon compound on the surface layer part 20 subjected to the argon plasma treatment.

Description

  The present invention relates to a resin product and a manufacturing method thereof, and more particularly to a resin product that can be suitably used as a resin glass (organic glass) and an advantageous manufacturing method of such a resin product.

  Conventionally, resin products having both excellent moldability and light weight have been widely used as, for example, interior and exterior parts of vehicles such as automobiles, electrical, electronic parts, and building parts. Among these resin products, for example, highly transparent resin products made of polycarbonate molded products are superior in terms of lightness, impact resistance and workability compared to inorganic glass. As resin glass which substitutes for glass, it is used for the window glass of vehicles, such as a car, various displays, or the cover of various instruments, etc., for example.

  As is generally known, such polycarbonate resin products have problems in weather resistance such as discoloration and strength reduction when exposed to ultraviolet rays, and are more resistant to abrasion than inorganic glass. It also has the disadvantage of being inferior (wear resistance and scratch resistance). Therefore, if the resin product made of polycarbonate is used outdoors, such as a window glass of an automobile, and the surface damage is a serious defect, such resin is used. It was necessary to take measures to improve the weather resistance and abrasion resistance of the product.

  Under such circumstances, for example, in Japanese Patent Application Laid-Open No. 2010-253683 (Patent Document 1), as a resin product (referred to as a plastic laminate in the above publication) applied to a window glass of an automobile, polycarbonate or the like is used. An undercoat layer made of an acrylic resin rich in weather resistance is laminated on the surface of a resin base material made of a resin molded body, and a plasma CVD layer of a silicon compound having excellent abrasion resistance on the undercoat layer A structure obtained by further laminating a top coat layer made of In such a resin product, sufficient weather resistance and abrasion resistance can be advantageously ensured.

  By the way, when forming a cured layer (cured film) of acrylic resin, either a thermosetting acrylic resin paint or a UV curable acrylic resin paint is generally used. As is well known, there is a large difference in curing time between the coating layer of the UV curable acrylic resin coating and the coating layer of the thermosetting acrylic resin coating. For example, the former is about several minutes. In the latter case, it takes several hours to complete the curing. Therefore, when manufacturing a resin product in which an undercoat layer made of a UV curable acrylic resin layer and a topcoat layer are laminated on the surface of a polycarbonate resin base material, as a material for forming the undercoat layer, Rather than using a thermosetting acrylic resin paint, the intended resin product can be produced more efficiently by using a UV curable acrylic resin paint. That is, a resin product having an undercoat layer made of a UV curable acrylic resin layer is superior in productivity to a resin product having an undercoat layer made of a thermosetting acrylic resin layer.

  However, the present inventor has developed a resin product in which an undercoat layer and a topcoat layer made of a UV curable acrylic resin layer are laminated on the surface of a polycarbonate resin substrate, and a polycarbonate resin substrate. Using a resin product in which an undercoat layer made of a thermosetting acrylic resin layer and a topcoat layer are laminated on the surface, a weather resistance test by ultraviolet irradiation was performed on these under various conditions. In a resin product in which the coat layer is a thermosetting acrylic resin layer, the undercoat layer is formed under the condition that no defects such as peeling of the topcoat layer from the undercoat layer and cracks in the topcoat layer were observed. In the resin product composed of the UV curable acrylic resin layer, peeling or cracking of the top coat layer was observed.

  For this reason, in resin products in which an undercoat layer and a topcoat layer are laminated on the surface of a polycarbonate resin substrate, if the undercoat layer is composed of a UV curable acrylic resin, Although the improvement of the property can be achieved, the inventor's research shows that there is a tendency for the adhesion between the undercoat layer and the topcoat layer to decrease or the crack to occur in the topcoat layer due to ultraviolet irradiation. It became clear.

JP 2010-253683 A

  Here, the present invention has been made in the background as described above, and the problem to be solved is an underlayer including a UV curable acrylic resin layer on the surface of a polycarbonate resin substrate. In resin products in which a coat layer and a top coat layer are laminated, the adhesiveness between the undercoat layer and the top coat layer due to ultraviolet irradiation and cracks in the top coat layer are advantageously prevented. It is to provide an improved structure as can be done. Another object of the present invention is to provide a method for advantageously producing such a resin product.

  And, as a result of intensive research to solve the above problems, the present inventor, by interposing a fluorine resin layer between the UV curable acrylic resin layer and the top coat layer made of a silicon compound, The present inventors have found that the problems of lowering the adhesion of the topcoat layer made of a silicon compound to the UV curable acrylic resin layer and cracking in the topcoat layer due to ultraviolet irradiation can be advantageously solved.

  That is, the present invention has been completed based on such knowledge, and the gist thereof includes a resin base material made of a resin molded product made of polycarbonate, and a UV curable acrylic resin layer. In a resin product comprising an undercoat layer formed on the surface of the resin base material, and a topcoat layer formed of a plasma CVD layer of a silicon compound formed on the undercoat layer, The undercoat layer is laminated on the surface of the resin base material, and a base layer portion made of the UV curable acrylic resin layer, and a surface layer portion made of a fluororesin layer further laminated on the base layer portion. It is in the resin product characterized by being comprised by these.

  According to one of the advantageous embodiments of the present invention, the topcoat layer is composed of a base layer portion formed on the undercoat layer and a surface layer portion further formed on the base layer portion. It is comprised and the silicon compound which comprises this surface layer part has a hardness higher than the silicon compound which comprises this base layer part.

  Moreover, according to one of the preferable aspects of this invention, between the said base layer part and the said surface layer part of the said topcoat layer, the silicon compound which comprises this base layer part, and the silicon compound which comprises this surface layer part A mixed intermediate layer is formed, and the content of the silicon compound constituting the base layer portion in the intermediate layer gradually decreases from the base layer portion side toward the surface layer portion side, while the surface layer portion is configured. The content ratio of the silicon compound in the intermediate layer is configured to gradually increase from the base layer portion side toward the surface layer portion side.

Furthermore, according to one of the advantageous aspects of the present invention, the top coat layer is formed by laminating a SiO ₂ plasma CVD layer laminated on the undercoat layer, and a laminate formed on the base layer portion. And a surface layer portion composed of a plasma CVD layer of SiON, and an intermediate layer composed of a plasma CVD layer in which SiO ₂ and SiON are mixed, interposed between the base layer portion and the surface layer portion. The SiO ₂ content in the intermediate layer gradually decreases from the base layer side toward the surface layer side, while the SiON content in the intermediate layer decreases from the base layer side to the surface layer portion. It will be comprised so that it may increase gradually toward the side.

  And this invention includes the resin base material which consists of a resin-made product made from polycarbonate, the undercoat layer laminated | stacked on the surface of this resin base material including the UV curable acrylic resin layer, and this undercoat layer A method for producing a resin product comprising a top coat layer made of a plasma CVD layer of a silicon compound laminated on the substrate, comprising: (a) a step of preparing the resin substrate; and (b) After forming a coating layer on the surface of the resin substrate using a UV curable acrylic resin coating, the coating layer is irradiated with ultraviolet rays to cure the coating layer. Forming a UV curable acrylic resin layer on the surface of the material, and then forming a fluororesin layer on the UV curable acrylic resin layer; , Laminated on the base layer A step of laminating and forming the undercoat layer composed of the surface layer portion made of the fluororesin layer formed on the surface of the resin substrate; and (c) the silicon compound is formed on the undercoat layer. The gist of the present invention is also a resin product manufacturing method including a step of laminating and forming a top coat layer made of a plasma CVD layer by a plasma CVD method.

  According to one of the desirable embodiments of the present invention, the surface layer portion of the undercoat layer that has been subjected to the argon plasma treatment is made of a low-hardness silicon compound of two types of silicon compounds having different hardnesses. After the plasma CVD layer to be formed is stacked by plasma CVD, a plasma CVD layer of a silicon compound having a high hardness of the two types of silicon compounds is further stacked by plasma CVD on the low-plasma CVD layer. By doing so, the top coat layer has a multilayer structure of a base layer portion made of a low-hardness silicon compound plasma CVD layer and a high-hardness silicon compound plasma CVD layer on the undercoat layer. It will be laminated and formed.

