JP2013227628A - Method of manufacturing resin product and resin product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing technology of a resin product that excels in wear resistance, water repellency, and antifouling properties, and in which high adhesion is secured at a laminate interface of a top coat layer.SOLUTION: A silicon compound layer 18 and a fluorine compound layer 20 are sequentially laminated and formed on an undercoat layer 14 in a reaction chamber 28 of a vacuum condition by a plasma CVD method. In addition, a reaction of the first gas for deposition by a plasma CVD method and a reaction of the second gas for deposition by a plasma CVD method are made at the same time from the start of the introduction of a second gas for deposition to form the fluorine compound layer 20 in the reaction chamber 28 to a time when an amount of at least the part of the gas component in the reaction chamber 28 becomes zero by gradually decreasing an introduction amount of at least a part of a gas component of a first gas for deposition to form the silicon compound layer 18 into the reaction chamber 28.

Description

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

  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. And among such resin products, for example, highly transparent resin products made of molded products made of polycarbonate are superior in lightness, impact resistance, and workability compared to inorganic glass, As resin glass (organic glass) that replaces inorganic glass, it is used, for example, for window glass of vehicles such as automobiles, various displays, covers for various instruments, and the like.

  By the way, 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 (abrasion resistance and scratch resistance) than inorganic glass. It also has the disadvantage of being inferior. 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 is 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), an undercoat layer made of an acrylic resin layer having a high weather resistance is formed on the surface of a resin base material made of a resin molded body such as polycarbonate. A resin product (resin molded product) is disclosed in which a top coat layer made of a plasma CVD layer of a silicon compound is further laminated on the undercoat layer. In such a resin product, the top coat layer is composed of a plasma CVD layer of a silicon compound, so that the formation operation of the top coat layer to the undercoat layer can be made more efficient, and the surface of the resin product can be improved. The abrasion resistance can be advantageously increased.

Further, in recent years, with the trend toward higher-grade automobiles, etc., further improvements in functionality have been demanded for window glass, providing better abrasion resistance and sufficient antifouling properties. It is becoming necessary to be. As one measure for satisfying such a demand, fluorine compounds containing silicon such as SiOF and SiF ₄ [in other words, silicon compounds containing fluorine (fluorine-containing silicon compounds)] and silicon such as fluorine resin are not contained. It is conceivable to form a fluorine compound layer made of a fluorine compound or the like on the surface of a polycarbonate resin product. That is, the topcoat layer formed on the surface of the resin base material has a multilayer structure of a fluorine compound layer containing or not containing silicon and a silicon compound layer. In this way, the abrasion resistance of the resin product can be advantageously enhanced by the lubricity effect of fluorine contained in the fluorine compound layer of the topcoat layer, and the water repellency peculiar to fluorine to the resin product can be improved. Dirtyness is effectively imparted. Further, by controlling the refractive index of light of the fluorine compound layer by the refractive index reduction effect by fluorine, there can be obtained an advantage that generation of interference fringes can be suppressed.

  When obtaining a topcoat layer having such a multilayer structure, the transparency of the polycarbonate resin substrate is sufficiently maintained, and the productivity of the resin product is reduced due to the multilayering of the topcoat layer. In order to prevent this, it is considered desirable to form a fluorine compound layer on the silicon compound layer in a thin film form by a dry method such as sputtering or plasma CVD.

  However, as is well known, the sputtering method has a drawback that the film formation rate (film thickness formed per unit time) is extremely small. Therefore, when the fluorine compound layer is formed by using this sputtering method, there is no problem when the fluorine compound layer is extremely thin, but in order to ensure sufficient abrasion resistance, the fluorine compound layer is used. If an attempt is made to form with a certain thickness, the formation time of the fluorine compound layer becomes very long, and thereby the productivity of the resin product is significantly reduced. Moreover, in order to provide a fluorine compound sputtered film on a silicon compound layer composed of a plasma CVD layer, both a plasma CVD apparatus and a sputtering apparatus are required, which causes a problem that the production cost of resin products increases. Is done.

  On the other hand, when the fluorine compound layer is formed on the silicon compound layer by using the plasma CVD method, the above-mentioned problems caused when the fluorine compound layer is formed by the sputtering method can be greatly solved. . However, in the case where a silicon compound plasma CVD layer and a fluorine compound plasma CVD layer are stacked in accordance with a general method performed when forming a plasma CVD layer having a multilayer structure, the following problems occur. However, it became clear by research of this inventor.

  That is, when a polycarbonate resin product in which a silicon compound layer and a fluorine compound layer are formed by a plasma CVD method is obtained by a conventional method, an undercoat layer is first formed on the surface in a vacuum reaction chamber. The made polycarbonate resin substrate is accommodated. Thereafter, a film-forming gas containing a silicon compound gas is introduced into the reaction chamber, and this film-forming gas is reacted by the plasma CVD method to form a plasma CVD layer on the undercoat layer of the resin substrate. A silicon compound layer is formed. When the silicon compound layer is formed, the gas for forming the silicon compound layer remaining in the vacuum chamber is completely discharged from the reaction chamber. Thereafter, a film-forming gas containing a fluorine compound gas is newly introduced into the reaction chamber, and this film-forming gas is reacted by the plasma CVD method to form a fluorine compound layer comprising a plasma CVD layer on the silicon compound layer. Is further laminated. According to such a method, although the silicon compound layer forming step and the fluorine compound layer forming step are performed in one reaction chamber, in the resin product thus obtained, the silicon compound layer and the fluorine compound layer are formed. According to the present inventors, there is a risk of peeling at the interface between the silicon compound layer and the fluorine compound layer due to, for example, long-term use or temperature changes in the use environment. It turns out.

  Further, in the above conventional method, after the silicon compound layer made of the plasma CVD layer is formed and before the operation of forming the fluorine compound layer made of the plasma CVD layer is started, the silicon compound layer remaining in the reaction chamber is formed. An operation for completely removing the working gas from the reaction chamber is performed. Therefore, not only does it take extra effort and time to remove the film forming gas, but also the film forming gas removed from the reaction chamber is wasted, which is the cost of forming a multi-layer topcoat layer, As a result, it became clear that problems such as pressure on the production cost of resin products were caused.

JP 2010-253683 A

  Here, the present invention has been made in the background as described above, and the problem to be solved is that it has superior abrasion resistance and sufficient water repellency and antifouling properties. A method for producing a resin product that can be produced at low cost and with high productivity, a polycarbonate resin product that is effectively exhibited and has improved adhesion at the laminated interface of the topcoat layer having a multilayer structure. Is to provide. In addition, the present invention advantageously exhibits superior abrasion resistance and sufficient water repellency and antifouling properties, and also effectively increases the adhesion at the laminated interface of the topcoat layer having a multilayer structure. Another object of the present invention is to provide a polycarbonate resin product.

  In order to solve the problems related to the method for producing a resin product, the gist of the present invention is that an undercoat layer is formed on the surface of a resin base material made of a polycarbonate resin molded product. And a method for producing a resin product in which a silicon compound layer is further laminated on the undercoat layer, comprising: (a) a step of preparing the resin substrate; and (b) the resin substrate. A step of laminating and forming the undercoat layer on the surface, and (c) placing the resin base material on which the undercoat layer is laminated in a reaction chamber, and then setting the reaction chamber to a vacuum state; (D) A first film-forming gas containing a silicon compound gas is introduced into the vacuum reaction chamber, the first film-forming gas is reacted by a plasma CVD method, and the reaction chamber is filled. The union of the contained base material A step of laminating and forming the silicon compound layer on the coat layer; and (e) containing fluorine gas or fluorine compound gas in the reaction chamber containing the resin base material on which the silicon compound layer is laminated. A step of introducing a second film-forming gas and reacting the second film-forming gas by a plasma CVD method to form a fluorine compound layer on the silicon compound layer; The introduction amount of at least a part of the gas component in the first film forming gas introduced into the reaction chamber is gradually reduced from the start of the introduction of the second film forming gas into the reaction chamber, By doing so, the first film-forming gas is used from the start of the introduction of the second film-forming gas into the reaction chamber until the amount of the at least some gas components in the reaction chamber becomes zero. Reaction of gas by plasma CVD method and for the second film formation Before the formation of the fluorine compound layer on the silicon compound layer, an intermediate layer in which the silicon compound and the fluorine compound are mixed is formed on the silicon compound layer. And a process for producing the resin product.

