JP2016044354A - Film deposition apparatus, film deposition method, and decorative article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film deposition apparatus capable of efficiently depositing a film having a desired shape and pattern by a method with reduced wasteful use of materials and a small environmental load.SOLUTION: A film deposition apparatus 100 comprises: a storage part 43 storing a material P3' for film formation; heating means 4 heating the material P3' stored in the storage part 43; a vapor generation chamber 15 installed with the storage part 43 and evaporating the material P3'; and a film deposition chamber 16 forming a coating film with respect to a substrate P1 using fine particles P31 formed by condensing the vapor of the material P3' generated in the vapor generation chamber 15, and further comprises material supply means 8 additionally supplying the material P3' into the storage part 43 in a state where the material P3' is evaporated.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film forming apparatus, a film forming method, and a decorative article.

  For example, various decorative items such as a timepiece and its components require excellent aesthetics (aesthetic appearance).

  For this reason, materials having excellent texture, such as various metal materials, are used for decorative items (see, for example, Patent Document 1).

  In order to further improve aesthetics, a decorative layer (film) is provided in a predetermined pattern.

  Conventionally, in order to provide a decorative layer (film) with a predetermined pattern, vapor deposition such as vacuum deposition is performed with a mask (resist etc.) arranged, or film formation is performed on the entire surface of the substrate. After that, a method of removing unnecessary portions by etching or the like is adopted.

  However, in these methods, the constituent material of the film included in the final decorative product is a very small part of the material used for manufacturing, and the material is wasted, which is not preferable from the viewpoint of resource saving.

  Further, the recovery of the film forming material, the recycling of the recovered material, the use of resists, etc., increase in processes and the use of chemical substances have caused problems of environmental burden and cost increase.

  Conventionally, it has not been possible to manufacture a decorative article provided with a film in a predetermined pattern with excellent productivity.

JP 2008-150660 A

  An object of the present invention is to provide a film formation apparatus that can efficiently form a desired shape and pattern by a method with less waste of materials and less burden on the environment, less waste of materials, To provide a film forming method capable of efficiently forming a desired shape and pattern by a method having a small environmental load, and to form a film formed by using the film forming apparatus and the film forming method. It is to provide a decorative product that is excellent in aesthetic appearance, has little waste of materials during manufacture, and has a low environmental impact.

Such an object is achieved by the present invention described below.
A film forming apparatus of the present invention includes a storage unit that stores a material for forming a film;
Heating means for heating the material accommodated in the accommodating portion;
A steam generation chamber in which the housing portion is installed and evaporates the material;
Using fine particles formed by condensation of the vapor of the material generated in the vapor generation chamber, and a film formation chamber for forming a film on the substrate,
In a state in which the material is evaporated, a material supply unit that additionally supplies the material to the housing portion is provided.

  Accordingly, it is possible to provide a film forming apparatus that can efficiently form a desired shape and pattern by a method with less waste of materials and less burden on the environment.

  The film forming apparatus of the present invention is preferably configured to additionally supply the preheated material to the housing portion.

  As a result, when the material is additionally supplied to the storage unit, the coarse particles of the material jump out of the storage unit, that is, the coarsening of the fine particles used for film formation can be more reliably prevented and formed. The quality of the coating film can be made more reliably superior.

  In the film forming apparatus of the present invention, it is preferable that the material supply means additionally supplies the particulate material.

  As a result, it becomes easy to store the material for additional supply and supply the material to the accommodating portion, and the film formation efficiency can be made particularly excellent. In addition, since it is easy to manage the amount of material to be additionally supplied to the storage unit, it is possible to prevent an unintentional temperature drop of the material in the storage unit, and to more reliably form a stable quality film. Can do.

  In the film forming apparatus according to the aspect of the invention, it is preferable that the material supply unit aligns the particulate material and intermittently additionally supplies the material to the housing portion.

  Thereby, the management of the amount of the material to be additionally supplied becomes easier, and a stable quality film can be more reliably formed.

  In the film forming apparatus of the present invention, it is preferable that the long material is additionally supplied to the accommodating portion sequentially along the longitudinal direction thereof.

  As a result, it is possible to finely adjust the amount of material additionally supplied to the housing portion, and the amount of material in the housing portion can be controlled with higher accuracy. In addition, the material existing outside the storage unit is also heated (preheated) due to heat conduction from the storage unit, and as a result, a rapid temperature change in the storage unit when the material is additionally supplied to the storage unit is further increased. It can prevent effectively and can make the quality of the film formed more reliable.

  In the film forming apparatus of the present invention, it is preferable that the additionally supplied material is a porous material.

  As a result, it is possible to effectively prevent the bumping phenomenon from occurring when the material is additionally supplied to the storage unit, and as a result, the quality of the formed film should be more stable and excellent. Can do.

  In the film forming apparatus of the present invention, the temperature of the material in the housing portion is lower when the material is additionally supplied by the material supply unit than when the film is formed in the film forming chamber. The temperature control is preferably performed.

  Thereby, it is possible to prevent the material from evaporating more than necessary and unintentional film formation from progressing while making the film formation efficiency sufficiently excellent.

The film forming apparatus of the present invention preferably includes an adhesion preventing unit that prevents the evaporated material from being supplied to and adhered to the base material when the material is additionally supplied by the material supply unit.
Thereby, the quality of the coating film formed can be made more excellent.

  In the film forming apparatus of the present invention, it is preferable that the adhesion preventing means is a guide member that guides the evaporated material to an exhaust port that exhausts the gas in the film forming chamber.

  Thereby, the quality of the formed film can be made more excellent. In addition, maintenance of the film forming apparatus becomes easy.

In the film forming apparatus of the present invention, the film forming apparatus includes an observation unit for observing the storage unit,
It is preferable to adjust the supply amount of the material from the material supply unit based on the observation result of the observation unit.
Thereby, the quantity of the material in an accommodating part can be adjusted to a suitable range more reliably.

The film forming method of the present invention is a film forming method for forming a film on a substrate,
A substrate preparation step of preparing the substrate;
Forming a film by depositing fine particles formed by condensing the vapor of the material after evaporating the film forming material housed in a housing unit installed in a system for film formation A process,
In the state where the material is evaporated, the material is additionally supplied to the housing portion.

  As a result, it is possible to provide a film forming method that can efficiently form a desired shape and pattern by a method with little waste of materials and a small load on the environment.

The film forming method of the present invention is characterized in that a film is formed using the film forming apparatus of the present invention.
As a result, it is possible to provide a film forming method that can efficiently form a desired shape and pattern by a method with little waste of materials and a small load on the environment.

  The decorative article of the present invention is characterized by including a film formed using the film forming apparatus of the present invention.

  As a result, it is possible to provide a decorative product that is excellent in aesthetic appearance, has little waste of materials during manufacture, and has a low environmental impact.

  The decorative article of the present invention is characterized by including a film formed by using the film forming method of the present invention.

  As a result, it is possible to provide a decorative product that is excellent in aesthetic appearance, has little waste of materials during manufacture, and has a low environmental impact.

It is a longitudinal section side view showing typically a 1st embodiment of a film deposition system of the present invention. It is a block diagram of the principal part of the film-forming apparatus shown in FIG. It is a longitudinal cross-sectional side view which shows typically 2nd Embodiment of the film-forming apparatus of this invention. It is a longitudinal cross-sectional side view which shows typically 3rd Embodiment of the film-forming apparatus of this invention, and is a figure which shows the state at the time of film-forming. It is a longitudinal cross-sectional side view which shows typically 3rd Embodiment of the film-forming apparatus of this invention, and is a figure which shows the state at the time of film-forming standby (state which supplies a material to an accommodating part additionally). It is a block diagram of the principal part of the film-forming apparatus shown in FIG. 4, FIG. It is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of a decorative article. It is a typical top view which shows suitable embodiment at the time of applying the ornament of this invention to the cover glass as an exterior | finish part for timepieces. It is sectional drawing which shows suitable embodiment at the time of applying the ornament of this invention to a timepiece (portable timepiece).