  According to another advantageous aspect of the present invention, there is provided a multi-layer structure of a base layer portion made of the low-hardness silicon compound plasma CVD layer and a surface layer portion made of the high-hardness silicon compound plasma CVD layer. The top coat layer thus formed is laminated on the undercoat layer as follows. That is, (a) after the step of accommodating the resin base material in the reaction chamber and making the reaction chamber in a vacuum state, (b) the first silicon compound gas in the reaction chamber in the vacuum state The first film-forming gas containing is introduced, the first film-forming gas is reacted by a plasma CVD method, and a silicon compound is formed on the undercoat layer of the substrate housed in the reaction chamber The step of laminating and forming the base layer portion made of the plasma CVD layer is performed, and then (c) a second silicon compound gas is contained in the reaction chamber containing the resin base material on which the base layer portion is laminated. A second film-forming gas capable of forming a silicon compound layer having a hardness higher than that of the base layer part is introduced, and the second film-forming gas is reacted by a plasma CVD method to form a base layer part. In contrast, plasma CVD of silicon compounds with higher hardness And (d) introducing an amount of at least a part of the gas component in the first film-forming gas introduced into the reaction chamber into the reaction chamber. The at least part of the gas in the reaction chamber from the start of the introduction of the second film-forming gas into the reaction chamber by gradually decreasing from the start of the introduction of the second film-forming gas to zero. Until the amount of the component becomes zero, the reaction by the plasma CVD method of the first film-forming gas and the reaction by the plasma CVD method of the second film-forming gas are performed simultaneously, and the base layer Before forming the surface layer portion on the base portion, by forming an intermediate layer on the base layer portion in which the silicon compound forming the base layer portion and the silicon compound forming the surface layer portion are mixed The base layer portion and the surface layer on the surface of the resin base material Than is formed by lamination of the topcoat layer having a multilayer structure.

  Further, the top coat layer having a multilayer structure of a base layer portion made of a plasma CVD layer of the low hardness silicon compound and a surface layer portion made of the plasma CVD layer of the high hardness silicon compound is formed on the undercoat layer. In addition, the laminate is formed as follows. That is, (a) after the step of accommodating the resin base material in the reaction chamber and making the reaction chamber in a vacuum state, (b) the first silicon compound gas in the reaction chamber in the vacuum state The first film-forming gas containing is introduced, the first film-forming gas is reacted by a plasma CVD method, and a silicon compound is formed on the undercoat layer of the substrate housed in the reaction chamber And (c) after forming the base layer portion in the reaction chamber containing the resin base material on which the base layer portion is stacked. In addition, while continuously introducing the first film-forming gas, a gas component that is not contained in the first film-forming gas is further introduced into the first film-forming gas. A gas component included and a gas component not included in the first film-forming gas. A second film-forming gas for forming a silicon compound layer having a hardness higher than that of the base layer portion is introduced into the reaction chamber, the second film-forming gas is reacted by a plasma CVD method, By carrying out a step of laminating and forming a surface layer portion made of a plasma CVD layer of a silicon compound having a hardness higher than that of the base layer portion, the base layer portion and the surface layer portion on the surface of the resin base material The top coat layer having a multilayer structure is formed by lamination.

Further, according to one of the preferred embodiments of the present invention, the topcoat layer comprises a base layer portion composed of a SiO ₂ plasma CVD layer laminated on the undercoat layer of the resin substrate, and the base layer portion. A surface layer portion composed of a plasma CVD layer of SiON laminated thereon, and an intermediate layer composed of a plasma CVD layer mixed with SiO ₂ and SiON interposed between the base layer portion and the surface layer portion. And the step of forming the topcoat layer comprises: (a) storing the resin substrate on which the undercoat layer is formed in a reaction chamber, and evacuating the reaction chamber; A silicon compound gas and an oxygen gas are introduced into a vacuum reaction chamber, the silicon compound gas and the oxygen gas are reacted by a plasma CVD method, and the resin base material contained in the reaction chamber is unloaded. A step of laminating a base layer portion composed of the SiO ₂ plasma CVD layer on the dark coat layer; and (c) containing the resin base material in which the base layer portion is laminated on the undercoat layer. By introducing nitrogen gas or nitrogen compound gas into the reaction chamber while continuously introducing the silicon compound gas and oxygen gas after the formation of the base layer portion on the undercoat layer, the silicon compound gas and A reaction by oxygen plasma plasma CVD method and a reaction by silicon compound gas and oxygen gas and nitrogen gas or nitrogen compound gas plasma CVD method are carried out simultaneously, and the base layer portion laminated on the undercoat layer is formed. in contrast, the the steps of the SiO ₂ and SiON is laminated an intermediate layer consisting of a plasma CVD layer that has a mixed the intermediate layer and the base layer part in (d) of the undercoat layer After the formation of the intermediate layer, the silicon compound gas and oxygen gas and nitrogen gas or nitrogen compound gas are reacted by the plasma CVD method in the reaction chamber containing the layered resin base material, and the underlayer is formed. Forming a surface layer portion made of the SiON plasma CVD layer on the intermediate layer laminated on the coat layer via the base layer portion.

  In the resin product according to the present invention, the undercoat layer has a base layer portion made of a UV curable acrylic resin layer, thereby achieving excellent productivity while stably providing sufficient weather resistance. Can be secured. Moreover, the undercoat layer has a multi-layer structure of a base layer portion made of such a UV curable acrylic resin layer and a surface layer portion made of a fluororesin layer, thereby comprising a UV curable acrylic resin layer and a silicon compound. A fluororesin layer is interposed between the top coat layer. Therefore, both the decrease in adhesion between the UV curable acrylic resin layer and the topcoat layer and the generation of cracks in the topcoat layer due to ultraviolet irradiation can be advantageously prevented.

  Therefore, in the resin product according to the present invention as described above, while realizing high productivity, excellent weather resistance and abrasion resistance can be stably exhibited over a longer period of time, and also by long-term use. Deterioration in appearance and quality can be prevented very effectively.

  Then, according to the method for producing a resin product according to the present invention, substantially the same operation / effect as the excellent operation / effect exhibited in the resin product having the structure according to the present invention can be enjoyed effectively. Resin products exhibiting such excellent characteristics can be advantageously produced industrially.

It is a fragmentary sectional view showing one embodiment of a resin product having a structure according to the present invention. It is explanatory drawing which shows an example of the process implemented when obtaining the resin product shown by FIG. 1, Comprising: The topcoat layer is further laminated | stacked and formed on the undercoat layer laminated | stacked and formed on the resin base material surface. It is explanatory drawing which shows the state which exists.

  Hereinafter, in order to clarify the present invention more specifically, embodiments of the present invention will be described in detail with reference to the drawings.

  First, FIG. 1 shows a resin glass 10 for a rear window of an automobile in a partial cross-sectional form as an embodiment of a resin product having a structure according to the present invention. As apparent from FIG. 1, the resin glass 10 has a resin base material 12, and an undercoat layer 14 is provided on the front and back surfaces (upper and lower surfaces in FIG. 1) of the resin base material 12. They are stacked. Further, a top coat layer 16 is further laminated on the surface of each of the undercoat layers 14 and 14 opposite to the resin substrate 12 side. In the following, for convenience, the upper surface in FIG. 1 is referred to as the front surface, and the lower surface in FIG. 1 is referred to as the back surface.

  More specifically, the resin base material 12 has a transparent flat plate shape and is formed of a resin molded product that is injection-molded using polycarbonate. The resin base material 12 may be molded by a method other than injection molding as long as it is a polycarbonate resin molded product. Moreover, the thickness of the resin base material 12 is not limited at all, and is appropriately determined according to the use and required characteristics of the resin glass 10. Here, the thickness is about 2 to 7 mm. Is done.

  In this embodiment, the undercoat layer 14 has a multilayer structure (two-layer structure) having a base layer portion 18 and a surface layer portion 20. The base layer portion 18 of the undercoat layer 14 is formed on both the front and back surfaces of the resin base material 12 for the purpose of providing the resin glass 10 with weather resistance based on ultraviolet resistance or the like. Each of these layers is directly laminated so as to cover the entire surface, and has a thin film form. Such a base layer portion 18 is constituted by a UV curable acrylic resin layer. That is, the base layer portion 18 is formed by curing a coating layer formed on both surfaces of the resin substrate 12 by UV irradiation using a UV curable acrylic resin paint.