  The present invention also provides a resin product in which an undercoat layer is laminated on the surface of a resin base material made of a polycarbonate resin molded product, and a silicon compound layer is further laminated on the undercoat layer. (A) a step of preparing the resin base material, (b) a step of laminating and forming the undercoat layer on the surface of the resin base material, and (c) the undercoat layer (D) a first film formation containing a silicon compound gas in the reaction chamber in a vacuum state after the resin base material formed in a stack is accommodated in the reaction chamber and then the reaction chamber is in a vacuum state; A base layer portion of the silicon compound layer is laminated on the undercoat layer of the base material accommodated in the reaction chamber by introducing a working gas and reacting the first film forming gas by a plasma CVD method. And (e) said silicon The first film-forming gas is formed after the silicon compound layer is formed on the surface of the resin base material in the reaction chamber containing the resin base material on which the base layer portion of the compound layer is laminated. The fluorine gas or the fluorine compound gas is further introduced while the first film forming gas and the second film forming gas containing the fluorine gas or the fluorine compound gas are introduced into the reaction chamber. Introducing and reacting the second film-forming gas by a plasma CVD method to form a surface layer portion of the silicon compound layer made of a silicon compound containing fluorine on the base layer portion of the silicon compound layer The gist of the method for producing a resin product comprising:

  Furthermore, a method for producing a resin product in which an undercoat layer is laminated on the surface of a resin base material made of a polycarbonate resin molded product, and a silicon compound layer is further laminated on the undercoat layer. (A) a step of preparing the resin base material; a step of forming the undercoat layer on the surface of the resin base material; and (b) the resin base material on which the undercoat layer is formed. (C) introducing a first film-forming gas containing a silicon compound gas into the vacuum reaction chamber after the reaction chamber is housed in a vacuum state; (D) forming a base layer portion of the silicon compound layer on the undercoat layer of the resin substrate housed in the reaction chamber by reacting the film forming gas with a plasma CVD method; Base layer portion of the silicon compound layer While the silicon compound layer is formed on the surface of the resin base material, the first film-forming gas is continuously introduced into the reaction chamber containing the laminated resin base material. Then, by further introducing fluorine gas or fluorine compound gas, the first film forming gas and a second film forming gas containing fluorine gas or fluorine compound gas are introduced into the reaction chamber, A reaction for forming a film-forming gas by the plasma CVD method and a reaction for forming the second film-forming gas by a plasma CVD method are simultaneously performed on the base layer portion of the silicon compound layer. A step of laminating and forming an intermediate layer in which a product produced by a reaction of a gas by a plasma CVD method and a product produced by a reaction of the second film-forming gas by a plasma CVD method are mixed (e ) On the undercoat layer, The second film-forming gas is introduced into the reaction chamber containing the resin base material in which the base layer portion and the intermediate layer of the elemental compound layer are stacked even after the formation of the intermediate layer of the silicon compound layer. And a step of laminating and forming a surface layer portion of the silicon compound layer on the intermediate layer of the silicon compound layer by reacting the second film-forming gas by a plasma CVD method. , With features.

  According to one of the advantageous embodiments of the present invention, the fluorine gas or the fluorine compound gas is introduced into the reaction chamber so as to gradually increase the introduction amount of the fluorine gas or the fluorine compound gas. From the start of introduction into the reaction chamber, the introduction amount of the reaction gas contained in the first film-forming gas into the reaction chamber is gradually reduced.

  And, in order to solve the problems related to the resin product described above, the gist of the present invention is that an undercoat layer is laminated on the surface of a resin base material made of a polycarbonate resin molded product. A resin product in which a silicon compound layer comprising a plasma CVD layer is further laminated on the undercoat layer, wherein a fluorine compound layer comprising a plasma CVD layer is laminated on the silicon compound layer. In addition, an intermediate layer composed of a plasma CVD layer in which the silicon compound constituting the silicon compound layer and the fluorine compound constituting the fluorine compound layer are mixed is formed between the silicon compound layer and the fluorine compound layer. And the content of the silicon compound in the intermediate layer gradually decreases from the silicon compound layer side toward the fluorine compound layer side, It said intermediate layer in a content of things, from 該珪 containing compound layer side resin product characterized in that gradually increases toward the fluorine compound layer side.

  In the present invention, an undercoat layer is laminated on the surface of a resin substrate made of a polycarbonate resin molded product, and a silicon compound layer made of a plasma CVD layer is further laminated on the undercoat layer. The silicon compound layer has a multilayer structure of a base layer portion located on the undercoat layer side and a surface layer portion laminated on the base layer portion, and the surface layer portion is Plasma CVD comprising a silicon compound containing fluorine, and further comprising a silicon compound constituting the base layer portion and a fluorine-containing silicon compound constituting the surface layer portion between the base layer portion and the surface layer portion. An 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. Parts A resin product characterized in that the content of the fluorine-containing silicon compound in the intermediate layer gradually increases from the base layer portion side to the surface layer portion side is also the gist thereof. .

  That is, according to the method for producing a resin product according to the present invention, the top coat layer has a silicon compound layer that exhibits high abrasion resistance due to its high hardness, and exhibits abrasion resistance due to a sliding effect, and also has repellent properties. Constructed with a multi-layer structure of fluorine compounds (including fluorine-containing silicon compounds) excellent in water resistance and antifouling properties, and such a top coat layer is formed with respect to the undercoat layer formed on the surface of the resin substrate. Then, the layers are formed by plasma CVD performed continuously in one reaction chamber. Therefore, while the silicon compound layer is formed by plasma CVD, unlike the case where the fluorine compound layer is formed by sputtering, the apparatus used for forming the topcoat layer is only one plasma CVD apparatus, In addition, a fluorine compound layer having a certain thickness can be formed at a sufficiently high deposition rate.

  In addition, in the method for producing a resin product according to the present invention, the step of reacting only the first film-forming gas containing the silicon compound gas by the plasma CVD method, and the second step including the fluorine gas or the fluorine compound gas performed thereafter. During the step of reacting only the second film-forming gas by the plasma CVD method, 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 simultaneously performed. The process to implement is performed. Therefore, according to the method of the present invention, the silicon compound layer is formed on the undercoat layer of the resin base material, and the fluorine compound layer is formed on the silicon compound layer. An intermediate layer in which a silicon compound and a fluorine compound are mixed is formed between the layer and the fluorine compound layer. This eliminates the interface between the silicon compound layer and the fluorine compound layer that clearly separates them, and as a result, the adhesion between the silicon compound layer and the fluorine compound layer is extremely effective. It can be increased.

  Furthermore, in the method for producing a resin product according to the present invention, the first component in which the intermediate layer in which the silicon compound and the fluorine compound are mixed still exists in the reaction chamber after the formation of the silicon compound layer on the surface of the resin base material. It is formed using a film gas. Therefore, unlike the conventional method, even if it is necessary to zero out at least a part of the gas component of the first film-forming gas to form the fluorine compound layer on the silicon compound layer, at least one such The need to perform the operation of removing the gas components in the reaction chamber from the reaction chamber is advantageously eliminated, thereby eliminating the extra effort required to remove at least some of the gas components of the first film-forming gas. And time can be advantageously saved. Moreover, at least some of the gas components are not wasted.

  Therefore, according to the method for producing a resin product according to the present invention as described above, not only the abrasion resistance can be further improved, but also sufficient water repellency and antifouling properties are advantageously exhibited, and a multilayer structure is obtained. It is possible to efficiently produce a resin product made of polycarbonate in which the adhesion at the laminated interface of the top coat layer having a structure is effectively enhanced with sufficiently low cost and high productivity.

  In the resin product according to the present invention, sufficient water repellency and antifouling properties are advantageously exhibited together with better abrasion resistance, and at the laminated interface of the topcoat layer having a multilayer structure. Adhesion can be advantageously increased.