  Hereinafter, a film forming apparatus, a film forming method, and a decorative article of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

<< Film Forming Apparatus, Film Forming Method >>
First, a film forming apparatus and a film forming method will be described.

<First Embodiment>
FIG. 1 is a longitudinal sectional side view schematically showing a first embodiment of a film forming apparatus of the present invention. FIG. 2 is a block diagram of a main part of the film forming apparatus shown in FIG. In the following, for convenience of explanation, the x axis, the y axis, and the z axis are shown as three axes orthogonal to each other in FIG. The x-axis is an axis along one of the horizontal directions, the y-axis is an axis along the horizontal direction and perpendicular to the x-axis, and the z-axis is a vertical direction (up and down Direction). In addition, the tip side of each illustrated arrow is a “positive side (+ side)” and the base end side is a “negative side (− side)”. Further, the upper side in FIG. 1 is referred to as “upper (upper)”, and the lower side is referred to as “lower (lower)”.

  The film forming apparatus 100 is an apparatus that performs film formation by ejecting particles (fine particles) P31 generated in the apparatus (inside the system) from a nozzle.

  As shown in FIGS. 1 and 2, the film forming apparatus 100 includes a first chamber (steam generation chamber) 15, a second chamber (film formation chamber) 16, a connecting pipe 2, a gas supply unit 3, and the like. , Heating means 4, pressure adjusting means 5, moving means 6, material supplying means 8, and control unit 7.

  The first chamber 15 is configured to maintain airtightness, and can house a solid base material (film forming material) P3 'used for forming the coating P3 therein.

  The second chamber 16 is provided independently of the first chamber 15. This 2nd chamber 16 is also comprised so that airtightness can be maintained, and the some base material P1 can be accommodated in the inside.

  In addition, the room temperature in the 1st chamber 15 and the 2nd chamber 16 is comprised by the water cooling, ie, the refrigerant | coolant which passes piping, and can be adjusted, for example. The temperature in the 1st chamber 15 and the 2nd chamber 16 can be adjusted to 20 degreeC or more and 90 degrees C or less, for example.

  The connecting pipe 2 connects the first chamber 15 and the second chamber 16, and the film-forming material P 3 ′ vaporized (evaporated) in the second chamber 16 passes through the inner cavity portion 22. Functions as a flow path.

  The connecting pipe 2 has a first opening (one end opening) 25 opened at one end thereof facing the first chamber 15 and a second opening (other end opening) 21 opened at the other end. Faces the second chamber 16. As a result, the first chamber 15 and the second chamber 16 communicate with each other via the connecting pipe 2.

  As shown in FIG. 1, the first opening 25 preferably faces the container (crucible) 43 of the heating means 4 in the first chamber 15 from above. As a result, the vaporized film-forming material P <b> 3 ′ can quickly flow toward the first opening 25.

  Further, the second opening 21 is arranged in parallel to the surface direction of the base material P <b> 1 accommodated in the second chamber 16. The vaporized film-forming material P3 ′ becomes particles (fine particles) P31 in the process of passing through the connecting pipe 2 (lumen portion 22), and the particles are sprayed from the second opening 21 to the substrate P1. . Thereby, the film P3 is formed on the base material P1. Thus, in the connecting pipe 2, the portion on the second opening 21 side functions as the nozzle portion 24.

  The average inner diameter of the connecting tube 2 is not particularly limited, but is preferably 1 mm or more and 10 mm or less, for example. Moreover, the internal diameter of the 2nd opening part 21 is although it does not specifically limit, For example, it is preferable that they are 0.1 mm or more and 1 mm or less.

  Moreover, it does not specifically limit as a constituent material of the connection pipe 2, For example, metal materials, such as stainless steel, can be used.

  In addition, a temperature adjustment mechanism 90 that adjusts the temperature of the connection pipe 2 is provided on the outer periphery of the connection pipe 2. By this temperature adjustment mechanism 90, the temperatures of the vaporized film forming material P3 'and the particles P31 that pass through the connecting pipe 2 can be suitably adjusted. Thereby, the magnitude | size of particle | grains P31 used for formation of the film P3 can be controlled easily and reliably. Further, by heating the connecting pipe 2 by the temperature adjusting mechanism 90, it is possible to prevent the particles P31 passing through the connecting pipe 2 from adhering to the inner peripheral portion (inner wall) of the connecting pipe 2. In addition, it does not specifically limit as temperature of the connecting pipe 2, For example, 30 to 300 degreeC is preferable and 50 to 300 degreeC is more preferable.

  As shown in FIG. 1, the gas supply means 3 supplies gas into the first chamber 15.

  The gas supplied from the gas supply means has a function of guiding the vaporized film forming material P3 'to the connecting pipe 2 and the second chamber (film forming chamber) 16 while cooling. That is, the gas supplied from the gas supply means 3 functions as a carrier gas. Then, the film forming material P3 'vaporized by this cooling is aggregated into particles P31 of a predetermined size in the transport process.

  The gas supply means 3 includes a tank 31 filled with gas, a connecting pipe 32 that connects the tank 31 and the first chamber 15, and an electromagnetic valve 33 that is installed in the middle of the connecting pipe 32. .

The tank 31 can store gas in an airtight manner.
The gas stored in the tank 31 is not particularly limited. For example, nitrogen gas can be used, and other inert gas such as helium or argon can also be used.

  The tank 31 and the first chamber 15 communicate with each other via a connecting pipe 32. The connecting tube 32 may be hard or flexible.

  The connecting pipe 32 is provided with an electromagnetic valve 33 in the middle of the longitudinal direction. The electromagnetic valve 33 opens and closes the connecting pipe 32. When the electromagnetic valve 33 is in the open state, the tank 31 and the first chamber 15 communicate with each other. As a result, the gas is supplied from the tank 31 to the first chamber 15. Further, when the electromagnetic valve 33 is closed, the communication between the tank 31 and the first chamber 15 is blocked. Thereby, the supply of gas from the tank 31 to the first chamber 15 is stopped.

Moreover, the solenoid valve 33 is comprised so that adjustment of an opening degree is possible.
Thereby, the flow volume of gas can be adjusted suitably.

  The heating means 4 heats the base material (film forming material) P3 'in the first chamber 15 until it is vaporized. The heating means 4 includes a container 43 installed in the first chamber 15, a coil 44 disposed on the outer peripheral side of the container 43, and an AC power source (high-frequency power source) as a voltage application unit that applies an AC voltage to the coil 44. ) 41, and a switch 42 disposed between the AC power supply 41 and the coil 44.

  The container 43 is formed of a member having a bottomed cylindrical shape, and can accommodate a base material (film forming material) P3 'in the inside (accommodating portion).

  In addition, although the internal diameter of the accommodating part of the container 43 is not specifically limited, For example, it is preferable that they are 1 mm or more and 15 mm or less.

Moreover, the volume of the accommodating part of the container 43 is not particularly limited, but is preferably 0.5 mm ³ or more and 2000 mm ³ or less, for example.

  Moreover, it does not specifically limit as a constituent material of the container 43, For example, carbon etc. can be used.

  The base material (film forming material) P3 ′ accommodated in the accommodating portion of the container 43 varies depending on the composition of the coating P3 to be formed. For example, various metals, various metal oxides, various metal nitrides, and various metal carbides Various metal borides, various metal sulfides, various carbon materials, various pigments, various resin materials, and the like can be used.

  Examples of the metal material include Au, Pt, Pd, Ni, Ag, Al, Cu, Ti, Cr, and an alloy containing at least one of them, but preferably contains Au.

  Examples of the metal oxide include aluminum oxide, titanium oxide, chromium oxide, and silicon oxide.

  Examples of the metal nitride include titanium nitride, chromium nitride, zirconium nitride, hafnium nitride, tantalum nitride, and silicon nitride.

  Examples of the metal carbide include titanium carbide, chromium carbide, zirconia carbide, aluminum carbide, calcium carbide, tungsten carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, and silicon carbide.

  Examples of the metal boride include zirconium boride and molybdenum boride.