  The thickness of the base layer portion 18 is not particularly limited, but is generally about 1 to 20 μm. This is because if the thickness of the base layer portion 18 is less than 1 μm, it is too thin and it may be difficult to give sufficient weather resistance to the resin glass 10. Even if the thickness of 18 is made larger than 20 μm, it is difficult to further improve the weather resistance of the resin glass 10. On the contrary, the material cost may be wasted or the formation time of the base layer portion 18 may be lengthened. Because there is.

  On the other hand, the surface layer portion 20 of the undercoat layer 14 is made of a fluororesin layer, here, a polytetrafluoroethylene (PTFE) layer, and has a thin film shape that is thinner than the base layer portion 18. The surface layer portion 20 is formed of each of the base layer portions 18 and 18 in order to protect the base layer portion 18 made of the UV curable acrylic resin layer during the argon plasma treatment applied to the undercoat layer 14 as will be described later. These are laminated on the surface opposite to the resin substrate 12 side.

  In addition, the kind of fluororesin which comprises the surface layer part 20 is not specifically limited, In addition to PTFE, tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride ( PVF), perfluoroalkoxy fluororesin (PFA) and the like can be exemplified. And these various fluororesins are used as a material for forming the surface layer portion 20 singly or in combination of a plurality of types as appropriate.

  The thickness of the surface layer portion 20 is not limited at all, but is generally about 1 to 20 μm. This is because if the thickness of the surface layer portion 20 is thinner than 1 μm, the protective function of the base layer portion 18 may not be sufficiently exhibited because it is too thin, and the thickness of the surface layer portion 20 is 20 μm. Even if it is thicker, it is difficult to further enhance the protective function of the base layer portion 18. On the other hand, the material cost may be wasted or the formation time of the surface layer portion 20 may be lengthened.

  In addition, the surface layer portion 20 made of such a fluororesin generally applies or sprays a fluororesin paint containing one or more of the various fluororesins as described above on the base layer portion 18. Alternatively, after the coating layer is formed on the base layer portion 18 by dipping or the like, the coating layer is heated, irradiated with ultraviolet rays, or the like to cure the coating layer. The surface layer portion 20 made of a fluororesin is preferably composed of an ultraviolet curable layer in order to simplify the formation process and reduce the equipment cost required for the formation.

  Furthermore, as a method for forming the surface layer portion 20, in addition to the above-described forming method by coating, for example, a known physical vapor deposition method such as a sputtering method, a vacuum vapor deposition method, a molecular beam vapor deposition method, an ion plating method, an ion beam vapor deposition method or the like. (PVD method) can also be employed.

The topcoat layer 16 has a base layer portion 22 located on the undercoat layer 14 side and a surface layer portion 24 laminated on the base layer portion 22. Here, the base layer portion 22 is composed of a plasma CVD layer made of SiO ₂ formed by a plasma CVD method, and the surface layer portion 24 is made of SiON formed by a plasma CVD method. It is composed of a plasma CVD layer.

  That is, in the present embodiment, the surface layer portion 24 that forms the surface layer portion including the entire surface of the top coat layer 16 is composed of very hard SiON. Thereby, the hardness of the surface of the topcoat layer 16 is sufficiently increased, and further excellent abrasion resistance is imparted to the resin glass 10.

Further, the base layer portion 22 that forms the portion of the undercoat layer 14 side including the entire surface of the interface between the top coat layer 16 and the undercoat layer 14 is inferior in hardness to SiON. SiO having a thermal expansion coefficient approximate to the thermal expansion coefficient of the acrylic resin constituting 18 and also exhibiting properties superior to those of SiON in adhesion to the fluororesin constituting the surface layer portion 20 of the undercoat layer 14 _It consists of _two . As a result, cracking of the topcoat layer 16 and peeling from the undercoat layer 14 due to thermal expansion differential stress with the undercoat layer 14 are possible without causing a decrease in the hardness of the topcoat layer 16. Therefore, the adhesiveness of the topcoat layer 16 to the undercoat layer 14 is advantageously improved.

  Although the total thickness of the top coat layer 16 is not limited at all, it is preferably about 1 to 20 μm. Thereby, it is possible to sufficiently impart abrasion resistance to the resin glass 10 without unnecessarily increasing the total thickness of the top coat layer 16.

And it is desirable for the thickness of the base layer part 22 to be about 0.5-10 micrometers among the topcoat layers 16 which have such thickness. This is because if the thickness of the base layer portion 22 made of SiO ₂ is thinner than 0.5 μm, the adhesion to the undercoat layer 14 may be insufficient because it is too thin. Further, when the thickness of the base layer portion 22 is larger than 10 μm, the proportion of the base layer portion 22 made of SiO _{2 in} the top coat layer 16 becomes large. In other words, in the top coat layer 16, The proportion of the surface layer portion 24 made of high-hardness SiON is reduced. Therefore, the effect of improving the abrasion resistance of the resin glass 10 obtained by configuring the surface layer portion 24 of the topcoat layer 16 with SiON is not good. This is because there is a risk of becoming sufficient.

  In the present embodiment, an intermediate layer 26 made of a plasma CVD layer is provided between the base layer portion 22 and the surface layer portion 24. That is, the top coat layer 16 has a multilayer structure including the base layer portion 22, the intermediate layer 26, and the surface layer portion 24.

In the intermediate layer 26, SiO ₂ constituting the base layer portion 22 and SiON constituting the surface layer portion 24 are mixed. That is, the intermediate layer 26 is composed of a plasma CVD layer formed by a plasma CVD method and having a portion made of SiO ₂ and a portion made of SiON. Then, in the take intermediate layer 26, the content of SiO ₂ is, while gradually decreases from the base portion 22 side toward the surface portion 24 side and the content of SiON is, surface from the base layer 22 side It gradually increases toward the portion 24 side. That is, the content of SiO _{2 and} the content of SiON ₂ in the intermediate layer 26 change in an inclined manner from the base layer portion 22 side toward the surface layer portion 24 side.

Thus, in the present embodiment, the intermediate layer 26 having the structure as described above is provided between the base layer portion 22 made of SiO ₂ and the surface layer portion 24 made of SiON. A clear interface between the surface layer portion 24 and the surface layer portion 24 can be eliminated. As a result, for example, the occurrence of separation at the interface between the base layer portion 22 and the surface layer portion 24 is prevented as much as possible due to changes in the surrounding thermal environment, and the base layer portion 22 and the surface layer portion 24 are prevented. Is effectively enhanced.

  The thickness of the intermediate layer 26 is not limited at all, but is preferably about 0.1 to 10 μm. This is because if the thickness of the intermediate layer 26 is less than 0.1 μm, it is too thin and the effect of improving the adhesion between the base layer portion 22 and the surface layer portion 24 may not be sufficiently expected. In addition, if the thickness of the intermediate layer 26 is greater than 10 μm, the formation time of the entire topcoat layer 16 becomes redundant, which may cause a decrease in productivity of the resin glass 10 and an increase in production cost. Because.

  By the way, the resin glass 10 having the structure as described above is manufactured, for example, according to the following procedure.

  That is, first, a polycarbonate resin substrate 12 is molded by injection molding or the like. Thereafter, the base layer portion 18 of the undercoat layer 14 made of a UV curable acrylic resin layer is laminated and formed on both the front and back surfaces of the resin base 12. The base layer portion 18 is formed by applying a UV curable acrylic resin paint to both surfaces of the resin base 12 using, for example, a roller or a brush, or spraying it using a spray gun or the like, or After each coating layer of UV curable acrylic resin is formed by dipping operation or the like, the coating layer is formed by irradiating the coating layer with ultraviolet rays.

  Next, the surface layer portion 22 of the undercoat layer 14 made of a fluororesin layer (here, PTFE layer) is formed on the base layer portions 18 and 18 of the undercoat layer 14 laminated on both surfaces of the resin base material 12. Each base layer portion 18 is further laminated and formed so that the entire surface of each base layer portion 18 is covered with each surface layer portion 20. The surface layer 20 is formed by applying a fluororesin paint (here, PTFE resin paint) on each base layer 18 using, for example, a roller or a brush, or spraying it using a spray gun or the like. Alternatively, after forming the coating layers of the fluororesin by dipping operation or the like, the coating layers are formed by irradiating with ultraviolet rays.