It is a fragmentary sectional view showing one embodiment of a resin product having a structure according to the present invention. It is a cross-sectional explanatory drawing which shows the plasma CVD apparatus used when manufacturing the resin product shown by FIG.

  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 laminated on both surfaces of the resin base material 12. 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.

  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.

  The undercoat layer 14 is laminated on the surface 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, and has a thin film form. Such an undercoat layer 14 is generally formed by applying a liquid acrylic resin or polyurethane resin on the surface of the resin substrate 12 to form a coating film, and then heating or irradiating with ultraviolet rays. It is formed by curing. Such an undercoat layer 14 is preferably composed of an ultraviolet curable film in order to simplify the formation process and reduce the equipment cost required for the formation. The undercoat layer 14 can also be formed by employing a resin material and a curing method other than those exemplified above. Further, the undercoat layer 14 may have a single layer structure or a multilayer structure in which a plurality of layers are laminated.

  The thickness of the undercoat layer 14 is not particularly limited, but generally, the total thickness is about 8 to 12 μm regardless of whether it is a single layer structure or a multilayer structure. This is because if the thickness of the undercoat layer 14 is less than 8 μm, it is too thin and it may be difficult to impart sufficient weather resistance to the resin glass 10. This is because even if the thickness of the undercoat layer 14 is greater than 12 μm, it is difficult to further improve the weather resistance of the resin glass 10, and there is a possibility that material costs may be wasted.

  The top coat layer 16 is in the form of a thin film made of a silicon compound. As is well known, a silicon compound has a high hardness and exhibits excellent wear resistance and scratch resistance on the basis thereof. Therefore, the top coat layer 16 made of such a silicon compound is laminated on the undercoat layer 14 to constitute the surface portion of the resin glass 10, so that the resin glass 10 has excellent abrasion resistance. It has been granted.

  Although the thickness of such a topcoat layer 16 is not limited at all, it is about 0.3 to 30 μm. This is because if the thickness of the topcoat layer 16 is thinner than 0.3 μm, it is too thin and it may be difficult to sufficiently impart abrasion resistance to the resin glass 10. Further, even if the thickness of the top coat layer 16 is made larger than 30 μm, it is difficult to further improve the abrasion resistance of the resin glass 10, and there is a possibility that material costs may be wasted. .

In the present embodiment, in particular, the top coat layer 16 has a multilayer structure including a base layer portion 18 positioned on the undercoat layer 14 side and a surface layer portion 20 laminated on the base layer portion 18. . The base layer portion 18 is composed of a SiO ₂ plasma CVD layer formed by the plasma CVD method, and the surface layer portion 20 is a kind of silicon compound containing fluorine formed by the plasma CVD method. It consists of a plasma CVD layer of SiOF.

As described above, in this embodiment, the base layer portion 18 made of SiO ₂ that has high hardness and thereby exhibits sufficient abrasion resistance (abrasion resistance and scratch resistance) is laminated on the undercoat layer 14. Thus, excellent abrasion resistance is imparted to the resin glass 10. Further, the surface layer portion 20 made of SiOF having excellent water repellency and antifouling properties is laminated on the base layer portion 18 while exhibiting abrasion resistance due to the lubricity effect, and the surface layer portion of the top coat layer 16 is formed on the surface layer. By being comprised in the part 20, the further superior abrasion resistance and sufficient water repellency and antifouling property are provided with respect to the surface of the resin glass 10. FIG.

  Although the thickness of the base layer part 18 of the topcoat layer 16 is not limited at all, it is preferably about 0.1 to 10 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.

  Further, the thickness of the surface layer portion 20 of the top coat layer 16 is also not particularly limited, but is desirably about 0.1 to 10 μm. This is because if the thickness of the surface layer portion 20 is thinner than 0.1 μm, it is too thin, so that the surface of the resin glass 10 is given more sufficient scratch resistance and excellent water repellency and antifouling properties. This is because it may be difficult. Moreover, even if the thickness of the surface layer part 20 is made thicker than 10 μm, it is not desired to further improve the abrasion resistance, water repellency and antifouling property of the surface of the resin glass 10.

  In the present embodiment, an intermediate layer 22 made of a plasma CVD layer is provided between the base layer portion 18 and the surface layer portion 20 in particular. That is, the top coat layer 16 has a multilayer structure including the base layer portion 18, the intermediate layer 22, and the surface layer portion 20.

In the intermediate layer 22, SiO ₂ constituting the base layer portion 18 and SiOOF constituting the surface layer portion 20 are mixed. That is, the intermediate layer 22 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 SiO OF. Then, in the take intermediate layer 22, the content of SiO ₂ is, while gradually decreases from the base portion 18 side toward the surface layer portion 20, the content of SiOF is, the surface layer from the base layer part 18 side It gradually increases toward the portion 20 side. That is, the content of SiO _{2 and} the content of SiO ₂ in the intermediate layer 22 change in an inclined manner from the base layer portion 18 side to the surface layer portion 20 side.

  Thus, in the present embodiment, the intermediate layer 22 having the structure as described above is provided between the base layer part 18 and the surface layer part 20, so that the base layer part 18 and the surface layer part 20 are between them. , The clear interface has been lost. As a result, for example, the occurrence of peeling at the interface between the base layer portion 18 and the surface layer portion 20 is prevented as much as possible due to, for example, long-term use or changes in the surrounding thermal environment. The adhesion between the surface layer 18 and the surface layer portion 20 is effectively enhanced.

  Although the thickness of the intermediate layer 22 is not limited at all, it is preferably about 0.1 to 10 μm. This is because if the thickness of the intermediate layer 22 is less than 0.1 μm, the effect of improving the adhesion between the base layer portion 18 and the surface layer portion 20 may not be sufficiently expected because it is too thin. In addition, if the thickness of the intermediate layer 22 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, undercoat layers 14 and 14 in which a coating film such as an acrylic resin or a polyurethane resin is heat-cured or ultraviolet-cured are respectively laminated on both surfaces of the resin base material 12, and an intermediate product 24 (see FIG. 2) is formed. obtain.

  Next, the top coat layer 16 is further laminated on the undercoat layers 14 and 14 of the intermediate product 24 using the plasma CVD apparatus 26 having the structure shown in FIG.

  As shown in FIG. 2, the plasma CVD apparatus 26 used here has the same basic structure as a conventional plasma CVD apparatus that employs a parallel plate method. More specifically, the plasma CVD apparatus 26 has a vacuum chamber 28 as a reaction chamber. The vacuum chamber 28 further includes a chamber body 30 and a lid 32. The chamber body 30 has a bottomed cylindrical shape or a casing shape including a cylindrical side wall portion 34 and a lower bottom wall portion 36 that closes a lower opening of the side wall portion 34. The lid body 32 is configured by a flat plate having a size capable of covering the entire upper opening 38 of the chamber body 30. The chamber body 30 is hermetically sealed by being locked by a lock mechanism (not shown) while the lid body 32 covers the upper opening 38 of the chamber body 30.

  Further, upper holders 40, 40 are erected integrally on the lower surface of the lid 32. Support protrusions 42 and 42 are integrally provided on the upper holders 40 and 40. The cathode electrode 44 accommodated in the chamber body 30 is supported by the support protrusions 42 and 42 and is held by the upper holders 40 and 40. Further, one end of a power supply line 46 is connected to the cathode electrode 44, and the other end of the power supply line 46 is connected to a high frequency power supply 48 installed outside the vacuum chamber 28.

  On the lower bottom wall portion 36 of the chamber body 30, lower holders 50 and 50 are erected integrally. On the lower holders 50, 50, upper support protrusions 52, 52 and lower support protrusions 54, 54 are integrally protruded apart from each other in the vertical direction. Then, the anode electrode 56 accommodated in the chamber body 30 faces the lower support protrusions 54, 54 in a state of facing the cathode electrode 44 held by the upper holders 40, 40 with a predetermined distance in the vertical direction. Supported by the lower holders 50 and 50. The anode electrode 56 is grounded. Further, the upper support protrusions 52, 52 of the lower holders 50, 50 can support the intermediate product 24.

