JP2012005949A - Method for production of nozzle and coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent liquid droplets floating in air without adhering to an object to be coated from falling on the object to be coated and causing a defective coating film.SOLUTION: Misty floating coating liquid floating in air without adhering to an object to be coated even after discharged through a nozzle 22 and a nozzle extension 38 to the object to be coated is sucked in through sucking flow paths 36. This configuration therefore prevents the floating coating liquid from falling on the object to be coated by self-weight.

Description

  The present invention relates to a nozzle and a method for producing a coating film.

  Patent Document 1 discloses a configuration in which a cylindrical or pipe-shaped resin guide is inserted and fixed in a spray nozzle of a spray gun and resin coating is applied to the liquid contact portions of the coating liquid inlet and outlet of the spray gun. Has been.

JP 2005-288375 A

  It is an object of the present invention to suppress defects in a coating film that occur when a liquid droplet that has floated without adhering to a coating object falls onto the coating object.

  The invention of claim 1 is a nozzle comprising an ejection channel for ejecting droplets to an object to be coated, and a suction channel for attracting droplets ejected from the ejection channel and floating from the suction port.

  A second aspect of the present invention is the nozzle according to the first aspect, wherein the suction channel has a discharge port provided downstream of the suction port and communicates with the ejection channel.

  A third aspect of the present invention is the nozzle according to the second aspect, wherein the suction flow path has a smaller cross-sectional area of a discharge port provided downstream of the suction port than a cross-sectional area of the suction port.

  According to a fourth aspect of the present invention, in the suction channel, a discharge port provided downstream of the suction port communicates with the ejection channel, and droplets sucked in the suction channel re-eject from the ejection channel. The nozzle according to claim 1.

  According to a fifth aspect of the present invention, in the nozzle according to the fourth aspect, the suction channel sucks the liquid droplets by a pressure difference between the suction port and the discharge port that is generated along with the ejection in the ejection channel. is there.

  A sixth aspect of the present invention is the nozzle according to any one of the first to fifth aspects, further comprising a guide member that is provided on an outer periphery of the suction port and guides the droplet to the suction port.

  A seventh aspect of the present invention is the nozzle according to the sixth aspect, wherein the leading end of the guide member protrudes in the ejection direction from the ejection port of the ejection flow path.

  According to an eighth aspect of the present invention, there is provided a jetting step for jetting droplets onto an object to be coated, a suction step for sucking droplets ejected and floating in the jetting step, and a droplet sucked in the suction step. A re-ejecting step of re-ejecting the object to be coated.

  According to the configuration of the first aspect of the present invention, compared to the configuration without the suction flow path, the coating film defects caused by dropping of the suspended droplets on the coating object without adhering to the coating object are suppressed. it can.

  According to the configuration of the second aspect of the present invention, compared to the configuration in which the discharge port of the suction channel does not communicate with the ejection channel, the adhesion efficiency of the droplets to the coating object is improved.

  According to the configuration of the third aspect of the present invention, a power source for sucking droplets is not required.

  According to the configuration of the fourth aspect of the present invention, compared to a configuration in which the droplets sucked in the suction channel are not re-ejected from the ejection channel, the adhesion efficiency of the droplets to the coating object is improved.

  According to the configuration of claim 5 of the present invention, a power source for sucking droplets is not required.

  According to the configuration of the sixth aspect of the present invention, it is possible to efficiently suck floating droplets as compared with the configuration not including the guide member.

  According to the configuration of the seventh aspect of the present invention, the floating droplet can be efficiently sucked compared to the configuration in which the tip of the guide member does not protrude.

  According to the structure of Claim 8 of this invention, compared with the structure which does not have a re-ejecting process, the defect of the coating film which arises when the droplet which floated without adhering to a to-be-coated object falls to a to-be-coated object is suppressed. In addition, the adhesion efficiency of droplets to an object to be coated is improved.