  Thus, an undercoat having a multilayer structure (two-layer structure) of the base layer portion 18 made of a UV curable acrylic resin layer and the surface layer portion 20 made of a fluororesin layer on both the front and back surfaces of the resin base 12. The layers 14 are laminated to obtain an intermediate laminate 28 (see FIG. 2).

  Next, using the plasma CVD apparatus 30 having the structure shown in FIG. 2, the undercoat layers 14 and 14 of the intermediate laminate 28, specifically, the surface layer made of a fluororesin of the undercoat layers 14 and 14 is used. After performing the argon plasma process with respect to the parts 20 and 20 as needed, the topcoat layer 16 is further laminated | stacked on the surface layer parts 20 and 20 of those undercoat layers 14 and 14, respectively.

  As shown in FIG. 2, the plasma CVD apparatus 30 used here has the same basic structure as a conventional plasma CVD apparatus employing a parallel plate method. More specifically, the plasma CVD apparatus 30 has a vacuum chamber 32 as a reaction chamber. The vacuum chamber 32 further includes a chamber body 34 and a lid body 36. The chamber body 34 has a bottomed cylindrical shape or a casing shape including a cylindrical side wall portion 38 and a lower bottom wall portion 40 that closes a lower opening of the side wall portion 38. The lid body 36 is configured by a flat plate having a size capable of covering the entire upper opening 42 of the chamber body 34. Then, the chamber body 34 is hermetically sealed by being locked by a lock mechanism (not shown) while the lid body 36 covers the upper opening 42 of the chamber body 34.

  Further, upper holders 44, 44 are integrally provided on the lower surface of the lid body 36. Support protrusions 46 and 46 are integrally projected on the upper holders 44 and 44. The cathode electrode 48 accommodated in the chamber body 34 is supported by the support protrusions 46 and 46 and is held by the upper holders 44 and 44. In addition, one end of a power supply line 50 is connected to the cathode electrode 48, and the other end of the power supply line 50 is connected to a high-frequency power source 52 installed outside the vacuum chamber 32.

  On the lower bottom wall portion 40 of the chamber body 34, lower holders 54, 54 are integrally provided upright. On the lower holders 54, 54, upper support projections 56, 56 and lower support projections 58, 58 are integrally protruded apart from each other in the vertical direction. Then, the anode electrode 60 accommodated in the chamber body 34 faces the lower support protrusions 58, 58 in a state of facing the cathode electrode 48 held by the upper holders 44, 44 with a predetermined distance in the vertical direction. Supported by the lower holders 54 and 54. The anode electrode 60 is grounded. Further, the upper support protrusions 56, 56 of the lower holders 54, 54 can support the intermediate laminate 28.

  An exhaust pipe 62 is installed at one place on the circumference at the lower end of the side wall 38 of the chamber body 34 so as to penetrate the side wall 38 so as to communicate with the inside and outside of the chamber main body 34. A vacuum pump 64 is provided on the exhaust pipe 62. Then, by the operation of the vacuum pump 64, the gas in the chamber body 34 is discharged to the outside through the exhaust pipe 62, and the chamber body 34 is decompressed.

  In addition, four first, second, third, and fourth introduction pipes 66 a, 66 b, 66 c, 66 d are installed in the upper end side portion of the side wall portion 38 so as to penetrate the side wall portion 38. Yes. In each of the first, second, third, and fourth introduction pipes 66a, 66b, 66c, and 66d, the one end side openings that enter and open into the chamber body 34 are the first, second, and second, respectively. , Third and fourth gas introduction ports 68a, 68b, 68c, 68d. A first cylinder 70a for storing a silicon compound gas is connected to the other end of the first introduction pipe 66a that extends to the outside of the chamber body 34. A second cylinder 70b for storing oxygen gas is connected to the other end of the second introduction pipe 66b on the side of the chamber main body 34 that extends to the outside. A third cylinder 70c that stores nitrogen gas is connected to the other end of the third introduction pipe 66c on the side of the chamber main body 34 that extends to the outside. A fourth cylinder 70d for storing argon gas is connected to the other end of the fourth introduction pipe 66d on the side of the chamber main body 34 extending to the outside. Furthermore, the connection parts of the first, second, third, and fourth cylinders 70a, 70b, 70c, 70d with the first, second, third, and fourth introduction pipes 66a, 66b, 66c, 66d include: First, second, third, and fourth on-off valves 72a, 72b, 72c, and 72d are provided, respectively.

  As will be described later, the silicon compound gas accommodated in the first cylinder 70a is used as a source gas for the first film forming gas for forming the base layer portion 22 of the topcoat layer 16, It is also used as a source gas for the second film-forming gas for forming the surface layer portion 24 of the topcoat layer 16. The oxygen gas stored in the second cylinder 70b is used as a reaction gas for the first film-forming gas and also as a reaction gas constituting the second film-forming gas. The nitrogen gas stored in the third cylinder 70c is used as a reactive gas for the second film forming gas together with the oxygen gas stored in the second cylinder 70b. The argon gas accommodated in the fourth cylinder 70d is used for argon plasma treatment of the undercoat layers 14 and 14. The silicon compound gas, oxygen gas, nitrogen gas, and argon gas are all stored in the first to fourth cylinders 70a, 70b, 70c, and 70d at a pressure exceeding the atmospheric pressure.

The silicon compound constituting the silicon compound gas contained in the first cylinder 70a and used as the source gas of the first film forming gas is not particularly limited, and is generally monosilane (SiH). ₄ ) and inorganic silicon compounds such as disilane (Si ₂ H ₆ ) are used alone or in combination. Moreover, it is also possible to use an organosilicon compound as this silicon compound. And as this organosilicon compound, siloxanes such as tetramethyldisiloxane, hexamethyldisiloxane, hexamethylcyclotrisiloxane, methoxytrimethylsilane, ethoxytrimethylsilane, dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiphenylsilane, Trimethoxysilane, trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane, triethoxymethylsilane, triethoxydimethylsilane, triethoxyethylsilane, triethoxyphenylsilane, tetramethylsilane, tetramethoxysilane, tetraethoxysilane Examples thereof include silanes such as hexamethyldisilazane and silazanes such as tetramethyldisilazane. And one of them is used alone, or two or more of them are used in combination. When two or more types of silicon compound gases are used, the plurality of types of silicon compound gases may be mixed and accommodated in one first cylinder 70a, or two or more types of silicon compound gases may be stored. May be separately accommodated in the plurality of first cylinders 70a.

  When the top coat layer 16 is formed on each of the undercoat layers 14 and 14 laminated on both surfaces of the resin base material 12 using the plasma CVD apparatus 30 having such a structure, Prior to this, argon plasma treatment is performed on the surface layers 20 and 20 of the undercoat layers 14 and 14 as necessary.

  For this purpose, first, as shown in FIG. 2, an intermediate laminate 28 in which the undercoat layer 14 is laminated on both surfaces of the resin base material 12, a lower holder 54 provided in the chamber body 34, It is supported by the upper support projections 56, 56 of the 54 and held by the lower holders 54, 54.

Next, after the upper opening 42 is covered with the lid 36, the lid 36 is locked to the chamber body 34 by a lock mechanism (not shown). Thereby, the inside of the vacuum chamber 32 is hermetically sealed. Thereafter, the vacuum pump 64 is operated to reduce the pressure in the vacuum chamber 32. By this depressurization operation, the pressure in the vacuum chamber 32 is set to about 10 ⁻⁵ to 10 ⁻³ Pa, for example.

  When the pressure in the vacuum chamber 32 reaches a predetermined value, the fourth open / close valve 72d of the fourth cylinder 70d connected to the fourth introduction pipe 66d is opened while the vacuum pump 64 is kept operating. Thereby, the argon gas in the fourth cylinder 70d is circulated in the fourth introduction pipe 66d and introduced into the vacuum chamber 32 from the fourth gas introduction port 68d.