  An exhaust pipe 58 is installed at one place on the periphery of the lower end of the side wall 34 of the chamber body 30 so as to penetrate the side wall 34 so as to communicate with the inside and outside of the chamber main body 30. A vacuum pump 60 is provided on the exhaust pipe 58. By the operation of the vacuum pump 60, the gas in the chamber body 30 is discharged to the outside through the exhaust pipe 58, and the chamber body 30 is decompressed.

  Further, first, second, and third three introduction pipes 62 a, 62 b, and 62 c are installed in the upper end side portion of the side wall portion 34 so as to penetrate the side wall portion 34. In the first, second, and third introduction pipes 62a, 62b, and 62c, the one end side openings that enter and open into the chamber body 30 are the first, second, and third gases, respectively. The inlets 64a, 64b, and 64c are used. In addition, a first cylinder 66a that stores a silicon compound gas is connected to the other end of the first introduction pipe 62a that extends to the outside of the chamber body 30. A second cylinder 66b for storing oxygen gas is connected to the other end of the second introduction pipe 62b on the side of the chamber main body 30 extending to the outside. A third cylinder 66c that stores fluorine gas is connected to the other end of the third introduction pipe 62c that extends to the outside of the chamber body 30. Further, the first, second, and third cylinders 66a, 66b, 66c are connected to the first, second, and third introduction pipes 62a, 62b, 62c at the first, second, and third cylinders. Open / close valves 68a, 68b and 68c are provided, respectively.

  As will be described later, the silicon compound gas accommodated in the first cylinder 66a is used as a source gas for the first film forming gas for forming the base layer portion 18 and forms the surface layer portion 20. It is also used as a raw material gas for the second film forming gas. The oxygen gas stored in the second cylinder 66b is used as a reaction gas for the first film formation gas and also as a reaction gas constituting the second film formation gas. The fluorine gas stored in the third cylinder 66c is used as the source gas for the second film-forming gas together with the oxygen gas stored in the second cylinder 66b. And these silicon compound gas, oxygen gas, and fluorine gas are accommodated in the 1st thru | or 3rd cylinder 66a, 66b, 66c by the pressure exceeding atmospheric pressure.

The silicon compound constituting the silicon compound gas contained in the first cylinder 66a 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 66a, or two or more types of silicon compound gases may be stored. May be separately accommodated in the plurality of first cylinders 66a.

  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 by using the plasma CVD apparatus 26 having such a structure, first, As shown in FIG. 2, the intermediate product 24 in which the undercoat layer 14 is laminated on both surfaces of the resin base material 12, and the upper support protrusions of the lower holders 50, 50 provided in the chamber body 30. The lower holders 50 and 50 are supported by 52 and 52.

Next, after the upper opening 38 is covered with the lid 32, the lid 32 is locked to the chamber body 30 by a lock mechanism (not shown). Thereby, the inside of the vacuum chamber 28 is hermetically sealed. Thereafter, the vacuum pump 60 is operated to reduce the pressure in the vacuum chamber 28. By this depressurization operation, the pressure in the vacuum chamber 28 is, for example, about 10 ⁻⁵ to 10 ⁻³ Pa.

  When the pressure in the vacuum chamber 28 reaches a predetermined value, the first opening and closing of the first cylinder 66a connected to the first introduction pipe 62a and the second introduction pipe 62b, respectively, with the vacuum pump 60 being operated. The valve 68a and the second opening / closing valve 68b of the second cylinder 66b are opened. Thereby, the silicon compound gas in the first cylinder 66a is circulated in the first introduction pipe 62a and introduced into the vacuum chamber 28 from the first gas introduction port 64a. At the same time, the oxygen gas in the second cylinder 66b is circulated into the second introduction pipe 62b and introduced into the vacuum chamber 28 from the second gas introduction port 64b. Thus, the first film-forming gas composed of the silicon compound gas and the oxygen gas for forming the base layer portion 18 is introduced into the vacuum chamber 28 and filled.

  When the silicon chamber gas and oxygen gas are filled in the vacuum chamber 28 and the internal pressure of the vacuum chamber 28 reaches a predetermined value, the high frequency power supply 48 is turned on, and the cathode electrode 44 disposed in the vacuum chamber 28 is turned on. On the other hand, a high-frequency current is supplied through the feeder line 46. As a result, a discharge phenomenon is caused between the cathode electrode 44 and the anode electrode 56, and the silicon compound gas and the oxygen gas filled in the vacuum chamber 28 are turned into plasma, respectively. Are generated in the vacuum chamber 28 at a relatively low temperature.

Then, 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 in the space in the vacuum chamber 28 or on the surface of the intermediate product 24, and SiO 2 ₂ and deposit it on the entire surface of the intermediate product 24. Accordingly, the base layer portion 18 made of SiO ₂ is laminated on the undercoat layers 14 and 14 of the intermediate product 24 at a relatively low temperature and at a sufficiently high speed.

  In this step, the opening operation of the first opening / closing valve 68a of the first cylinder 66a and the second opening / closing valve 68b of the second cylinder 66b is preset in a certain amount without changing the opening amount. For a certain amount of time. As a result, the amount of silicon compound gas and oxygen gas introduced into the vacuum chamber 28 per unit time is made constant, and the ratio of the amount of silicon compound gas and oxygen gas in the vacuum chamber 28 is constant. The internal pressure of the vacuum chamber 28 is also maintained at a constant value.

  The thickness of the base layer 18 formed on the undercoat layers 14 and 14 is such that the silicon compound gas and the oxygen gas are introduced into the vacuum chamber 28 at a constant introduction amount, that is, the silicon compound gas and The oxygen gas is appropriately adjusted according to the time for reacting with the oxygen gas by the plasma CVD method. In other words, the opening operation time at a certain amount of the first opening / closing valve 68a of the first cylinder 66a and the second opening / closing valve 68b of the second cylinder 66b is a preset value of the thickness of the base layer 18 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 68a and 68b of the first and second cylinders 66a and 66b, that is, the start of introduction of the silicon compound gas and oxygen gas into the vacuum chamber 28. When (a time set according to the film thickness of the base layer portion 18) has elapsed, the introduction of the fluorine gas in the third cylinder 66c into the vacuum chamber 28 is started. As a result, introduction of the silicon compound gas, oxygen gas, and fluorine gas constituting the film forming gas for forming the surface layer portion 20 into the vacuum chamber 28 is started. At this time, since the supply of the high-frequency current to the cathode electrode 44 is continued, the fluorine gas introduced into the vacuum chamber 28 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 fluorine gas into the vacuum chamber 28 may be set to 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 lapse of time, the amount of oxygen gas introduced per unit time and the amount of fluorine gas introduced per unit time are adjusted to a ratio of 1: 1. When silicon compound gas, oxygen gas, and fluorine gas are introduced into the vacuum chamber 28, the total amount of oxygen gas and fluorine gas introduced per unit time, and the amount of silicon compound gas per unit time. 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 28. It is more desirable that the ratio is the same. As a result, it is possible to prevent as much as possible the pressure in the vacuum chamber 28 from being increased by newly introducing fluorine gas into the vacuum chamber 28. It should be noted that in order to form the surface layer portion 20, the amount of gas components newly introduced into the vacuum chamber 28 and the respective gas components of the film forming gas introduced into the vacuum chamber 28 when the base layer portion 18 is formed. It is a matter of course that the ratio of the introduction amount of is appropriately changed depending on the types of the silicon compound constituting the base layer portion 18 and the fluorine compound constituting the surface layer portion 20.

When the introduction of fluorine gas into the vacuum chamber 28 is started in addition to the silicon compound gas and oxygen gas, the fluorine gas is initially introduced from all of the gases existing in the vacuum chamber 28. 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 introduction of fluorine gas into the vacuum chamber 28, the proportion of fluorine gas in all the gases present in the vacuum chamber 28 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 fluorine gas by the plasma CVD method (silicon compound gas plasma, oxygen gas plasma and fluorine gas). Reaction with plasma). Thereby, SiO ₂ and SiOF are generated simultaneously. When the amount of fluorine gas in the vacuum chamber 28 increases with the passage of time, the plasma of the silicon compound gas, oxygen gas, and fluorine 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 production amount of SiO ₂ exceeds the production amount of SiO ₂ .