  Examples of the metal sulfide include zinc sulfide, chromium sulfide, cadmium sulfide and the like.

  Examples of the carbon material include graphite, graphene, diamond, carbon nanotube, fullerene, and the like.

Examples of the pigment include the following.
That is, examples of the black pigment include carbon black such as furnace black, channel black, acetylene black, and thermal black, copper oxide, manganese dioxide, titanium oxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

  Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Is mentioned.

  Examples of the orange pigment include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.

  Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C , Rose bengal, oxin red, alizarin lake and the like.

  Examples of the blue pigment include, for example, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, indanthrene blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, and phthalocyanine green. And malachite green oxalelate.

  Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.

Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  Examples of the resin material include (meth) acrylic resins, polystyrene resins, styrene- (meth) acrylic resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, Vinyl chloride-vinyl acetate copolymer, fiber-based resin (eg, cellulose acetate butyrate, hydroxypropyl cellulose, etc.), polyvinyl butyral, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyurethane resin, urea resin, etc. Is mentioned.

  A coil 44 is concentrically disposed on the outer peripheral side of the container 43. The coil 44 is formed by winding an element wire 441 made of a conductive material. Further, the inner peripheral portion 442 of the coil 44 and the outer peripheral portion 431 of the container 43 are preferably separated from each other.

  The conductive material forming the strand 441 is not particularly limited, and for example, a material having a relatively high electrical resistance such as tungsten can be used.

  The AC power supply 41 is electrically connected to the coil 44 and can apply an AC voltage to the coil 44. Then, by operating the switch 42, it is possible to switch between a voltage application state in which an AC voltage is applied to the coil 44 and an application stop state in which the application is stopped. In the voltage application state, that is, by operating the heating means 4, the film forming material P 3 ′ can be heated together with the container 43. As a result, the film-forming material P3 'is melted at the melting point and further heated to an extent exceeding the melting point. At this time, the film forming material P <b> 3 ′ evaporates and flows down along with the gas supplied from the gas supply means 3 through the lumen portion 22 of the connection pipe 2. This vaporized film-forming material P3 'is cooled in the process of passing through the connecting pipe 2 to become particles P31, and is sprayed from the second opening 21 to the substrate P1. And this particle | grain P31 will collide and adhere to the base material P1, As a result, the film P3 is formed.

  The average particle diameter of the particles (fine particles) P31 is preferably from 0.5 nm to 150 μm, and more preferably from 1 nm to 100 μm.

  Thereby, the aesthetic appearance of the coating P3 can be made particularly excellent. Further, the adhesion between the substrate P1 and the coating P3 can be made particularly excellent, and the durability of the coating P3 can be made particularly excellent. Further, the formation efficiency of the coating P3 can be made particularly excellent.

  In the present specification, “average particle diameter” refers to an average particle diameter based on mass. This average particle diameter can be obtained, for example, by measuring the mobility of the aerosol and determining the aerodynamic diameter. For the measurement of the particle diameter, for example, a differential electrostatic classifier manufactured by TSI can be used. In addition, you may obtain | require an average particle diameter from the measurement result of a scanning electron microscope or a transmission electron microscope.

  Note that the power supplied by applying the AC voltage is preferably 1 kW or more and 90 kW or less, and more preferably 5 kW or more and 50 kW or less. The frequency of the alternating voltage is preferably 100 kHz or more and 600 MHz or less, more preferably 150 kHz or more and 500 MHz or less, and further preferably 200 kHz. With such a numerical range, the solid film-forming material P3 'can be reliably vaporized by heating without excess or deficiency.

  The pressure adjusting means 5 makes the pressure in the second chamber 16 lower than the pressure in the first chamber 15.

  As shown in FIG. 1, the pressure adjusting means 5 is installed in the middle of the connecting pipe 52, a pump 51 that sucks the inside of the second chamber 16, a connecting pipe 52 that connects the pump 51 and the second chamber 16. The electromagnetic valve 53 is provided.

The pump 51 sucks the gas G ₂ in the second chamber 16. By this suction, the gas G ₂ in the second chamber 16 is discharged through the connecting pipe 52, so that the pressure in the second chamber 16 is surely lower than the pressure in the first chamber 15. As a result, the particles P31 can surely flow out into the second chamber 16, and thus the coating P3 can be reliably formed.

  The pressure in the second chamber 16 depends on the pressure in the first chamber 15, but for example, when the pressure in the first chamber 15 is 0.1 atm or more and 10 atm or less, 0 It can be less than 1 atm.

  Moreover, it does not specifically limit as the pump 51, For example, a turbo-molecular pump, a dry pump, a mechanical booster pump, a rotary pump etc. can be used.

  The pump 51 is connected to the second chamber 16 via a connecting pipe 52. The connecting pipe 52 may be hard or flexible.

  The connecting pipe 52 is provided with an electromagnetic valve 53 in the middle of its longitudinal direction. The electromagnetic valve 53 opens and closes the connecting pipe 52. When the electromagnetic valve 53 is in the open state, the inside of the second chamber 16 can be sucked by the suction force of the pump 51, and therefore the inside of the second chamber 16 can be decompressed. Further, when the electromagnetic valve 53 is in the closed state, the suction force of the pump 51 is prevented from reaching the second chamber 16.

  As shown in FIG. 1, the moving means 6 moves the base material P1 with respect to the 2nd opening part 21 toward the y-axis direction. As shown in FIGS. 1 and 2, the moving unit 6 includes a stage (table) 61 that transports a plurality of base materials P1, a y-axis motor 62y that moves the stage 61 in the y-axis direction, and a y-axis motor. A y-axis motor driver 63y for controlling the driving of 62y. The moving means 6 can also move the stage 61 in the x-axis direction, and has an x-axis motor 62x that moves the x-axis motor driver 63x that controls the driving of the x-axis motor 62x. ing.

  The stage 61 is a plate-like member made of a metal material such as stainless steel. This stage 61 is supported horizontally.

  The y-axis motor 62y is a servomotor, for example, and is connected to the stage 61 via a ball screw (not shown) or the like. Then, as the y-axis motor 62y rotates, the rotational force is transmitted to the stage 61 via the ball screw. Accordingly, the plurality of base materials P1 placed on the stage 61 can be moved together with the stage 61 in the y-axis direction.

  The y-axis motor 62y is electrically connected to the y-axis motor driver 63y.

  The number of rotations of the y-axis motor 62y can be changed by the control of the y-axis motor driver 63y. As a result, the speed at which the stage 61 moves, that is, the speed when the moving means 6 is actuated is variable. And according to the magnitude of the said speed, the thickness of the coating film P3 formed can be adjusted, respectively. For example, when the speed is “large”, a “thin” film P3 is formed, and when the speed is “small”, a “thick” film P3 is formed.

  Similar to the y-axis motor 62y, the x-axis motor 62x is a servo motor, for example, and is connected to the stage 61 via a ball screw (not shown) or the like. Then, when the x-axis motor 62x rotates, the rotational force is transmitted to the stage 61 via the ball screw. Thereby, the plurality of substrates P1 placed on the stage 61 can be moved together with the stage 61 in the x-axis direction.

  The x-axis motor 62x is electrically connected to the x-axis motor driver 63x.

  Each operation of the gas supply means 3, the heating means 4, the pressure adjusting means 5 and the moving means 6 is controlled by the control unit 7. The control unit 7 is, for example, a personal computer (PC) with a built-in CPU (Central Processing Unit).

  The material supply means 8 has a function of additionally supplying the film forming material P3 'to the accommodating portion of the container 43 in a state where the base material (film forming material) P3' is evaporated.

  In this manner, in the state where the base material (film forming material) P3 ′ is evaporated, the film forming material P3 ′ in the container is supplied by additionally supplying the film forming material P3 ′ to the accommodating portion of the container 43. Even when 'decreases, film formation can be continued without interrupting the operation of the film formation apparatus 100. Therefore, the efficiency of film formation can be improved, and for example, the productivity of a member (for example, a decorative article) provided with a film (film) formed by a film forming apparatus can be improved.