  Thereafter, when the internal pressure of the vacuum chamber 32 reaches a predetermined value due to the introduction of argon gas into the vacuum chamber 32, the high-frequency power source 52 is turned on, and the cathode electrode 48 disposed in the vacuum chamber 32 is turned on. The high frequency current is supplied through the feeder line 50. As a result, a discharge phenomenon is caused between the cathode electrode 48 and the anode electrode 60 to turn the argon gas filled in the vacuum chamber 32 into plasma, and the argon gas plasma is turned into a relatively low temperature in the vacuum chamber 32. Generate in state.

  Thus, an argon plasma gas is generated in the vacuum chamber 32, and the argon plasma gas is brought into contact with the surface layer portion 20 made of a fluororesin of the undercoat layer 14 that forms the front and back surfaces of the intermediate laminate 28. . Thereby, the argon plasma treatment is performed on the surface layer portion 20 of the undercoat layer 14, thereby improving the adhesion of the topcoat layer 16 to the undercoat layer 14.

  Then, when a preset time has elapsed from the start of the introduction of the argon gas into the vacuum chamber 32, the fourth open / close valve 72d of the fourth cylinder 70d is closed to introduce the argon gas into the vacuum chamber 32. And the high frequency power supply 52 is turned off. Thereby, the argon plasma treatment for the undercoat layer 14 in the vacuum chamber 32 is completed.

  Thereafter, the argon pump or the argon plasma gas in the vacuum chamber 32 is discharged to the outside by the vacuum pump 64. Then, when the internal pressure of the vacuum chamber 32 becomes the pressure before the introduction of the argon gas, the process of forming the top coat layer 16 on the surface layer portion 20 of the undercoat layer 14 subjected to the argon plasma treatment is started.

  First, the first opening / closing valve 72a of the first cylinder 70a and the second opening / closing valve 72b of the second cylinder 70b connected to the first introduction pipe 66a and the second introduction pipe 66b are opened. Thereby, the silicon compound gas in the first cylinder 70a is circulated in the first introduction pipe 66a and introduced into the vacuum chamber 32 from the first gas introduction port 68a. At the same time, the oxygen gas in the second cylinder 70b is circulated into the second introduction pipe 66b and introduced into the vacuum chamber 32 from the second gas introduction port 72b. Thus, the first film-forming gas composed of the silicon compound gas and the oxygen gas for forming the base layer portion 22 is introduced into the vacuum chamber 32 and filled.

  When the vacuum chamber 32 is filled with the silicon compound gas and the oxygen gas and the internal pressure of the vacuum chamber 32 reaches a predetermined value, the high frequency power supply 52 is turned on, and the cathode electrode 48 disposed in the vacuum chamber 32 is applied. On the other hand, a high-frequency current is supplied through the feeder line 50. As a result, a discharge phenomenon is caused between the cathode electrode 48 and the anode electrode 60, and the silicon compound gas and the oxygen gas filled in the vacuum chamber 32 are turned into plasma, respectively. Are generated in the vacuum chamber 32 at a relatively low temperature.

Then, in the space in the vacuum chamber 32 and the surface of the intermediate laminate 28, a reaction between the plasma of the silicon compound gas and the plasma of the oxygen gas (reaction by the plasma CVD method of the silicon compound gas and the oxygen gas) is caused. SiO ₂ is produced and deposited on the entire surface of the intermediate stack 28. Therefore, the base layer portion 22 made of SiO _{2 is} laminated on the surface layer portions 20 and 20 of the undercoat layers 14 and 14 of the intermediate laminate 28 at a relatively low temperature and at a sufficiently high speed, respectively. Form.

  In this step, the opening operation of the first opening / closing valve 72a of the first cylinder 70a and the second opening / closing valve 72b of the second cylinder 70b is preset in a certain amount without changing the opening amount. For a certain period of time. As a result, the amount of silicon compound gas and oxygen gas introduced into the vacuum chamber 32 per unit time is made constant, and the ratio of the amount of silicon compound gas and oxygen gas in the vacuum chamber 32 is constant. The internal pressure of the vacuum chamber 32 is also maintained at a constant value.

  The thickness of the base layer portion 22 of the topcoat layer 16 laminated on the undercoat layers 14 and 14 is the time during which the silicon compound gas and oxygen gas are introduced into the vacuum chamber 32 at a constant introduction amount, that is, The silicon compound gas and the oxygen gas are appropriately adjusted according to the time for reacting the gas by the plasma CVD method. In other words, the opening operation time at a certain amount of the first opening / closing valve 72a of the first cylinder 70a and the second opening / closing valve 72b of the second cylinder 70b is a preset value of the thickness of the base layer portion 22 or the like. It is determined appropriately depending on the situation.

  A predetermined time from the start of operation of the first and second on-off valves 72a and 72b of the first and second cylinders 70a and 70b, that is, the start of introduction of the silicon compound gas and oxygen gas into the vacuum chamber 32. When (a time set according to the film thickness of the base layer portion 22) has elapsed, the introduction of the nitrogen gas in the third cylinder 70c into the vacuum chamber 32 is started. As a result, introduction of silicon compound gas, oxygen gas, and nitrogen gas, which form the film forming gas for forming the surface layer portion 24, into the vacuum chamber 32 is started. At this time, since the supply of the high-frequency current to the cathode electrode 48 is continued, the nitrogen gas introduced into the vacuum chamber 32 is also converted into plasma at any time, like the silicon compound gas and the oxygen gas.

  It should be noted that the introduction amount per unit time of each of the silicon compound gas, the oxygen gas, and the newly introduced nitrogen gas into the vacuum chamber 32 may be a constant value, but preferably the silicon compound gas The amount of oxygen gas introduced per unit time is gradually decreased while the amount of oxygen gas introduced per unit time is gradually increased while the amount of oxygen gas introduced per unit time is kept constant. After the elapse of time, the introduction amount of oxygen gas per unit time and the introduction amount of nitrogen gas per unit time are adjusted to be a ratio of 1: 1. When silicon compound gas, oxygen gas, and nitrogen gas are introduced into the vacuum chamber 32, the total amount of oxygen gas and nitrogen gas introduced per unit time and the amount of silicon compound gas per unit time are calculated. The ratio of the introduction amount is the ratio between the introduction amount of oxygen gas per unit time and the introduction amount of silicon compound gas per unit time when only the silicon compound gas and oxygen gas are introduced into the vacuum chamber 32. It is more desirable that the ratio is the same. Accordingly, it is possible to prevent as much as possible the pressure in the vacuum chamber 32 from being increased by newly introducing nitrogen gas into the vacuum chamber 32. It should be noted that in order to form the surface layer portion 24, the amount of gas components newly introduced into the vacuum chamber 32 and the respective gas components of the film forming gas introduced into the vacuum chamber 32 when the base layer portion 22 is formed. It is a matter of course that the ratio of the amount introduced is appropriately changed depending on the types of the silicon compound constituting the base layer portion 22 and the silicon compound constituting the surface layer portion 24.

When the introduction of nitrogen gas into the vacuum chamber 32 is started in addition to the silicon compound gas and the oxygen gas, the nitrogen gas is initially introduced from all the gases existing in the vacuum chamber 32 at the beginning of the introduction of the nitrogen gas. Since the gas occupies a small proportion, the reaction by the plasma CVD method between the silicon compound gas and the oxygen gas (reaction between the plasma of the silicon compound gas and the plasma of the oxygen gas) occurs preferentially, thereby producing a large amount of SiO _2. Is done. In addition, when a certain amount of time has elapsed from the start of the introduction of nitrogen gas into the vacuum chamber 32, the proportion of nitrogen gas in all the gas present in the vacuum chamber 32 gradually increases, and accordingly In parallel with the reaction of the silicon compound gas and oxygen gas by the plasma CVD method, the reaction of the silicon compound gas, oxygen gas and nitrogen gas by the plasma CVD method (silicon compound gas plasma, oxygen gas plasma and nitrogen gas). Reaction with plasma). As a result, SiO ₂ and SiON are generated simultaneously. When the amount of nitrogen gas in the vacuum chamber 32 increases as time elapses, the plasma of the silicon compound gas, oxygen gas, and nitrogen gas rather than the reaction of the silicon compound gas and oxygen gas by the plasma CVD method. The reaction by the CVD method preferentially proceeds, so that the amount of SiON produced exceeds the amount of SiO ₂ produced.