Thus, in addition to the silicon compound gas and the oxygen gas, the introduction of fluorine gas into the vacuum chamber 28 is started, whereby the intermediate layer 22 in which SiO ₂ and SiO OF are mixed is formed on the base layer portion 18. Will be. In the intermediate layer 22, the content of SiO ₂ gradually decreases from the base layer 18 side toward the opposite side, while the content of SiO ₂ gradually increases. That is, the content ratio of SiO _{2 and} the content ratio of SiOOF in the intermediate layer 22 change from the base layer portion 18 side to the surface layer portion 20 side in an inclined manner.

  Thereafter, when more time passes and the amount of fluorine gas in the vacuum chamber 28 reaches a sufficient amount, only the reaction of the silicon compound gas, oxygen gas, and fluorine gas by the plasma CVD method proceeds, and SiOF. Will only be generated. When the elapsed time from the start of introduction of fluorine gas into the vacuum chamber 28 reaches a preset time, the first, second, and third on-off valves 68a, 68b, 68c are all closed. Then, the introduction of the silicon compound gas, oxygen gas, and fluorine gas into the vacuum chamber 28 is stopped. As a result, the surface layer portion 20 made of SiOF 3 is formed on the intermediate layer 22 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 20 made of SiOF is determined by the amount of oxygen gas and fluorine gas introduced into the vacuum chamber 28 per unit time by the opening / closing operation of the second and third opening / closing valves 68b and 68c as described above. The time from when the pressure becomes constant to when the introduction of the silicon compound gas, oxygen gas, and fluorine gas into the vacuum chamber 28 is stopped is adjusted as appropriate.

As described above, in the present embodiment, the intermediate product 24 in which the undercoat layer 14 is laminated on the surface of the resin base material 12 is accommodated and disposed in one vacuum chamber 28, and the base layer portion 18 made of SiO _2. And a topcoat layer 16 having a surface layer portion 20 made of SiOF 3 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 18 to the formation operation of the surface layer portion 20, a film forming gas (first film forming gas) for forming the base layer portion 18 is exhausted from the vacuum chamber 28. Therefore, it can be freed from the troublesome and time-consuming work of exhausting the film-forming gas from the vacuum chamber 28.

  In addition, the oxygen gas contained as a reaction gas in the film forming gas for forming the base layer portion 18 is a film forming gas for forming the surface layer portion 20 (second film forming gas) in the operation of forming the surface layer portion 20. 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 18 that exhibits abrasion resistance and the water repellency and antifouling properties are exhibited while further improving the abrasion resistance. The top coat layer 16 including the surface layer portion 20 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 22 in which SiO ₂ and SiOOF constituting them are mixed between the base layer portion 18 and the surface layer portion 20. Therefore, a clear interface is not formed between the base layer portion 18 and the surface layer portion 20, thereby preventing occurrence of peeling or the like at the interface between the base layer portion 18 and the surface layer portion 20 as much as possible. The adhesion between the base layer portion 18 and the surface layer portion 20 can be effectively enhanced.

  And as a result thereof, according to the present embodiment, the occurrence of interference fringes is suppressed, and excellent properties in abrasion resistance, water repellency and antifouling properties, despite changes in the use environment, etc. The resin glass 10 that is stably exhibited over a longer period of time can be obtained efficiently and at low cost by a simple operation.

By the way, in the first embodiment described above, when switching from the formation operation of the base layer portion 18 made of SiO ₂ to the formation operation of the surface layer portion 20 made of SiO ₂ , the film forming gas in the base layer portion 18 has a vacuum chamber 28. In addition, the introduction of fluorine gas contained in the film forming gas of the surface layer portion 20 as a reactive gas into the vacuum chamber 28 is started while maintaining the introduction to the vacuum chamber 28. However, for example, while the base layer portion 18 is made of SiO ₂ , the surface layer portion 20 is made of polytetrafluoroethylene (PTFE), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride ( Included in the film-forming gas for forming the base layer 18 such as when it is made of various fluorine resins such as PVF) and perfluoroalkoxy fluororesin (PFA), etc. When the gas component contained in the film forming gas for forming the surface layer portion 20 is completely different from the gas component, the operation performed in the first embodiment is partly different. By performing the operation, the base layer portion 18, the surface layer portion 20, and the intermediate layer 22 are formed.

That is, for example, when the multi-layered topcoat layer 16 having the base layer portion 18 made of SiO ₂ and the surface layer portion 20 made of PTFE is laminated on the undercoat layer 14 of the resin base material 12, first, A base layer portion 18 made of SiO ₂ is formed on the undercoat layer 14 of the intermediate product 24. The base layer portion 18 is formed using the plasma CVD apparatus 26 shown in FIG. 2 in the same manner as described above.

Here, in the first cylinder 66a and the second cylinder 66b of the plasma CVD apparatus 26, the film forming gas (first film forming gas) made of SiO ₂ is included as a source gas. A silicon compound gas and an oxygen gas contained as a reaction gas are accommodated. The third cylinder 66c contains a fluorine compound gas contained in a film forming gas (second film forming gas) of the surface layer portion 20 made of PTFE.

As the silicon compound gas accommodated in the first cylinder 66a, any of those exemplified above can be used. Moreover, CF ₄ etc. are illustrated as a fluorine compound which comprises the fluorine compound gas accommodated in the 3rd cylinder 66c. Note that the type of fluorine compound gas contained in the film forming gas of the surface layer portion 20 is appropriately changed according to the type of fluorine compound constituting the surface layer portion 20.

  When the base layer portion 18 is formed on the undercoat layer 14 of the intermediate product 24 using the plasma CVD apparatus 26, the intermediate product 24 is first accommodated in the vacuum chamber 28 as shown in FIG. Deploy. Thereafter, after the inside of the vacuum chamber 28 is brought into a predetermined vacuum state, the first and second on-off valves 68a and 68b are opened, and the silicon compound gas in the first cylinder 66a and the oxygen gas in the second cylinder 66b Is introduced into the vacuum chamber 28 at a constant introduction amount per unit time, and the vacuum chamber 28 is filled with a film forming gas composed of the silicon compound gas and the oxygen gas for forming the base layer portion 18. Let

Next, a voltage is applied between the cathode electrode 44 and the anode electrode 56 installed in the vacuum chamber 28, and the silicon compound gas and the oxygen gas in the vacuum chamber 28 are turned into plasma, respectively. As a result, the silicon compound gas and the oxygen gas are reacted by the plasma CVD method in the vacuum chamber 28 to form the base layer portion 18 made of SiO ₂ on the undercoat layer 14 of the intermediate product 24.

Then, when a preset time has elapsed after the first and second opening / closing valves 68a, 68b of the first and second cylinders 66a, 66b are opened, the first opening / closing valve 68a and the second opening / closing valve 68b. The first and second on-off valves 68a and 68b are completely closed when a preset time has elapsed since the start of the closing operation, so that their opening amounts are gradually reduced. To do. That is, the introduction amount of the silicon compound gas, which is the raw material gas of the first film forming gas introduced into the vacuum chamber 28 to form the silicon compound layer 18, and the oxygen gas, which is the reaction gas, into the vacuum chamber 28 is gradually reduced. We will let it go to zero before long. In this way, after a preset time has elapsed from the start of introduction of the silicon compound gas and oxygen gas into the vacuum chamber 28, the introduction amount of the silicon compound gas and oxygen gas into the vacuum chamber 28 becomes zero, and the vacuum When the amounts of silicon compound gas and oxygen gas stored in the chamber 28 become zero, the generation of SiO ₂ is terminated.

  Further, the third opening / closing valve 68c is opened substantially simultaneously with the start of the closing operation of the first and second opening / closing valves 68a, 68b. At this time, the third opening / closing valve 68c is opened so that the opening amount of the third opening / closing valve 68c gradually increases as the opening amount of the first and second opening / closing valves 68a, 68b decreases. Then, from the time when the first opening / closing valve 68a and the second opening / closing valve 68b are completely closed, the opening amount of the third opening / closing valve 68c is not increased but is set to a constant amount. Thereby, after the introduction amount of the silicon compound gas and the oxygen gas into the vacuum chamber 28 is started to be reduced, the introduction of the fluorine compound gas into the vacuum chamber 28 is started and the introduction amount thereof is gradually increased. . Then, after the introduction amount of the silicon compound gas and the oxygen gas into the vacuum chamber 28 becomes zero, the introduction amount per unit time of the fluorine compound gas into the vacuum chamber 28 is made constant.