  Even when the container 43 is small in size, it is possible to form a film with a large area and to prevent the film forming apparatus 100 from becoming large.

  Further, since the container 43 can be reduced in size, the heating efficiency of the film forming material P <b> 3 ′ in the container 43 is excellent. Further, it is not necessary to store an excessive amount of the film forming material P3 ′ in the container 43 in advance and melt it, and the film forming material P3 ′ actually used for film forming may be changed as needed. Since it is sufficient to apply energy necessary for evaporating ', it is not necessary to use excessive energy for heating the film-forming material P3'. As described above, film formation can be efficiently performed with less energy, which is preferable from the viewpoint of energy saving.

  On the other hand, when the operation of the film forming apparatus is interrupted and the film forming material is added, more specifically, for example, when the film forming material is added, the heating of the film forming material is stopped, and the container In the case where a film forming material is added while the temperature is sufficiently low, the film forming efficiency is low.

  The material supply means 8 includes a storage unit 81 that stores the film forming material P3 ′ that is additionally supplied to the storage unit of the container 43, and a transport path 82 that transports the film formation material to the storage unit of the container 43. Yes.

  In particular, in the present embodiment, the material supply means 8 additionally supplies a particulate film forming material P3 '.

  This facilitates the storage of the film-forming material P3 'and the supply of the film-forming material P3' to the accommodating portion of the container 43, so that the formation efficiency of the coating P3 'can be made particularly excellent. In addition, since it is easy to manage the amount of the film-forming material P3 ′ to be additionally supplied, it is possible to prevent an undesired drop in temperature of the film-forming material P3 ′ in the container 43, and so on. The coating P3 can be more reliably formed.

  The average particle diameter of the film-forming material additionally supplied is preferably from 0.3 mm to 2.0 mm, and more preferably from 0.5 mm to 1.5 mm.

  The film forming material P3 'additionally supplied by the material supply means 8 is preferably a porous material.

  Thereby, when the film-forming material P3 ′ is additionally supplied to the container 43, the bumping phenomenon can be effectively prevented, and as a result, the quality of the formed film P3 can be further improved. It can be stably excellent.

  The porosity of the film-forming material P3 ′ additionally supplied is preferably 50% by volume or less, and more preferably 30% by volume or less.

  Further, the material supply means 8 includes a shutter 83, and is configured such that the particulate film-forming material P3 ′ aligned in a line in the transport path 82 is intermittently additionally supplied to the accommodating portion of the container 43. Has been.

  This makes it easier to manage the amount of the film-forming material P3 'to be additionally supplied, and to form the coating P3 with stable quality more reliably.

  Further, in the present embodiment, the material supply unit 8 includes a heating unit (preheating unit) 84 that heats (preheats) the film forming material P <b> 3 ′ before being additionally supplied to the accommodating portion of the container 43.

  As a result, the film forming material in the container 43 is stored in the container 43 due to the difference between the temperature of the film forming material P3 ′ previously stored in the container 43 and the temperature of the additionally supplied film forming material P3 ′. When P3 ′ is additionally supplied, it is possible to more reliably prevent the coarse particles of the film forming material P3 ′ from jumping out of the container, that is, the fine particles P31 used for film formation can be more reliably prevented. The quality of the coating film P3 to be applied can be made more excellent.

  The heating temperature (preheating temperature) of the film forming material P3 ′ by the heating means (preheating means) 84 depends on the composition of the film forming material P3 ′ and the like, but the melting point of the film forming material P3 ′ is Tm. It is preferably (Tm−600) ° C. or more and (Tm−10) ° C. or less, and preferably (Tm−500) ° C. or more and (Tm−50) ° C. or less.

  As a result, the above-described effects can be exhibited more remarkably while sufficiently improving the stability and transportability of the shape of the additionally supplied film forming material P3 '.

  When the film-forming material P3 ′ is additionally supplied by the material supply means 8, the temperature of the film-forming material P3 ′ in the housing portion of the container 43 is lower than when film formation is performed in the film-forming chamber. As described above, the heating by the heating means 4 may be adjusted.

  As a result, it is possible to prevent the film formation material P3 'from evaporating more than necessary and unintentional film formation from proceeding while sufficiently improving the film formation efficiency.

In addition, the film forming apparatus 100 includes an observation unit 1 that observes the accommodating portion of the container 43.
Thereby, the quantity of film-forming material P3 'in the accommodating part of the container 43 can be adjusted to a suitable range more reliably. More specifically, for example, when the film forming material P3 ′ accommodated in the accommodating portion of the container 43 becomes equal to or larger than a predetermined amount, film formation from the material supply unit 8 is performed by the control unit 7 described in detail later. The supply of the material P3 ′ is interrupted, and it is possible to reliably prevent the occurrence of adverse effects caused by the excessive film forming material P3 ′ being accommodated in the accommodating portion. Further, for example, when the amount of the film-forming material P3 ′ accommodated in the container 43 is equal to or less than a predetermined value, the supply of the film-forming material P3 ′ from the material supply unit 8 is started. Can be configured.

  As the observation means 1, for example, various sensors, a CCD (Charge Coupled Device) camera, or the like can be used.

  As shown in FIG. 2, the control unit 7 includes an electromagnetic valve 33 of the gas supply unit 3, an AC power supply 41 and a switch 42 of the heating unit 4, a pump 51 and an electromagnetic valve 53 of the pressure adjustment unit 5, and a moving unit 6. Are electrically connected to the x-axis motor driver 63x and the y-axis motor driver 63y, the material supply means 8 (particularly, the shutter 83 and the heating means (preheating means) 84), the observation means 1, and the temperature adjustment mechanism 90, respectively. Has been. And the control part 7 can operate these each independently. The control program is stored in advance in a storage unit (recording medium) 71 built in the control unit 7.

  The storage unit 71 includes, for example, RAM (Random Access Memory: including both volatile and nonvolatile), FD (Floppy Disk (Floppy is a registered trademark)), HD (Hard Disk), CD-ROM (Compact It is composed of a magnetic or optical recording medium such as a disc read-only memory or a semiconductor memory.

Next, the operation of the film forming apparatus 100 in the film forming process will be described in detail.
In the film forming step, as shown in FIG. 1, the stage 61 is aligned with the second opening 21 of the connecting pipe 2 so that the second opening 21 of the connecting pipe 2 faces the substrate P1. Do. This alignment is performed using a CCD (Charge Coupled Device) camera based on an image captured by the CCD camera.

  At this time, the pressure adjusting means 5 is operating in the film forming apparatus 100. As a result, the pressure in the second chamber 16 becomes lower than the pressure in the first chamber 15. This state is maintained until the formation of the coating P3 on the substrate P1 is completed.

In the film forming apparatus 100, the heating unit 4 is also operating. Thereby, as described above, the film forming material P3 ′ in the container 43 is vaporized. The vaporized film forming material P 3 ′ passes through the connecting pipe 2 due to the difference between the pressure in the first chamber 15 and the pressure in the second chamber 16.
Further, in the film forming apparatus 100, the gas supply means 3 is also operating.

  Then, the moving means 6 is operated, that is, the stage 61 is moved in the positive y-axis direction.

  As described above, when the gas supply unit 3, the heating unit 4, the pressure adjusting unit 5, and the moving unit 6 are operated, the film-forming material P 3 ′ vaporized in the first chamber 15 is transferred to the second chamber 16. It surely passes through the connecting pipe 2. During this passage, the vaporized film-forming material P3 ′ becomes particles P31 of a predetermined size, and the particles P31 smoothly pass through the connecting pipe 2 by the gas introduced into the first chamber 15. be able to. The particles P31 are discharged from the second opening 21 and are sprayed and adhered to the respective base materials P1 in order.

  In the state where the film-forming material P3 'is evaporated, the film-forming material P3' is additionally supplied from the material supply means 8 to the housing portion of the container 43 as needed.

  According to the film forming apparatus and the film forming method of the present invention as described above, it is possible to efficiently form a film with a desired shape and pattern by a method with little waste of materials and a small load on the environment.