In this way, the introduction of nitrogen gas into the vacuum chamber 32 in addition to the silicon compound gas and oxygen gas is started, whereby the intermediate layer 26 in which SiO ₂ and SiON are mixed is formed on the base layer portion 22. The Rukoto. Further, in the intermediate layer 26, the content of SiO ₂ gradually decreases from the base layer 22 side toward the opposite side, while the content of SiON gradually increases. That is, the content of SiO _{2 and} the content of SiON ₂ in the intermediate layer 26 change in an inclined manner from the base layer portion 22 side toward the surface layer portion 24 side.

  Thereafter, when more time passes and the amount of nitrogen gas in the vacuum chamber 32 reaches a sufficient amount, only the reaction of silicon compound gas, oxygen gas, and nitrogen gas by the plasma CVD method proceeds, and SiON Will only be generated. When the elapsed time from the start of introduction of nitrogen gas into the vacuum chamber 32 reaches a preset time, the first, second, and third on-off valves 72a, 72b, 72c are all closed. Then, the introduction of the silicon compound gas, the oxygen gas, and the nitrogen gas into the vacuum chamber 32 is stopped. Thus, the surface layer portion 24 made of SiON is formed on the intermediate layer 26 with a predetermined thickness. Thus, the intended resin glass 10 having the structure as shown in FIG. 1 is obtained.

  The thickness of the surface layer portion 24 made of SiON is determined by the unit time of oxygen gas and nitrogen gas into the vacuum chamber 32 by the opening / closing operation of the first, second and third opening / closing valves 72a, 72b, 72c as described above. The time until the introduction of the silicon compound gas, the oxygen gas, and the nitrogen gas into the vacuum chamber 32 is stopped as a guide is adjusted appropriately when the amount of the permeation introduced becomes constant.

As described above, in the present embodiment, the base layer portion made of SiO _{2 while the} intermediate laminated body 28 in which the undercoat layer 14 is laminated and formed on the surface of the resin base material 12 is accommodated in the single vacuum chamber 32. The topcoat layer 16 having a multilayer structure having 22 and a surface layer portion 24 made of SiON can be formed on the undercoat layer 14 by a series of operations using a plasma CVD method.

  Further, when switching from the formation operation of the base layer portion 22 to the formation operation of the surface layer portion 24, a film forming gas (first film forming gas) for forming the base layer portion 22 is exhausted from the vacuum chamber 32. Therefore, it can be freed from troublesome and time-consuming work for exhausting such film forming gas from the vacuum chamber 32.

  In addition, a silicon compound gas contained as a source gas in the film forming gas for forming the base layer part 22 is used to form a film forming gas for forming the surface layer part 24 (second composition gas). The raw material gas contained in the film gas is used as it is. In addition, an oxygen gas contained as a reaction gas in a film forming gas for forming the base layer portion 22 is used to form a film forming gas for forming the surface layer portion 24 (second film formation) in the operation of forming the surface layer portion 24. It is used as it is as a kind of reaction gas contained in the gas.

  Therefore, according to this embodiment, on the undercoat layer 14 of the resin substrate 12, the base layer portion 22 having excellent adhesion to the undercoat layer 14 and the surface layer portion 24 exhibiting more excellent abrasion resistance are provided. The top coat layer 16 can be formed efficiently and at low cost by a simple operation.

Further, in the present embodiment, the top coat layer 16 is configured by forming an intermediate layer 26 in which SiO ₂ and SiON constituting them are mixed between the base layer portion 22 and the surface layer portion 24. Therefore, a clear interface is not formed between the base layer portion 22 and the surface layer portion 24, thereby preventing the occurrence of peeling or the like at the interface between the base layer portion 22 and the surface layer portion 24 as much as possible. The adhesion between the base layer portion 22 and the surface layer portion 24 can be effectively increased.

  Furthermore, in the resin glass 10 of the present embodiment, the base layer portion 18 of the undercoat layer 14 is composed of a UV curable acrylic resin layer, and the surface layer portion 20 is composed of a UV curable fluororesin layer. Yes. Therefore, unlike the case where the base layer portion 18 and the surface layer portion 20 of the undercoat layer 14 are made of, for example, a thermosetting acrylic resin or a fluororesin, The curing time of the surface layer portion 20 can be sufficiently shortened, whereby the efficiency of the formation process of the undercoat layer 14 and the improvement of the productivity of the resin glass 10 can be advantageously achieved.

  Therefore, in the resin glass 10 according to this embodiment as described above, excellent weather resistance and abrasion resistance obtained by the undercoat layer 14 and the topcoat layer 16 are achieved while realizing high productivity. It can be secured stably over a longer period. At the same time, deterioration in appearance and quality due to long-term use can be extremely effectively prevented.

By the way, in the first embodiment described above, when switching from the operation of forming the base layer portion 22 of the top coat layer 16 made of SiO ₂ to the operation of forming the surface layer portion 24 of the top coat layer 16 made of SiON, the base layer In addition to maintaining the introduction of the film forming gas in the part 22 into the vacuum chamber 32, in addition, the introduction of nitrogen gas contained as a reactive gas in the film forming gas in the surface layer part 24 into the vacuum chamber 32 is started. It was supposed to be. However, for example, the gas contained in the film forming gas for forming the base layer portion 22 as in the case where the base layer portion 22 is made of SiO ₂ and the surface layer portion 24 is made of a silicon compound such as Si ₃ N _4. When the component and the gas component contained in the film forming gas for forming the surface layer portion 24 are different from each other only in some gas components (for example, reaction gas), the first The operation performed when manufacturing the resin glass 10 according to the embodiment is partially different, and the base layer portion 22, the surface layer portion 24, and the intermediate layer 26 of the top coat layer 16 are respectively formed. Will be.

  That is, as in the first embodiment, the argon plasma treatment is performed on the undercoat layer 14 as necessary under the condition that the intermediate laminate 28 is accommodated in the vacuum chamber 32 of the plasma CVD apparatus 30.

Thereafter, after the argon gas and the argon plasma gas in the vacuum chamber 32 are discharged to the outside, the silicon compound gas and the oxygen gas are introduced, and the silicon compound gas and the oxygen gas are reacted by the plasma CVD method. Thus, the base layer portion 22 made of the SiO ₂ plasma CVD layer is formed on the surface layer portion 20 of the undercoat layer 14 of the intermediate laminate 28.

  When a predetermined time has elapsed from the start of introduction of the silicon compound gas and oxygen gas into the vacuum chamber 32, nitrogen gas is introduced into the vacuum chamber 32 while gradually reducing the amount of oxygen gas introduced into the vacuum chamber 32 in advance. Introduce so that the introduction amount gradually increases. Then, when the amount of oxygen gas introduced eventually becomes zero, the amount of nitrogen gas introduced into the vacuum chamber 32 per unit time is set to a constant value. At this time, the silicon compound gas is introduced into the vacuum chamber 32 at a constant introduction amount regardless of variations in the introduction amount of oxygen gas or nitrogen gas.

Then, while the amount of oxygen gas introduced into the vacuum chamber 32 is gradually reduced to zero, the reaction of the silicon compound gas and the oxygen gas by the plasma CVD method is performed in the vacuum chamber 32. In parallel, the reaction of silicon compound gas and nitrogen gas by the plasma CVD method is performed. As a result, the intermediate layer 26 in which SiO ₂ and Si ₃ N ₄ are mixed is formed on the base layer portion 22 in a stacked manner. In the intermediate layer 26, the content of SiO ₂ gradually decreases from the base layer portion 22 side (undercoat layer 14 side) of the top coat layer 16 toward the opposite side, while the content of Si ₃ N ₄ Will gradually increase. That is, the content ratio of SiO _{2 and} the content ratio of Si ₃ N _{4 in} the intermediate layer 26 change from the base layer portion 22 side to the surface layer portion 24 side in an inclined manner.