  As described above, when the introduction amount of the fluorine compound gas is increased while reducing the introduction amount of the silicon compound gas and the oxygen gas into the vacuum chamber 28, the silicon compound gas, the oxygen gas, and the fluorine gas are increased. The total amount of compound gas introduced per unit time is the amount of silicon compound gas and oxygen gas per unit time in the stage before the amount of silicon compound gas and oxygen gas introduced into the vacuum chamber 28 is reduced. It is preferable that the total amount of introduction be the same. In addition, even when the introduction amount of the fluorine compound gas per unit time into the vacuum chamber 28 is constant, the introduction amount of the fluorine compound gas per unit time is within the vacuum chamber 28 of the silicon compound gas and the oxygen gas. It is desirable that the total introduction amount per unit time of each of the silicon compound gas and the oxygen gas in the stage before the introduction amount is reduced. Thereby, the internal pressure of the vacuum chamber 28 can be always kept constant.

  The timing for starting the opening operation of the third opening / closing valve 68c, that is, the timing for starting the introduction of the fluorine compound gas into the vacuum chamber 28 is not necessarily the start of the closing operation for the first and second opening / closing valves 68a, 68b. It is not necessary to be exactly the same as the start of the reduction of the introduction amount of the silicon compound gas and the oxygen gas into the vacuum chamber 28 by the It may be slightly shifted back and forth. Further, the high-frequency current is continuously supplied to the cathode electrode 44 regardless of the type of gas introduced into the vacuum chamber 28 or the increase or decrease in the amount introduced.

  Thus, since the introduction of the fluorine compound gas into the vacuum chamber 28 is started, the amount of silicon compound gas and oxygen gas introduced into the vacuum chamber 28 is set to zero, and the silicon compound gas and oxygen gas in the vacuum chamber 28 are reduced. Until completely disappeared, the silicon compound gas, oxygen gas, and fluorine compound gas in the vacuum chamber 28 are turned into plasma, respectively.

Thereby, since the introduction of the fluorine compound gas into the vacuum chamber 28 is started, the introduction amount of the silicon compound gas and the oxygen gas into the vacuum chamber 28 becomes zero, and the silicon compound gas and the oxygen gas in the vacuum chamber 28 are further reduced. Until the amount of oxygen reaches zero, the reaction between the plasma of the silicon compound gas and the plasma of the oxygen gas (by the plasma CVD method of the silicon compound gas and the oxygen gas) in the space in the vacuum chamber 28 and the surface of the intermediate product 24. (Reaction) is performed to generate SiO _2, and in parallel therewith, a reaction of a fluorine compound gas by a plasma CVD method is also performed to generate PTFE. At this time, as the amount of silicon compound gas and oxygen gas introduced into the vacuum chamber 28 decreases, the amount of SiO ₂ produced gradually decreases, while the amount of fluorine compound gas introduced into the vacuum chamber 28 increases. The amount of PTFE produced gradually increases with the increase of.

Thus, laminated formed on the undercoat layer 14 of the intermediate product 24, on the base layer part 18 made of SiO _2, is deposited SiO ₂ and PTFE, hereinafter Te, on such base layer part 18, SiO ₂ and the PTFE is The mixed intermediate layer 22 is formed at a relatively low temperature and at a sufficiently high speed.

As described above, since the introduction of the fluorine compound gas into the vacuum chamber 28 is started, the introduction amount of the silicon compound gas and the oxygen gas into the vacuum chamber 28 is zero, and the silicon compound in the vacuum chamber 28 is reduced. Until the amounts of gas and oxygen gas become zero, the amount of SiO ₂ produced gradually decreases, while the amount of PTFE produced gradually increases. Therefore, in the intermediate layer 22, the content of SiO ₂ gradually decreases while the content of PTFE gradually increases from the base layer portion 18 side (undercoat layer 14 side) to the opposite side. It becomes. That is, the content ratio of SiO _{2 and} the content ratio of PTFE in the intermediate layer 22 change in an inclined manner from the base layer portion 18 side to the surface layer portion 20 side.

  Then, the introduction amount of the silicon compound gas and oxygen gas into the vacuum chamber 28 becomes zero, and only the fluorine compound gas is introduced into the vacuum chamber 28. Also, the silicon compound gas in the vacuum chamber 28 is introduced. After the remaining amount of oxygen gas becomes zero, only the reaction of the fluorine compound gas by the plasma CVD method proceeds in the space in the vacuum chamber 28 or on the surface of the intermediate product 24 (on the base layer portion 18).

  This produces only PTFE and deposits it on the intermediate layer 22 laminated to the intermediate product 24. Then, when the elapsed time from the start of introduction of the fluorine compound gas into the vacuum chamber 28 reaches a preset time, the third opening / closing valve 68c is closed and the fluorine compound gas in the vacuum chamber 28 is closed. Stop introducing to. Therefore, the surface layer portion 20 having a predetermined thickness is formed on the intermediate layer 22 at a relatively low temperature and at a sufficiently high speed.

  Thus, on the undercoat layer 14 of the intermediate product 24, the topcoat layer 16 having a multilayer structure in which the base layer portion 18, the intermediate layer 22, and the surface layer portion 20 are laminated in that order is laminated. Thus, the intended resin glass 10 having the structure shown in FIG. 1 is obtained.

  The thickness of the surface layer portion 20 is such that the introduction amount of the fluorine compound gas per unit time into the vacuum chamber 28 is constant by the opening / closing operation of the third opening / closing valve 68c as described above, and the inside of the vacuum chamber 28 The amount is appropriately adjusted according to the time from when the residual amounts of the silicon compound gas and oxygen gas become zero until the introduction of the fluorine compound gas into the vacuum chamber 28 is stopped. In other words, the opening operation time of the third opening / closing valve 68c with a certain opening amount is appropriately determined according to a preset value of the thickness of the surface layer portion 20 or the like.

  As described above, even in the present embodiment, the top coat layer 16 is formed on the undercoat layer 14 by a series of operations using the plasma CVD method in a state where the intermediate product 24 is accommodated in one vacuum chamber 28. Can be formed. Further, when switching from the formation operation of the base layer portion 18 to the formation operation of the surface layer portion 20, the operation of once exhausting all the gas in the vacuum chamber 28 is not performed, and all of the gas introduced into the vacuum chamber 28 is not performed. Is effectively used for the reaction by the plasma CVD method.

  Therefore, even in the present embodiment, the topcoat layer 16 can be formed efficiently and at low cost on the undercoat layer 14 of the resin base material 12 by a simple operation.

Further, in the present embodiment, between the base portion 18 and the surface layer portion 20, mixed with SiO ₂ constituting them and the PTFE and their content towards the surface layer portion 20 from the base portion 18 side The top coat layer 16 is formed by forming an intermediate layer 22 that changes in an inclined manner. Therefore, a clear interface is not formed between the base layer portion 18 and the surface layer portion 20, thereby improving the adhesion between the base layer portion 18 and the surface layer portion 20 effectively.

  As a result, according to the present embodiment, the occurrence of interference fringes is suppressed, and the excellent wear resistance, water repellency, and antifouling properties can be stably ensured over a long period of time. Can be obtained very advantageously.

Further, for example, when the base layer portion 18 is made of SiO ₂ and the surface layer portion 20 is made of a fluorine-containing silicon compound such as SiF ₄ , the film forming gas for forming the base layer portion 18 is used. In the case where the gas component included and the gas component included in the film forming gas for forming the surface layer portion 20 are different from each other only in some gas components (for example, reactive gas) The operations performed in the production of the first embodiment and the second embodiment are further partially different from each other, and the base layer portion 18 and the surface layer portion 20 of the topcoat layer 16 and the intermediate layer 22 are performed. Are formed respectively.