Second Embodiment
Next, a second embodiment of the film forming apparatus and film forming method of the present invention will be described.

  FIG. 3 is a vertical cross-sectional side view schematically showing a second embodiment of the film forming apparatus of the present invention. In the following description, differences from the above-described embodiment will be mainly described, and description of similar matters will be omitted.

  As shown in FIG. 3, the present embodiment is different in the form of additional supply of the film forming material P <b> 3 ′ to the accommodating portion of the container 43 by the material supply unit 8. More specifically, in the present embodiment, the film-forming material P3 ′ that is additionally supplied to the accommodating portion of the container 43 has a long shape (wire shape), and the material supply means 8 includes a roller 85. In this configuration, the film forming material P <b> 3 ′ having a long shape (wire shape) is additionally supplied sequentially to the accommodating portion of the container 43 by the rotation of the roller 85.

  With such a configuration, it is possible to finely adjust the amount of the film forming material P3 ′ additionally supplied to the accommodating portion of the container 43, and the amount of the film forming material P3 ′ in the accommodating portion of the container 43 can be adjusted. It can be controlled with higher accuracy. In addition, if the film-forming material P3 ′ additionally supplied to the housing part of the container 43 has a long shape (wire shape), the film is present outside the housing part due to heat conduction from the housing part. The material P3 ′ is also heated (preheated). As a result, it is possible to more effectively prevent a rapid temperature change in the housing portion when the film forming material P3 ′ is additionally supplied to the housing portion, and the quality of the formed film P3 is more reliably improved. It can be.

  The width (the diameter when the cross-sectional shape is circular) of the film-forming material P3 ′ having a long shape (wire shape) is preferably 10 μm or more and 1000 μm or less, and more preferably 20 μm or more and 500 μm or less. preferable.

  Thereby, the stability of the shape of the film-forming material P3 ′ supplied to the housing part of the container 43 is excellent, and the supply amount of the film-forming material P3 ′ to the housing part of the container 43 is more finely adjusted. It can be performed. As a result, the amount of the film forming material P3 ′ in the container 43 can be controlled with higher accuracy. Further, the balance between the heat conduction from the housing portion and the heat radiation can be made more preferable, and the film-forming material P3 ′ having a long shape (wire shape) before being supplied into the housing portion is formed. The temperature can be more reliably set to a value within the preferred range.

<Third Embodiment>
Next, a third embodiment of the film forming apparatus and film forming method of the present invention will be described.

  FIG. 4 is a longitudinal sectional side view schematically showing a third embodiment of the film forming apparatus of the present invention, and is a view showing a state during film formation. FIG. 5 is a vertical cross-sectional side view schematically showing a third embodiment of the film forming apparatus of the present invention, and is a view showing a state during standby for film formation (a state in which a material is additionally supplied to the accommodating portion). . FIG. 6 is a block diagram of a main part of the film forming apparatus shown in FIGS.

  As shown in FIGS. 4 and 5, when the film forming apparatus 100 of the present embodiment additionally supplies the film forming material P3 ′ to the container 43, the evaporated film forming material P3 ′ is the base material. There is provided an adhesion preventing means 9 for preventing the material from being supplied and adhered to P1.

  Thereby, for example, when the film forming material P3 ′ is additionally supplied to the housing portion of the container 43, an unexpected temperature change occurs in the housing portion, and coarse particles of the film forming material P3 ′ jump out of the housing portion. Even if it is a case, it can prevent that the said coarse particle is contained in the film P3, and can make the quality of the film P3 more excellent reliably.

  In particular, in the configuration shown in the figure, the adhesion preventing means 9 is a guide member that guides the evaporated film forming material P3 'to the exhaust port 521 for exhausting the gas in the film forming chamber 16.

  This not only prevents the coarse particles of the film-forming material P3 ′ from directly adhering to the base material P1, but also causes the coarse particles of the film-forming material P3 ′ to adhere to the vapor generation chamber (first (Chamber) 15 or the like, and it is preferable to prevent the peeled material from being used for forming the coating P3 after once adhering to the wall surface of the steam generation chamber (first chamber) 15 or the like. Can do. As a result, the quality of the formed coating film P3 can be made even better. In addition, maintenance of the film forming apparatus 100 is facilitated.

  In the illustrated configuration, the guide member (adhesion prevention means) 9 has a tubular shape having a hollow portion through which the film-forming material P3 '(including particles P31; the same applies hereinafter) flows.

  With such a structure, the film forming material P3 ′ can be taken into the guide member 9, and the film forming material P3 ′ once taken in effectively leaks. Therefore, it is possible to more effectively prevent the film-forming material P3 ′ from adhering to an unintended portion. In addition, by incorporating a fluid containing the film forming material P3 'into the hollow portion, a gas flow toward the exhaust port 521 is efficiently generated in the hollow portion. Therefore, the deposition material P3 'can be more effectively prevented from adhering to the guide member 9, and the efficiency of discharging the deposition material P3' to the outside of the deposition chamber 16 can be improved.

  The angle θ formed between the supply direction of the gas flow including the film forming material P3 ′ from the nozzle portion 24 and the normal line of the surface of the guide member 9 that is in contact with the film forming material P3 ′ is 40 ° or more. Is more preferable, and it is more preferably 45 ° or more and 85 ° or less.

  Thereby, adhesion of the film-forming material P3 'to the guide member 9 can be more effectively prevented. As a result, the efficiency of discharging the film forming material P3 'to the outside of the film forming chamber 16 can be made particularly excellent, and the frequency of maintenance of the film forming apparatus 100 can be reduced. In addition, the retention of the film forming material P3 'in the film forming chamber 16 can be more effectively prevented, and the yield of a member (for example, a decorative article) having the film P3 can be improved.

  The guide member 9 may be made of any material. Examples of the constituent material of the guide member 9 include various metal materials such as stainless steel, ceramic materials such as titanium carbide, and various resin materials. It is done.

  Further, the surface of the guide member 9 on which the film forming material P3 'can come into contact may be subjected to a surface treatment for preventing the adhesion of the particles P31.

  Thereby, adhesion of the film-forming material P3 'to the guide member 9 can be more effectively prevented. As a result, the efficiency of discharging the film forming material P3 'to the outside of the film forming chamber 16 can be made particularly excellent, and the frequency of maintenance of the film forming apparatus 100 can be reduced.

  The surface treatment may be any process that prevents the deposition of the film forming material P3 ', but it is preferable to form an adhesion preventing film.

  Thereby, adhesion of the particles P31 to the guide member 9 can be further effectively prevented. As a result, the efficiency of discharging the particles P31 to the outside of the film forming chamber 16 can be further improved, and the frequency of maintenance of the film forming apparatus 100 can be further reduced. Even if the shape of the guide member 9 is complicated, the above-described effects can be obtained easily and reliably.

  Examples of the constituent material of the adhesion preventing film include fluorine resins such as polytetrafluoroethylene, DLC (diamond-like carbon), and the like.

  The thickness of the adhesion preventing film is not particularly limited, but is preferably 50 μm or more and 3 mm or less, and more preferably 100 μm or more and 1 mm or less.

  Thereby, the effect mentioned above can be acquired more stably over a longer period, suppressing the production cost of the guide member 9.

The guide member 9 includes a motor 92 that moves in the y-axis direction and a motor driver 93 that controls driving of the motor 92.
The motor 92 is electrically connected to the motor driver 93.

  As shown in FIG. 6, in the present embodiment, the control unit 7 includes the electromagnetic valve 33 of the gas supply means 3, the AC power supply 41 and the switch 42 of the heating means 4, the pump 51 and the electromagnetic valve 53 of the pressure adjustment means 5, movement In addition to the x-axis motor driver 63x and the y-axis motor driver 63y of the means 6, the material supply means 8, the observation means 1, and the temperature adjustment mechanism 90, the motor driver 93 of the guide member 9 is also electrically connected. And the control part 7 can operate these each independently.