When the introduction of oxygen gas into the vacuum chamber 32 is stopped and the amount of nitrogen gas introduced into the vacuum chamber 32 per unit time is set to a constant value, a silicon compound is formed in the vacuum chamber 32. Only the reaction of the gas and nitrogen gas by the plasma CVD method proceeds. As a result, the surface layer portion 24 made of the Si ₃ N ₄ plasma CVD layer is laminated on the intermediate layer 26. Thereafter, when a predetermined time has elapsed after the introduction of the oxygen gas into the vacuum chamber 32 is stopped, the introduction of the silicon compound gas and the nitrogen gas into the vacuum chamber 32 is stopped.

  Thus, the top coat layer 16 having a multilayer structure in which the base layer portion 22, the intermediate layer 26, and the surface layer portion 24 are laminated in that order on the surface layer portion 20 of the undercoat layer 14 of the intermediate laminate 28 is laminated. Form. Thus, the intended resin glass 10 having the structure shown in FIG. 1 is obtained.

  Even in this embodiment as described above, it is possible to effectively enjoy the same operations and effects as those provided in the first embodiment.

  Hereinafter, representative examples of the present invention will be shown to clarify the present invention more specifically, but the present invention is not limited by the description of such examples. It goes without saying. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements can be made.

  First, publicly known injection molding was performed using a commercially available polycarbonate resin to obtain two transparent resin base materials composed of rectangular flat plates having a length × width × thickness of 100 × 100 × 5 mm.

  Next, a commercially available UV curable acrylic resin coating was applied to the entire surface of each of the two resin substrates, and this was cured by irradiation with ultraviolet rays. As a result, UV curable acrylic resin layers were respectively formed on the entire surfaces of the two resin substrates. The thickness of the UV curable acrylic resin layer on the surface of these two resin base materials was 20 μm.

  Subsequently, one of two resin base materials each having a UV curable acrylic resin layer formed on the surface thereof is used, and a commercially available UV is formed on the UV curable acrylic resin layer of the one resin base material. A curable PTFE resin coating was applied so as to cover the entire surface of the UV curable acrylic resin layer, and was then cured by irradiating with ultraviolet rays. As a result, a UV curable PTFE resin layer was laminated on the UV curable acrylic resin layer of the resin substrate. The thickness of the UV curable PTFE resin layer on the UV curable acrylic resin layer of the resin substrate was 20 μm.

  Thus, an intermediate laminate in which an undercoat layer having a multilayer structure of a base layer portion made of a UV curable acrylic resin layer and a surface layer portion made of a UV curable PTFE resin layer is laminated on the surface of the resin base material. A was obtained. Also, without forming any UV curable PTFE resin layer on the UV curable acrylic resin layer of the resin base material, an underlayer having a single layer structure consisting of only the UV curable acrylic resin layer is formed on the surface of the resin base material. An intermediate laminate B was obtained by laminating a coat layer.

And after accommodating the intermediate laminated body A in the vacuum chamber of the plasma CVD apparatus which has a structure as shown in FIG. 2, the inside of the vacuum chamber was made into the vacuum state. The internal pressure of the vacuum chamber at this time was 10 ⁻⁴ Pa.

  Thereafter, argon gas was introduced into the vacuum chamber to fill it, and then a high frequency current was supplied from a high frequency power source to the cathode electrode to generate argon gas plasma. And the argon plasma process was implemented with respect to the surface layer part of an undercoat layer by making this argon plasma gas contact the surface layer part of the undercoat layer in the intermediate | middle laminated body A in a vacuum chamber. The argon plasma treatment time was 10 minutes.

Next, after argon gas and argon plasma gas are discharged to the outside in the vacuum chamber, monosilane gas and oxygen gas as silicon compound gas are introduced into the vacuum chamber so that the introduction amount per unit time becomes constant. Introduced and filled. Thereafter, a high-frequency current is supplied from a high-frequency power source to the cathode electrode to generate oxygen gas plasma and monosilane gas plasma, and react these plasma gases to form SiO ₂ on the surface layer of the undercoat layer. The base layer portion of the top coat layer was formed. In addition, the formation operation of this base layer part was continued for 1200 seconds. The amount of monosilane gas introduced into the vacuum chamber was 50 ml / sec, and the amount of oxygen gas introduced into the vacuum chamber was 50 ml / sec. Furthermore, the output value of the high frequency power source was set to 3000W. The base layer thus formed had a thickness of 1 μm.

  After 1 to 5 minutes have elapsed from the start of introduction of oxygen gas and monosilane gas into the vacuum chamber (start of the base layer forming operation), nitrogen gas is gradually introduced into the vacuum chamber at a unit time. Introduced over 20 minutes. Monosilane gas and oxygen gas were continuously introduced at the same introduction amount per unit time as when the base layer portion was formed.

While the monosilane gas, oxygen gas, and nitrogen gas are introduced into the vacuum chamber, the monosilane gas and oxygen gas are continuously supplied to the cathode electrode while keeping the output value of the high frequency power supply at 3000 W. And nitrogen gas were converted into plasma to react monosilane gas plasma and oxygen gas plasma, respectively, and in parallel, monosilane gas plasma, oxygen gas plasma and nitrogen gas plasma were reacted. As a result, an intermediate layer in which SiO ₂ and SiON were mixed was formed on the base layer portion. The amount of nitrogen gas introduced into the vacuum chamber was increased by 500 ml / sec. The amounts of monosilane gas and oxygen gas introduced into the vacuum chamber were 50 ml / sec, respectively. The thickness of the intermediate layer thus formed was 0.1 to 10 μm.

  Further, with the output value of the high-frequency power source kept at 3000 W, a high-frequency current is continuously supplied to the cathode electrode to generate a monosilane gas plasma, a nitrogen gas plasma, and an oxygen gas plasma. The surface layer portion of the topcoat layer made of SiON was formed on the intermediate layer. The thickness of the surface layer portion was 1 μm.

Thus, as shown in FIG. 1, an undercoat layer having a two-layer structure of a base layer portion made of a UV curable acrylic resin layer and a surface layer portion made of a UV curable PTFE resin layer on the surface of a polycarbonate resin substrate. together but are formed, a base layer portion made of SiO _2, an intermediate layer SiO ₂ and SiON are mixed, the topcoat layer having a three-layer structure of surface layer portion made of SiON is formed and layered on the undercoat layer A transparent resin glass was obtained. This resin glass was designated as Test Example 1.

On the other hand, for comparison, the intermediate laminate B was housed in a vacuum chamber of a plasma CVD apparatus used in the production of the resin glass of Test Example 1, and then the vacuum chamber was evacuated. The internal pressure of the vacuum chamber at this time was 10 ⁻⁴ Pa.

Then, the undercoat layer having a single layer structure formed on the intermediate laminate B UV curable acrylic resin layer, a base layer portion made of SiO _2, an intermediate layer SiO ₂ and SiON are mixed, of SiON A top coat layer having a three-layer structure of the surface layer portion was laminated and formed in the same manner as in the production of the resin glass of Test Example 1. Thus, the surface of the polycarbonate resin substrate with an undercoat layer having a single layer structure comprising only UV curable acrylic resin layer is formed, a base layer portion made of SiO _2, SiO ₂ and SiON are mixed A transparent resin glass was obtained in which a top coat layer having a three-layer structure of an intermediate layer and a surface layer portion made of SiON was formed on the undercoat layer. This resin glass was designated as Test Example 2. The thicknesses of the base layer portion, the intermediate layer, and the surface layer portion of the top coat layer were the same as those of the resin glass of Test Example 1.

  And using two types of transparent resin glasses of Test Example 1 and Test Example 2 obtained as described above, the wear resistance of each resin glass and the adhesion between the topcoat layer and the undercoat layer The evaluation test regarding sex was carried out as follows. The results are shown in Table 1 below.

<Abrasion resistance>
The difference in haze value before and after the Taber abrasion test based on JIS R3211: ΔH was measured based on JIS R3212. And the measured value: ΔH is 2.0% or less, the wear resistance is excellent, the evaluation result is indicated by ○, and ΔH exceeds 2.0%, the wear resistance is inferior As a result, the evaluation result was shown by x. In carrying out the Taber abrasion test, a wear wheel of a model number: CS-10F (manufactured by Taber) was used. Moreover, the haze value measuring machine [model number: HZ-2P (made by Suga Test Instruments Co., Ltd.)] was used for the measurement of the haze value. Here, the evaluation result of ΔH having a value of 2.0% or less is evaluated as “◯” for the following reason. That is, the resin glass used for the windshield for automobiles is required to have a haze value difference ΔH of 2.0% or less before and after the Taber abrasion test according to JIS R3211. Therefore, here, the evaluation result regarding the wear resistance of those having a value of ΔH of 2.0% or less is indicated by “◯”.