That is, in the same manner as in the two embodiments, the silicon compound gas and the oxygen gas are introduced into the vacuum chamber 28 while the intermediate product 24 is accommodated in the vacuum chamber 28 of the plasma CVD apparatus 26. A base layer portion 18 made of a SiO ₂ plasma CVD layer is formed on the undercoat layer 14 of the intermediate product 24 by reacting a silicon compound gas and an oxygen gas by a plasma CVD method.

  When a predetermined time has elapsed from the start of introduction of the silicon compound gas and oxygen gas into the vacuum chamber 28, the fluorine gas is introduced into the vacuum chamber 28 while gradually reducing the amount of oxygen gas introduced into the vacuum chamber 28 in advance. Introduce so that the introduction amount gradually increases. Then, when the amount of oxygen gas introduced eventually becomes zero, the amount of fluorine gas introduced into the vacuum chamber 28 per unit time is set to a constant value. At this time, the silicon compound gas is introduced into the vacuum chamber 28 at a constant introduction amount regardless of variations in the introduction amount of oxygen gas or fluorine gas.

Then, while the amount of oxygen gas introduced into the vacuum chamber 28 is gradually reduced to zero, the reaction of the silicon compound gas and oxygen gas in the vacuum chamber 28 is performed by the plasma CVD method. In parallel, the reaction of the silicon compound gas and the fluorine gas by the plasma CVD method is performed. Thus, the intermediate layer 22 in which SiO ₂ and SiF ₄ are mixed is formed on the base layer portion 18 in a stacked manner. In the intermediate layer 22, the SiO ₂ content gradually decreases from the base layer 18 side (undercoat layer 14 side) to the opposite side, while the SiF ₄ content increases gradually. Become. That is, the content ratio of SiO _{2 and} the content ratio of SiF _{4 in} the intermediate layer 22 change from the base layer portion 18 side to the surface layer portion 20 side in an inclined manner.

When the introduction of oxygen gas into the vacuum chamber 28 is stopped and the amount of fluorine gas introduced into the vacuum chamber 28 per unit time is set to a constant value, a silicon compound is formed in the vacuum chamber 28. Only the reaction of the gas and fluorine gas by the plasma CVD method proceeds. As a result, the surface layer portion 20 made of a SiF ₄ plasma CVD layer is laminated on the intermediate layer 22. Thereafter, when a predetermined time has elapsed after the introduction of the oxygen gas into the vacuum chamber 28 is stopped, the introduction of the silicon compound gas and the fluorine gas into the vacuum chamber 28 is stopped.

  Thus, on the undercoat layer 14 of the intermediate product 24, the topcoat layer 16 having a multilayer structure in which the base layer portion 18, the intermediate layer 22, and the surface layer portion 20 are laminated in that order is laminated. Thus, the intended resin glass 10 having the structure shown in FIG. 1 is obtained.

  Even in this embodiment as described above, substantially the same operations and effects as those provided in the first and second embodiments can be enjoyed effectively.

  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 acrylic resin was applied to the entire surface of each of the two resin substrates, and this was cured by irradiation with ultraviolet rays. Thereby, the undercoat layer which consists of a coating film of an acrylic resin was formed in the whole surface of each surface of two resin base materials. The thicknesses of the undercoat layers on the two resin substrate surfaces were each 10 μm.

Then, after one of the two resin base materials having an undercoat layer formed on the surface is accommodated in a vacuum chamber of a plasma CVD apparatus having a structure as shown in FIG. 2, the vacuum chamber is evacuated. It was in a state. The internal pressure of the vacuum chamber at this time was 10 ⁻⁴ Pa.

After that, monosilane gas and oxygen gas, which are silicon compound gases, are introduced into the vacuum chamber so that the introduction amount per unit time is constant and filled, and then a high frequency current is supplied from the high frequency power source to the cathode electrode. A base layer portion made of SiO ₂ was formed on the undercoat layer by generating plasma of oxygen gas and plasma of monosilane gas and reacting these plasma gases. In addition, formation operation of this base layer part was implemented continuously for 30 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 2000 W. The base layer thus formed had a thickness of 1 μm.

  Then, after 30 seconds have elapsed from the start of introduction of oxygen gas and monosilane gas into the vacuum chamber (start of base layer forming operation), the amount of fluorine gas introduced into the vacuum chamber gradually increases per unit time. Introduced to be. Oxygen gas and monosilane gas were continuously introduced at the same introduction amount per unit time as in the formation of the base layer portion.

While the monosilane gas, oxygen gas and fluorine gas are introduced into the vacuum chamber, the high frequency current is continuously supplied to the cathode electrode while the output value of the high frequency power source is kept at 2000 W, so that the monosilane gas and oxygen gas are supplied. The plasma of monosilane gas and the plasma of oxygen gas were reacted with each other, while the plasma of monosilane gas, the plasma of oxygen gas, and the plasma of fluorine gas were reacted in parallel. As a result, an intermediate layer 22 in which SiO ₂ and SiOOF were mixed was formed on the base layer portion. The amount of fluorine gas introduced into the vacuum chamber was increased by 500 ml / sec. The thickness of the intermediate layer thus formed was 10 μm.

  Subsequently, 30 seconds after the start of reducing the amount of fluorine gas introduced into the vacuum chamber, the amount of fluorine gas introduced into the vacuum chamber per unit time was set to 50 ml / sec. At this time, oxygen gas and monosilane gas were continuously introduced at a constant introduction amount per unit time regardless of the introduction amount of fluorine gas into the vacuum chamber.

  Further, while maintaining the output value of the high frequency power source at 2000 W, a high frequency current is continuously supplied to the cathode electrode to generate monosilane gas plasma, fluorine gas plasma, and oxygen gas plasma. To form a surface layer portion made of SiOF on the intermediate layer. The surface layer portion had a thickness of 1 μm.

Thus, as shown in FIG. 1, the surface of the polycarbonate resin substrate with an undercoat layer is formed, a base layer portion made of SiO _2, an intermediate layer SiO ₂ and SiOF are mixed, consisting of SiOF A transparent resin glass was obtained in which a topcoat layer having a three-layer structure of the surface layer was laminated on the undercoat layer. This resin glass was designated as Test Example 1.

On the other hand, for the sake of comparison, the remaining one resin base material having an undercoat layer formed on the surface is accommodated in the vacuum chamber of the plasma CVD apparatus used in the production of the resin glass of Test Example 1. After that, the vacuum chamber was evacuated. The internal pressure of the vacuum chamber at this time was 10 ⁻⁴ Pa.

Thereafter, oxygen gas and monosilane gas are introduced into the vacuum chamber so that the introduction amount per unit time is constant and filled, and then a high frequency current is supplied from the high frequency power source to the cathode electrode, A base layer portion made of SiO ₂ was formed on the undercoat layer by generating plasma and plasma of monosilane gas and reacting these plasma gases. In addition, formation operation of this base layer part was continuously implemented for 30 seconds. At this time, 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. The output value of the high frequency power source was 2000 W. The thickness of the formed base layer portion was 0.5 μm.

  Next, after 30 seconds from the start of introduction of oxygen gas and monosilane gas into the vacuum chamber (start of formation of the base layer portion), the introduction of oxygen gas and monosilane gas into the vacuum chamber is stopped, and then the operation of the vacuum pump is performed. All oxygen gas and monosilane gas remaining in the vacuum chamber were exhausted from the vacuum chamber.

Thereafter, monosilane gas and oxygen gas are introduced into the vacuum chamber at an internal pressure of 10 ⁻⁴ Pa at the same introduction amount of 50 ml / sec and fluorine gas is introduced at an introduction amount of 500 ml / sec. Then, a high frequency current was supplied from the high frequency power source to the cathode electrode. As a result, plasma of monosilane gas, oxygen gas, and fluorine gas was generated, and these plasma gases were reacted to form a surface layer portion made of SiOF 3 on the base layer portion. In addition, formation operation of this surface layer part was implemented continuously for 30 seconds. The output value of the high frequency power source was 2000 W. The thickness of the formed surface layer portion was 0.5 μm.