  For example, when the film forming material P 3 ′ is additionally supplied by the material supply means 8, the film forming material P 3 ′ supplied from the second opening 21 is operated to the exhaust port 521 by operating the guide member 9. Thus, the film-forming material P3 ′ (particles P31) can be reliably prevented from colliding with the base material P1.

  Further, when the particles P31 are guided to the exhaust port 521 by the guide member 9, it is preferable to relatively move the stage 61 on which the base material P1 is installed and the nozzle portion 24.

  Thereby, it can prevent more reliably that adhesion of the unintentional particle P31 arises in the base material P1.

In particular, in the configuration shown in FIG. 5, the stage 61 is moved in the positive z-axis direction so that the distance from the nozzle portion 24 is increased.
Thereby, the effects as described above are more remarkably exhibited.

  The timing at which the particles P31 are guided to the exhaust port 521 by the guide member 9 is not limited to when the film forming material P3 ′ is additionally supplied to the accommodating portion of the container 43 by the material supply means 8, for example, It may be at the time of startup (when power is turned on) or the like.

<< Method for manufacturing decorative items >>
Next, a method for manufacturing a decorative article to which the film forming method of the present invention is applied will be described.

  As ornaments, for example, eyeglasses (including sunglasses, head mounted display (HMD), etc.), earrings, earrings, necklaces, watches (including smart watches, etc.), bracelets, rings, anklets, and other accessories, table clocks, wall clocks, etc. Various objects such as various objects, foreheads, baskets, vases, etc., and constituent members thereof can be mentioned.

  In the following description, the case where the film forming method of the present invention is applied to the manufacture of a watch exterior part as an example of a decorative article will be representatively described.

  In this specification, a watch exterior part is a component of a watch and means a part that is visible from the outside when the watch is used. It is a concept that includes parts housed inside the watch.

  Examples of watch exterior parts include cover glass (windshield), dial, hands (hour hand, minute hand, second hand, etc.), bezel, case, back cover, crown, disk hand, date wheel, day wheel, and age plate. Rotating display bodies such as

  FIG. 7: is sectional drawing which shows each process typically about suitable embodiment of the manufacturing method of a decorative article.

  As shown in FIG. 7, the method of the present embodiment includes a base material preparation step (1a) for preparing the base material P1, a base layer formation step (1b) for forming the base layer P2 on the surface of the base material P1, and Fine particles P31 formed by condensing the vapor of the film-forming material after evaporating the film-forming material (film-forming material) housed in the housing part installed in the film-forming system A film forming step (1c) for forming the film P3 by depositing, and an antireflection film forming step (1d) for forming the antireflection film P4 on the surface side of the substrate P1 on which the film P3 is provided. Yes.

  In the film forming step, the film forming material is additionally supplied to the housing portion in a state where the film forming material is evaporated.

  The film forming step can be suitably performed by using the film forming apparatus as described above.

<Base material preparation process>
In the base material preparation step, a base material P1 is prepared (1a).

  Although the base material P1 may be comprised with what kind of material, it is preferable that it is transparent.

  Thereby, for example, the aesthetic appearance of the watch exterior part (decoration) P10 can be made particularly excellent. Further, for example, in a timepiece equipped with a timepiece exterior component P10, even when the surface opposite to the surface provided with the coating P3 of the timepiece exterior component P10 is arranged to face the outer surface side, The user or the like can preferably visually recognize the coating P3, and can effectively prevent the coating P3 and the like from being damaged by friction or the like while effectively demonstrating the effects provided by the coating P3. The durability of the timepiece can be made particularly excellent. In the present specification, “the aesthetic appearance of the watch exterior part P10” means a state in which the watch exterior part P10 is incorporated in the watch in addition to the aesthetic appearance when the watch exterior part P10 is observed alone. The aesthetic appearance of the part is also included.

  In the present specification, “having transparency” is not limited as long as it transmits at least part of visible light, but has a light transmittance (wavelength: light transmittance of 600 nm) of 85%. The above is preferable, and 90% or more is more preferable.

  Suitable constituent materials for the substrate P1 include, for example, sapphire glass, quartz, plastic, and the like.

  When the base material P1 is composed of a material including one or more selected from these groups, the aesthetic appearance of the watch exterior part P10 can be further improved. Further, the durability of the timepiece including the timepiece exterior component P10 can be further improved.

  The base material P1 may have a uniform composition in each part, or may have a different composition. For example, it may be composed of a laminated body in which layers having different compositions in the thickness direction are laminated, or a gradient material whose composition changes in a gradient manner.

  The substrate P1 prepared in this step may be subjected to a cleaning treatment such as water washing, alkali washing, acid washing, washing with an organic solvent, or the like.

  Moreover, the surface treatment may be performed for the purpose of improving the adhesion with the layer formed on the substrate P1.

<Underlayer formation process>
In the foundation layer forming step, the foundation layer P2 is formed on the surface of the substrate P1 (1b).

  Thereby, for example, the adhesion between the substrate P1 and the coating P3 (adhesion via the base layer P2) can be made particularly excellent. Further, for example, by making the base layer P2 function as a colored layer, the aesthetic appearance of the watch exterior part P10 can be further improved. Further, by making the underlayer P2 function as a gap layer, it is possible to obtain a three-dimensional appearance such that the coating P3 is lifted.

The average thickness of the underlayer P2 is preferably 0.1 nm or more and 10 μm or less.
Thereby, the foundation layer P2 can more effectively exhibit the functions as described above.

  The underlayer P2 may be made of any material, and examples of the constituent material of the underlayer P2 include TiN, AlN, SiN, GaN, SiO, SiON, etc. , TiN, AlN, and SiN are preferably made of a material containing one or more selected from the group consisting of TiN, AlN, and SiN.

  As a result, adhesion between the substrate P1 and the coating P3 (adhesion through the base layer P2), particularly adhesion when the coating P3 is made of a metal material, metal oxide, or metal nitride. Can be made particularly excellent. Further, since TiN, AlN, and SiN are materials having a high thickness as described above, it is possible to more effectively prevent adverse effects on the appearance of the watch exterior part P10 as a whole. it can.

  In the configuration shown in the figure, the base layer P2 is formed on the entire surface of the base material P1 on which the coating P3 is provided. However, for example, the base layer P2 is selectively applied only to a portion in contact with the coating P3. It may be formed. In addition, the base layer P2 may be provided only in a part of the portion covered with the coating P3 of the substrate P1.

  In the configuration shown in the figure, one base layer P2 is formed, but two or more base layers may be formed.

  The underlayer P2 may have a uniform composition at each site or may have a different composition. For example, it may be composed of a laminated body in which layers having different compositions in the thickness direction are laminated, or a gradient material whose composition changes in a gradient manner.

  The underlayer P2 can be formed by, for example, a vapor deposition method (dry plating method) such as vacuum deposition, ion plating, sputtering, chemical vapor deposition (CVD), wet plating method, dipping, or the like.

  In addition, as a method for forming the underlayer P2, for example, an aerosol in which particles composed of the constituent material of the underlayer P2 are dispersed in a gas is sprayed from a nozzle toward the substrate P1, and the impact force is used. A method of forming the underlayer P2 may be employed. Thereby, the foundation layer P2 can be selectively and efficiently formed at a desired site.

  Further, as a method for forming the underlayer P2, for example, a method similar to that for the coating P3 may be employed. Thereby, the foundation layer P2 can be selectively and efficiently formed at a desired site.

<Film formation process>
Next, a coating P3 is formed on a part of the surface of the base layer P2 (1c).
In particular, the film P3 is formed using the film forming apparatus 100 as described above.

  As a result, it is possible to provide a watch exterior part (decorative article) P10 that is excellent in aesthetic appearance, has little waste of materials during manufacture, and has a low environmental impact. That is, a desired amount of particles P31 can be deposited at a desired site, and the coating film P3 to be formed can have a desired shape and pattern, and can be selected as a desired site. Since film formation can be performed automatically, waste of materials can be suppressed. Further, since the film forming material is additionally supplied without interrupting the operation of the film forming apparatus, the productivity of the watch exterior part (decorative article) P10 can be improved. In addition, the coating P3 made of a material having an excellent texture can be formed.