<Adhesion test>
It implemented based on JISK5600-5-6. And, as a result of the adhesion test, the evaluation result is shown as a case where there was no exfoliation, the evaluation result is indicated by ◯, and the exfoliation was slight, and the evaluation result was slightly inferior in adhesion Is indicated by Δ.

  As is clear from the results in Table 1, a topcoat layer is laminated on an undercoat layer having a two-layer structure of a base layer portion made of a UV curable acrylic resin layer and a surface layer portion made of a UV curable PTFE resin layer. When the resin glass of Test Example 1 was compared with the resin glass of Test Example 2 in which a topcoat layer was laminated on an undercoat layer having a single layer structure composed only of a UV curable acrylic resin layer, Test Example 1 The evaluation results of the abrasion resistance test and the adhesion test are both “good” for the resin glass. However, in the resin glass of Test Example 2, the evaluation result of the abrasion resistance test is x, and the evaluation result of the adhesion test is Δ. This clearly shows that the resin glass having a structure according to the present invention exhibits excellent characteristics in both wear resistance and adhesion.

  The specific configuration of the present invention has been described in detail above. However, this is merely an example, and the present invention is not limited by the above description.

For example, in the first embodiment, the base layer portion 22 and the surface layer portion 24 of the top coat layer 16 are respectively composed of a SiO ₂ plasma CVD layer and a SiON plasma CVD layer, In the embodiment, the base layer portion 22 and the surface layer portion 24 of the top coat layer 16 are composed of a SiO ₂ plasma CVD layer and a Si ₃ N ₄ plasma CVD layer, respectively. However, the top coat layer 16 may have a single layer structure as long as it is composed of a silicon compound plasma CVD layer.

  Also, when the topcoat layer 16 has a multi-layer structure having a plurality of silicon compound plasma CVD layers, the types of silicon compounds constituting each of the plurality of silicon compound plasma CVD layers are exemplified. There is no limitation. However, when the topcoat layer 16 has a multi-layer structure, it is desirable that the surface layer portion is composed of a plasma CVD layer of a silicon compound portion having a hardness higher than that of the base layer portion.

Further, the method of forming the multi-layered topcoat layer 16 is not particularly limited to the exemplified method as long as the plasma CVD method is used. And the kind of the gas component contained in the film forming gas for forming the base layer portion 22 and the surface layer portion 24 of the top coat layer 16 and the surface layer portion 24 introduced into the vacuum chamber 32, particularly the reactive gas, is not limited at all. Instead, the base layer portion 22 and the surface layer portion 24 can be appropriately changed according to the type of silicon compound. For example, as a gas component contained in the film forming gas for forming the surface layer portion 24 of the top coat layer 16 made of a plasma CVD layer of SiON or Si ₃ N ₄ , a nitrogen compound such as ammonia gas instead of nitrogen gas Gas can also be used.

  Further, as the plasma CVD apparatus used for forming the top coat layer 16, a device having a known structure can be appropriately employed in addition to the illustrated structure. For example, an inductive coupling method or a structure using a plasma gun that generates an arc can be employed.

  Furthermore, the undercoat layer 14 and the topcoat layer 16 may be provided only on one surface of the resin base material 12.

  In addition, in the above-described embodiment, specific examples of applying the present invention to a resin glass for an automobile rear window and a method for producing the same have been shown. However, the present invention is not limited to a resin base made of a resin molded product made of polycarbonate. The present invention is advantageously applied to any of a resin product in which an undercoat layer and a topcoat layer including a base layer portion are laminated in that order on the surface of the material, and a method for producing such a resin product. Of course, it can be done.

  In addition, although not enumerated one by one, the present invention can be carried out in a mode to which various changes, modifications, improvements, etc. are added based on the knowledge of those skilled in the art. It goes without saying that all are included in the scope of the present invention without departing from the spirit of the present invention.

DESCRIPTION OF SYMBOLS 10 Resin glass 12 Resin base material 14 Undercoat layer 16 Topcoat layer 18,22 Base layer part 20,24 Surface layer part 26 Intermediate layer 28 Intermediate laminated body 30 Plasma CVD apparatus

Claims (4)

A resin base material composed of a resin molded product made of polycarbonate, an UV curable acrylic resin layer, an undercoat layer formed on the surface of the resin base material, and a layer formed on the undercoat layer In a resin product configured to include a top coat layer composed of a plasma CVD layer of a silicon compound,
The undercoat layer is laminated on the surface of the resin base material, and a base layer portion made of the UV curable acrylic resin layer, and a surface layer portion made of a fluororesin layer further laminated on the base layer portion. A resin product characterized by comprising The top coat layer is a base layer portion made of a SiO ₂ plasma CVD layer formed on the under coat layer, a surface layer portion made of a SiON plasma CVD layer formed on the base layer portion, and the base layer And an intermediate layer composed of a plasma CVD layer in which SiO ₂ and SiON are mixed, interposed between the surface portion and the surface layer portion, and the content of SiO ₂ in the intermediate layer is 2. The SiON content in the intermediate layer gradually decreases from the base layer side toward the surface layer side, while the SiON content in the intermediate layer gradually increases from the base layer side toward the surface layer side. Resin products. A resin base material composed of a resin molded product made of polycarbonate, an UV curable acrylic resin layer, an undercoat layer formed on the surface of the resin base material, and a layer formed on the undercoat layer A method for producing a resin product comprising a top coat layer comprising a plasma CVD layer of a silicon compound,
Preparing the resin substrate;
After forming a coating layer on the surface of the resin substrate using a UV curable acrylic resin coating, the coating layer is irradiated with ultraviolet rays to cure the coating layer. Forming a UV curable acrylic resin layer on the surface of the material, and then forming a fluororesin layer on the UV curable acrylic resin layer; Laminating the undercoat layer composed of the fluororesin layer formed on the base layer portion on the surface of the resin substrate; and
A step of forming a top coat layer made of a plasma CVD layer of the silicon compound on the undercoat layer by a plasma CVD method; and
The manufacturing method of the resin product characterized by including. The top coat layer is a base layer portion composed of a plasma CVD layer of SiO ₂ laminated on the undercoat layer of the resin base material, and a surface layer consisting of a plasma CVD layer of SiON laminated on the base layer portion. And an intermediate layer composed of a plasma CVD layer in which SiO ₂ and SiON are mixed, interposed between the base layer portion and the surface layer portion. ) Housing the resin substrate on which the undercoat layer is formed in a reaction chamber, and evacuating the reaction chamber; and (b) a silicon compound gas and oxygen in the vacuum reaction chamber. The silicon compound gas and the oxygen gas are reacted by a plasma CVD method, and the SiO ₂ plasma CV is formed on the undercoat layer of the resin substrate accommodated in the reaction chamber. A step of laminating and forming a base layer portion comprising a D layer; and (c) onto the undercoat layer in the reaction chamber containing the resin base material on which the base layer portion is laminated on the undercoat layer. After the formation of the base layer portion, by introducing nitrogen gas or nitrogen compound gas while continuously introducing silicon compound gas and oxygen gas, reaction of silicon compound gas and oxygen gas by plasma CVD method, The silicon compound gas and oxygen gas and nitrogen gas or nitrogen compound gas are reacted by the plasma CVD method at the same time, and the SiO ₂ and SiON are formed on the base layer formed on the undercoat layer. A step of laminating and forming an intermediate layer composed of a mixed plasma CVD layer; and (d) containing the resin base material in which the base layer portion and the intermediate layer are laminated on the undercoat layer. Even after the formation of the intermediate layer in the reaction chamber, the silicon compound gas and the oxygen gas and the nitrogen gas or the nitrogen compound gas were reacted by a plasma CVD method, and were laminated on the undercoat layer via the base layer portion. The method for producing a resin product according to claim 3, further comprising: forming a surface layer portion made of the plasma CVD layer of SiON 3 on the intermediate layer.

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