Thus, an undercoat layer is formed on the surface of the polycarbonate resin base material, and a topcoat layer having a two-layer structure of a base layer portion made of SiO ₂ and a surface layer portion made of SiOOF is formed on the undercoat layer. A transparent resin glass was obtained. This resin glass was determined as Test Example 2.

  And, using the two types of transparent resin glasses of Test Example 1 and Test Example 2 obtained as described above, the abrasion resistance of each resin glass, the base layer portion and the surface layer portion constituting the top coat layer, An evaluation test on the adhesion between the two was performed as follows. The results are shown in Table 1 below.

<Abrasion resistance test>
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% was 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 when the value of ΔH is 2.0% 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 apparent from the results of such Table 1, the top coat layer, a base layer portion made of SiO _2, three layers and the intermediate layer, and a surface layer portion consisting of SiOF, layered in that order to SiO ₂ and SiOF coexist When the resin glass of Test Example 1 having a structure is compared with the resin glass of Test Example 2 in which the top coat layer has a two-layer structure of a base layer portion made of SiO ₂ and a surface layer portion made of SiO OF, As for these two types of resin glasses, the evaluation results of the abrasion resistance test are both good. However, although the evaluation result of the adhesion test of the resin glass of Test Example 1 is ◯, the evaluation result of the adhesion test of the resin glass of Test Example 2 is Δ. This clearly shows that the resin glass in which the topcoat layer is formed according to the method of 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 above embodiment, the base layer portion 18 of the topcoat layer 16 is composed of SiO ₂ , but the type of silicon compound that constitutes the base layer portion 18 is not limited in any way. Can be configured with, for example, SiON or Si ₃ N ₄ instead of the illustrated SiO ₂ .

  Moreover, if the surface layer part 20 of the topcoat layer 16 is comprised by the plasma CVD layer of the compound containing a fluorine, the kind of compound which comprises this surface layer part 20 will not be limited at all. Therefore, the kind of the gas component contained in the second film-forming gas for forming the surface layer portion 20 by the plasma CVD method, particularly the fluorine gas or the fluorine compound gas, is also the kind of the compound constituting the surface layer portion 20. It can be appropriately changed according to the above.

Note that the amount of the film-forming gas (first film-forming gas) for forming the base layer portion 18 introduced into the vacuum chamber 28 is gradually reduced to eventually reach zero, while the surface layer portion 20 When forming the intermediate layer 22 by introducing a film-forming gas (second film-forming gas) into the vacuum chamber 28, or for forming the base layer 18 In addition to the gas, when the intermediate layer 22 is formed by introducing a film forming gas for forming the surface layer 20 into the vacuum chamber 28, the film forming gas for forming the surface layer 20 is used as the film forming gas for forming the surface layer 20. Includes fluorine gas or fluorine compound gas. In the former case, as the fluorine compound gas contained in the film forming gas for forming the surface layer portion 20, those exemplified above can be used. In the latter case, the surface layer portion 20 can be used. As the fluorine compound gas contained in the film forming gas for forming the film, for example, SiF ₄ gas, CF ₄ gas, or the like is used alone or in combination depending on the type of fluorine compound constituting the surface layer portion 20. It is done.

  Furthermore, as the plasma CVD apparatus used for forming the base layer portion 18 and the surface layer portion 20, 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.

  Further, the top coat layer 16 having a laminated structure of the base layer portion 18, the intermediate layer 22, and the surface layer portion 20 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 Base layer part 20 Surface layer part 22 Intermediate layer 24 Intermediate product 26 Plasma CVD apparatus

Claims (5)

A method for producing a resin product, wherein an undercoat layer is laminated on the surface of a resin base material made of a polycarbonate resin molded product, and a silicon compound layer is further laminated on the undercoat layer. ,
Preparing the resin substrate;
A step of laminating and forming the undercoat layer on the surface of the resin substrate;
A step of accommodating the resin base material on which the undercoat layer is laminated in a reaction chamber and then evacuating the reaction chamber;
A first film-forming gas containing a silicon compound gas was introduced into the vacuum reaction chamber, and the first film-forming gas was reacted by a plasma CVD method and was accommodated in the reaction chamber. A step of laminating the silicon compound layer on the undercoat layer of the substrate;
A second film-forming gas containing fluorine gas or fluorine compound gas is introduced into the reaction chamber containing the resin base material on which the silicon compound layer is formed, and the second film-forming gas is introduced. To form a fluorine compound layer on the silicon compound layer by reacting with a plasma CVD method;
The introduction amount of at least a part of the gas component in the first film-forming gas introduced into the reaction chamber is gradually reduced from the start of the introduction of the second film-forming gas into the reaction chamber, and zero Thus, the first film formation is started from the start of the introduction of the second film formation gas into the reaction chamber until the amount of the at least some gas components in the reaction chamber becomes zero. The silicon compound is formed before the fluorine compound layer is formed on the silicon compound layer by simultaneously performing the reaction of the working gas by the plasma CVD method and the reaction of the second film forming gas by the plasma CVD method. Forming an intermediate layer in which a silicon compound and a fluorine compound are mixed on the layer;
The manufacturing method of the resin product characterized by including. A method for producing a resin product, wherein an undercoat layer is laminated on the surface of a resin base material made of a polycarbonate resin molded product, and a silicon compound layer is further laminated on the undercoat layer. ,
Preparing the resin substrate;
A step of laminating and forming the undercoat layer on the surface of the resin substrate;
A step of accommodating the resin base material on which the undercoat layer is laminated in a reaction chamber and then evacuating the reaction chamber;
A first film-forming gas containing a silicon compound gas was introduced into the vacuum reaction chamber, and the first film-forming gas was reacted by a plasma CVD method and was accommodated in the reaction chamber. A step of laminating a base layer portion of the silicon compound layer on the undercoat layer of the substrate;
The first film-forming layer is formed after the formation of the silicon compound layer on the surface of the resin base material in the reaction chamber containing the resin base material on which the base layer portion of the silicon compound layer is formed. While the gas is continuously introduced, the fluorine gas or the fluorine compound gas is further introduced, whereby the first film forming gas and the second film forming gas containing the fluorine gas or the fluorine compound gas are supplied into the reaction chamber. And the second film-forming gas is reacted by a plasma CVD method to form a surface layer portion of the silicon compound layer made of a silicon compound containing fluorine on the base layer portion of the silicon compound layer. Process,
The manufacturing method of the resin product characterized by including.   The fluorine gas or the fluorine compound gas is introduced into the reaction chamber so that the introduction amount gradually increases, while the introduction of the fluorine gas or the fluorine compound gas into the reaction chamber starts from the first film formation. The method for producing a resin product according to claim 2, wherein the amount of reaction gas contained in the gas is gradually reduced into the reaction chamber. A resin product in which an undercoat layer is laminated on the surface of a resin substrate made of a polycarbonate resin molded product, and a silicon compound layer made of a plasma CVD layer is further laminated on the undercoat layer. There,
A fluorine compound layer composed of a plasma CVD layer is formed on the silicon compound layer, and the silicon compound and the fluorine compound layer constituting the silicon compound layer are interposed between the silicon compound layer and the fluorine compound layer. An intermediate layer made of a plasma CVD layer is formed, and the content of the silicon compound in the intermediate layer is changed from the silicon compound layer side to the fluorine compound layer side. The resin product, wherein the content rate of the fluorine compound in the intermediate layer gradually increases toward the fluorine compound layer side from the silicon compound layer side. A resin product in which an undercoat layer is laminated on the surface of a resin substrate made of a polycarbonate resin molded product, and a silicon compound layer made of a plasma CVD layer is further laminated on the undercoat layer. There,
The silicon compound layer has a multilayer structure of a base layer portion positioned on the undercoat layer side and a surface layer portion laminated on the base layer portion, and the surface layer portion is composed of a silicon compound containing fluorine. Furthermore, an intermediate layer composed of a plasma CVD layer is formed between the base layer portion and the surface layer portion, in which a silicon compound constituting the base layer portion and a fluorine-containing silicon compound constituting the surface layer portion are mixed. 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 fluorine-containing silicon compound constituting the surface layer portion A resin product, characterized in that the content in the intermediate layer gradually increases from the base layer side toward the surface layer side.

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