  Further, in such a method, since it is not necessary to use a volatile solvent or the like, a problem caused by volatilization of a volatile component (volatile organic compound) in a state where the watch exterior part P10 is incorporated in the watch (movement) Occurrence of trouble, occurrence of trouble, fogging of cover glass, etc.) can be effectively prevented.

  The coating P3 is preferably provided selectively on a part of the observable part in the state where the watch exterior part P10 is incorporated in the watch.

  As a result, due to the effect that the coating P3 itself has a specific pattern and the effect of the combination of the portion where the coating P3 is provided and the portion where the coating P3 is not provided, the watch exterior part P10, the watch The aesthetic appearance can be made particularly excellent.

  Further, conventionally, when the watch exterior part is incorporated in the watch, when the coating is selectively provided in a part of the observable part, Although there has been a problem that the waste of materials during production is particularly large, according to the present invention, the occurrence of such a problem can be reliably prevented. Therefore, when the coating P3 is selectively provided on a part of the portion that can be observed in the state where the watch exterior part (decorative article) P10 is incorporated in the watch, the effect of the present invention is more remarkable. To be demonstrated.

In the state in which the watch exterior part P10 is incorporated in the watch, the area ratio occupied by the part provided with the coating P3 among the observable parts of the watch exterior part P10 (the surface of the watch exterior part P10 is flat) If it is, the area ratio when observed from the normal direction of the surface is not particularly limited, it is preferably 70% or less, more preferably 2% or more and 50% or less.
Thereby, the effects as described above are more remarkably exhibited.

  The average thickness of the coating P3 is preferably 0.01 μm or more and 300 μm or less, more preferably 0.05 μm or more and 160 μm or less, and further preferably 0.10 μm or more and 70 μm or less.

  Thereby, the aesthetic appearance of the timepiece exterior component P10 can be made particularly excellent. Further, the durability of the watch exterior part P10 can be made particularly excellent. Further, the productivity of the watch exterior part P10 can be made particularly excellent.

  The coating P3 formed in this step may have a uniform composition at each site or may have a different composition. For example, the watch exterior part P10 may have a plurality of types of coatings P3 having different textures (for example, different colors) in a predetermined pattern. Thereby, the further improvement of the aesthetic appearance of timepiece exterior component P10 can be aimed at.

<Antireflection film formation process>
In the antireflection film forming step, an antireflection film P4 is formed on the surface side of the substrate P1 on which the coating P3 is provided (1d).

  Thereby, unintentional reflection of external light can be effectively prevented, and the aesthetic appearance of the watch exterior part P10 can be made particularly excellent.

  Further, when the watch exterior part P10 is applied to a cover glass (windshield), the effect of improving the aesthetic appearance as described above can be obtained, and the visibility of the dial can be improved. The overall aesthetic appearance can be made particularly excellent. In addition, the function as a practical product is improved, for example, the distinguishability such as time is improved.

  The antireflection film P4 can be formed by, for example, a vapor deposition method (dry plating method) such as vacuum deposition, ion plating, sputtering, chemical vapor deposition (CVD), wet plating method, dipping or the like.

  The thickness of the antireflection film P4 is not particularly limited, but is preferably 0.2 μm or more and 10 μm or less, and more preferably 0.3 μm or more and 7 μm or less.

  Thereby, the functions as described above can be more effectively exhibited while effectively preventing the watch exterior part P10 from becoming larger and thicker.

  In the illustrated configuration, the antireflection film P4 is formed on the entire surface of the base material P1 on which the coating P3 is provided. For example, the antireflection film P4 is provided with the coating P3 of the base material P1. It may be selectively provided only on a part of the surface on the other side.

<< decoration >>
Next, the decorative article of the present invention will be described.

  The decorative article of the present invention includes a film formed using the film forming apparatus of the present invention as described above, or a film formed using the film forming method of the present invention as described above. It is.

  As a result, it is possible to provide a decorative product having a desired shape and pattern coating, excellent in aesthetic appearance, less waste of materials at the time of manufacture, and less burden on the environment.

  As described above, the present invention can be applied to various types of ornaments. Hereinafter, a specific example in which the ornaments of the present invention are applied to a cover glass (windshield) as a watch exterior part. Will be described.

  FIG. 8 is a schematic plan view showing a preferred embodiment when the decorative article of the present invention is applied to a cover glass as a watch exterior part.

  As shown in FIG. 8, the watch exterior part (decorative article) P <b> 10 of this embodiment as a cover glass is selectively provided with a coating P <b> 3 in the vicinity of the outer periphery when viewed in plan.

  The watch exterior part (decorative article) is preferably arranged so that the surface on which the coating film of the base material is provided faces inward when incorporated in the watch. Thereby, unintentional peeling of the film can be prevented more effectively, and the durability of the watch can be made particularly excellent.

  In particular, in the illustrated configuration, the coating is provided in a predetermined pattern (arabesque pattern). As described above, even if the coating film P3 has a complicated pattern, according to the present invention, it is possible to obtain the coating material P3 with a small waste of materials at the time of manufacture and a small burden on the environment.

Next, a specific example when the decorative article of the present invention is applied to a watch will be described.
FIG. 9 is a cross-sectional view showing a preferred embodiment when the decorative article of the present invention is applied to a watch (portable watch).

As shown in FIG. 9, a wristwatch (portable watch) P100 of the present embodiment includes a trunk (case) P82, a back cover P83, a bezel (edge) P84, and a glass plate (cover glass) P85. . Further, in the case P82, a timepiece dial plate P7, a solar battery P94, and a movement P81 are housed, and a hand (pointer) (not shown) and the like are housed.
The timepiece P100 only needs to apply the present invention to at least one of its components.

The glass plate P85 is usually made of highly transparent transparent glass, sapphire, or the like. As a result, the visibility of the timepiece dial P7, hands, etc. can be made sufficiently excellent, and a sufficient amount of light can be made incident on the solar cell P94.
Movement P81 drives the pointer using the electromotive force of solar cell P94.

  Although omitted in FIG. 9, in the movement P81, for example, an electric double layer capacitor for storing the electromotive force of the solar battery P94, a lithium ion secondary battery, a crystal oscillator as a time reference source, and a crystal vibration A semiconductor integrated circuit that generates a driving pulse for driving a clock based on the oscillation frequency of the child, a step motor that drives the pointer every second in response to this driving pulse, and a wheel that transmits the movement of the step motor to the pointer A row mechanism is provided.

  The movement P81 includes a radio wave receiving antenna (not shown). And it has the function to perform time adjustment etc. using the received electromagnetic wave.

  The solar cell P94 has a function of converting light energy into electric energy. The electric energy converted by the solar battery P94 is used for driving the movement.

  In the solar cell P94, for example, a p-type impurity and an n-type impurity are selectively introduced into a non-single-crystal silicon thin film, and a p-type non-single-crystal silicon thin film and an n-type non-single-crystal silicon thin film It has a pin structure provided with an i-type non-single-crystal silicon thin film with a low impurity concentration in between.

  A winding stem pipe P86 is fitted and fixed to the trunk P82, and a shaft portion P871 of a crown P87 is rotatably inserted into the winding stem pipe P86.

  The body P82 and the bezel P84 are fixed by a plastic packing P88, and the bezel P84 and the glass plate P85 are fixed by a plastic packing P89.

  Further, a back cover P83 is fitted (or screwed) to the body P82, and a ring-shaped rubber packing (back cover packing) P92 is inserted in a compressed state at the joint (seal part) P93. Has been. With this configuration, the seal portion P93 is sealed in a liquid-tight manner, and a waterproof function is obtained.

  A groove P872 is formed on the outer periphery of the shaft portion P871 of the crown P87, and a ring-shaped rubber packing (crown packing) P91 is fitted in the groove P872. The rubber packing P91 is in close contact with the inner peripheral surface of the winding stem pipe P86 and is compressed between the inner peripheral surface and the inner surface of the groove P872. With this configuration, the space between the crown P87 and the winding stem pipe P86 is sealed in a liquid-tight manner to obtain a waterproof function. When the crown P87 is rotated, the rubber packing P91 rotates together with the shaft portion P871 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe P86.

  In the above description, a wristwatch (portable clock) as a solar radio timepiece has been described as an example of a clock. However, the present invention is applicable to other types of clocks such as a portable clock, a table clock, and a wall clock other than a wristwatch. Can be applied similarly. Further, the present invention can be applied to any timepiece such as a solar timepiece excluding a solar radio timepiece and a radio timepiece excluding a solar radio timepiece.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above.

  For example, in the film forming apparatus and the ornament of the present invention, the configuration of each part can be replaced with an arbitrary configuration that exhibits the same function, and an arbitrary configuration can be added.

  In addition, the opening of the connecting pipe of the film forming apparatus faces the z-axis negative direction in the above-described embodiment, but is not limited to this. For example, the x-axis positive direction, the x-axis negative direction, and the y-axis positive direction , May be directed in the negative y-axis direction or positive z-axis direction.

  Further, the moving means of the film forming apparatus is configured to move the base material with respect to the nozzle portion of the connecting pipe in the embodiment, but is not limited thereto, for example, the nozzle portion of the connecting pipe is used as the base material. However, it may be configured to move.

Further, the film forming apparatus may be configured such that the stage is rotatable.
In the above-described embodiment, the film forming apparatus is described as including a temperature adjusting mechanism that heats the connecting pipe. However, a film that does not include the temperature adjusting mechanism may be used for forming the coating film.

  In the above-described third embodiment, the case where the guide member (adhesion preventing means) has a tubular structure has been representatively described. However, the guide member may have any shape. For example, the guide member may be a plate-like member having a groove that generates a gas flow for guiding particles to the exhaust port.

  In the above-described embodiment, the description has been focused on the configuration in which the pressure adjusting exhaust port of the film forming chamber also serves as the exhaust port for discharging the gas in the film forming chamber together with the particles guided by the guide member. The pressure adjusting exhaust port of the film forming chamber and the exhaust port for discharging particles guided by the guide member may be separate.

  The adhesion preventing means may be any means having a function of preventing the evaporated film forming material from being supplied to and adhered to the base material when the material supplying means additionally supplies the film forming material. Such a guide member (a member that guides the evaporated film forming material to the exhaust port for exhausting the gas in the film forming chamber) may not be used. For example, the adhesion preventing means may be a deposition preventing plate (shutter member) or the like.

  In the above-described embodiment, the case where the gas supplied by the gas supply unit is an inert gas has been described. However, the gas supplied by the gas supply unit may be a reactive gas. Thereby, for example, in the process of forming the film forming material into fine particles, the film can be reacted with the gas to form a film having a composition different from that of the film forming material.

  In the above-described embodiment, the film forming apparatus is described as including only one gas supply unit and supplying one type of gas. However, the film formation apparatus includes a plurality of gas supply units and supplies different types of gases. You may comprise. Thereby, for example, an inert gas and a reactive gas can be used together as the gas supplied by the gas supply means, and the coating film can have a different composition at each site.

  Further, in the embodiment described above, the case where the exterior part for a watch (decoration product) includes a base layer and an antireflection film in addition to the base material and the coating has been mainly described. What is necessary is just to provide a material and a film, and the thing which is not equipped with a base layer and an antireflection film may be sufficient.

  Moreover, in the film-forming method of this invention, you may perform a pre-processing process, an intermediate processing process, and a post-processing process as needed.

  In the embodiment described above, the case where the decorative article is manufactured using the film forming apparatus of the present invention has been mainly described. However, the film forming apparatus of the present invention is not used for manufacturing the decorative article. May be.

P100 …… Watch (portable watch)
P10 …… Exterior parts for watches (decorations)
P1 …… Substrate P2 …… Underlayer P3 …… Coating P3 ′ …… Base material (film forming material)
P31 …… Particles (fine particles)
P4: Anti-reflective coating P7: Dial for watch P81: Movement P82: Case (case)
P83 …… Back cover P84 …… Bezel (edge)
P85 …… Glass plate (cover glass)
P86 ... Winding pipe P87 ... Crown P871 ... Shaft P872 ... Groove P88 ... Plastic packing P89 ... Plastic packing P91 ... Rubber packing (Crown packing)
P92 …… Rubber packing (back cover packing)
P93 …… Joint part (seal part)
P94 …… Solar cell 100 …… Deposition device 1 …… Observation means 2 …… Connecting tube 21 …… Second opening (the other end opening)
22 …… Luminous part 24 …… Nozzle part 25 …… First opening (one-end opening)
3 ... Gas supply means 31 ... Tank 32 ... Connecting pipe 33 ... Solenoid valve 4 ... Heating means 41 ... AC power supply (high frequency power supply)
42 …… Switch 43 …… Container (Crucible)
431 ... Outer peripheral part 44 ... Coil 441 ... Wire 442 ... Inner peripheral part 5 ... Pressure adjusting means 51 ... Pump 52 ... Connecting pipe 521 ... Exhaust port 53 ... Solenoid valve 6 ... Moving means 61 …… Stage (table)
62x …… x-axis motor 62y …… y-axis motor 63x …… x-axis motor driver 63y …… y-axis motor driver 7 …… control unit 71 …… storage unit (recording medium)
8 …… Material supply means 81 …… Storage unit 82 …… Conveying path 83 …… Shutter 84 …… Heating means (preheating means)
85 …… Roller 15 …… First chamber (steam generation chamber)
16 …… Second chamber (deposition chamber)
9 …… Adhesion prevention means (guide member)
92 …… Motor 93 …… Motor driver 90 …… Temperature adjustment mechanism G ₂ …… Gas

Claims (14)

An accommodating portion for accommodating a film-forming material;
Heating means for heating the material accommodated in the accommodating portion;
A steam generation chamber in which the housing portion is installed and evaporates the material;
Using fine particles formed by condensation of the vapor of the material generated in the vapor generation chamber, and a film formation chamber for forming a film on the substrate,
A film forming apparatus comprising: a material supply unit that additionally supplies the material to the housing portion in a state where the material is evaporated.   The film forming apparatus according to claim 1, configured to additionally supply the preheated material to the housing portion.   The film forming apparatus according to claim 1, wherein the material supply unit additionally supplies the particulate material.   4. The film forming apparatus according to claim 1, wherein the material supply unit aligns the particulate material and intermittently supplies the material to the housing portion. 5.   5. The film forming apparatus according to claim 1, wherein the long material is additionally supplied to the housing portion sequentially along the longitudinal direction thereof. 6.   The film forming apparatus according to claim 1, wherein the additionally supplied material is a porous material.   The temperature is adjusted so that the temperature of the material in the housing portion is lower when the material is additionally supplied by the material supply means than when the film is formed in the film formation chamber. The film forming apparatus according to any one of claims 1 to 6.   8. The apparatus according to claim 1, further comprising an adhesion preventing unit configured to prevent the evaporated material from being supplied to and adhered to the base material when the material is additionally supplied by the material supply unit. Film forming equipment.   The film forming apparatus according to claim 8, wherein the adhesion preventing unit is a guide member that guides the evaporated material to an exhaust port that exhausts gas in the film forming chamber. An observation means for observing the accommodating portion;
The film forming apparatus according to claim 1, wherein a supply amount of the material from the material supply unit is adjusted based on an observation result of the observation unit. A film forming method for forming a film on a substrate,
A substrate preparation step of preparing the substrate;
Forming a film by depositing fine particles formed by condensing the vapor of the material after evaporating the film forming material housed in a housing unit installed in a system for film formation A process,
A film forming method, wherein the material is additionally supplied to the housing portion in a state where the material is evaporated.   A film forming method, wherein a film is formed using the film forming apparatus according to claim 1.   An ornament comprising a film formed using the film forming apparatus according to claim 1.   A decorative article comprising a film formed using the film forming method according to claim 11.

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