It is the schematic which shows the whole structure of the coating device which concerns on this embodiment. It is the schematic which shows the supply mechanism of the coating device which concerns on this embodiment. It is the schematic which shows the modification of the supply mechanism of the coating device which concerns on this embodiment. It is a sectional side view which shows roughly the structure of the nozzle which concerns on this embodiment. It is the figure which looked at the nozzle which concerns on this embodiment from the front end side. In the nozzle which concerns on this embodiment, it is a figure which shows the positional relationship of the guide member with respect to a to-be-coated object, and a jet nozzle. In the nozzle which concerns on this embodiment, it is a sectional side view which shows the structure which the front-end | tip of the guide member retracted | retracted to the back end side rather than the jet nozzle. In the nozzle which concerns on this embodiment, it is a sectional side view which shows the structure where the position of the front-end | tip of a guide member and a jet nozzle corresponds. In the nozzle which concerns on this embodiment, it is a sectional side view which shows the structure by which the guide member is not provided. In the nozzle which concerns on this embodiment, it is a sectional side view which shows the structure which a part in the circumferential direction of the guide member protruded largely on the outer peripheral side. In the structure shown in FIG. 10, it is the figure which looked at the nozzle from the front end side. In the structure using a some nozzle, it is a sectional side view which shows the structure where the guide member enclosed the outer periphery of the nozzle part collectively. In the structure shown in FIG. 12, it is the figure which looked at the nozzle from the front end side. It is a sectional side view which shows typically the structure which performs suction | attraction and re-ejection of a floating coating liquid using the driving force of a pump. It is a sectional side view showing typically the composition which performs only suction of floating application liquid using the driving force of a pump. It is the schematic which shows typically the structure of the photoreceptor manufactured with a coating device. It is the schematic which shows typically the modification of the photoreceptor manufactured with the coating device. It is the schematic which shows typically the structure of the organic electroluminescent element manufactured with a coating device. It is a sectional side view which shows the structure of the nozzle which concerns on a comparative example roughly. It is a result table | surface which shows the evaluation result of an Example and a comparative example.

Below, an example of an embodiment concerning the present invention is described based on a drawing.
(Overall configuration of coating apparatus 50 according to the present embodiment)
First, the overall configuration of the coating apparatus 50 according to the present embodiment will be described. FIG. 1 is a schematic diagram illustrating an overall configuration of a coating apparatus 50 according to the present embodiment.

  As shown in FIG. 1, the coating apparatus 50 according to the present embodiment includes a coating chamber 52 for coating a coating liquid on a workpiece 54 in a room. In the example shown in FIG. 1, a cylindrical substrate is used as the object to be coated 54, but is not limited thereto.

  In the coating chamber 52, an air supply port 52A capable of supplying air from the outside to the room and an exhaust port 52B capable of discharging air from the room to the outside are formed. In the coating chamber 52, clean air is supplied into the chamber through the air supply port 52A, so that air contaminated with the coating liquid and dust is discharged from the exhaust port 52B.

  In the coating chamber 52, a driving device 56 that rotationally drives the coating object 54, a nozzle 10 that ejects droplets of coating liquid onto the coating material 54, and a rotation of the coating material 54 that is rotated by the driving device 56. And a moving mechanism 58 for moving the nozzle 10 along the axial direction.

  Further, as shown in FIG. 2, the coating apparatus 50 includes a supply mechanism 60 that supplies the coating liquid to the nozzle 10. The supply mechanism 60 includes a storage unit 62 that stores the coating liquid, and a pump 64 that supplies the coating liquid stored in the storage unit 62 to the nozzle 10.

  The supply mechanism that supplies the coating liquid to the nozzle 10 may be a supply mechanism 70 that can circulate the coating liquid as shown in FIG. The supply mechanism 70 includes a storage section 72 that stores the coating liquid, a forward path 74A that sends the coating liquid from the storage section 72 to the nozzle 10, and a circulation path 74 that returns the coating liquid from the nozzle 10 to the storage section 72. And.

  In the forward path 74A of the circulation path 74, a circulation pump 76, a first valve 78, and a metering pump 80 are provided in this order along the flow direction. A second valve 79 is provided in the return path 74 </ b> B of the circulation path 74.

  When the application liquid is not applied at the nozzle 10, the circulation pump 76 is driven with the first valve 78 and the second valve 79 open, and the application liquid in the storage section 72 is circulated through the circulation path 74. ing. When applying the coating liquid at the nozzle 10, the metering pump 80 is driven with the first valve 78 opened and the second valve 79 closed, so that the coating liquid is quantitatively supplied to the nozzle 10. Yes. As described above, in the supply mechanism 70, the coating liquid is circulated when the coating liquid is not applied, thereby suppressing precipitation of pigments and the like contained in the coating liquid.

(Configuration of the nozzle 10 according to the present embodiment)
Next, the configuration of the nozzle 10 according to the present embodiment will be described. FIG. 4 is a side sectional view schematically showing the configuration of the nozzle 10 according to the present embodiment. In the following description, in the nozzle 10, the side from which the coating liquid is ejected (the lower side in FIG. 4 and the arrow S side) is the tip side, and the opposite side (the upper side in FIG. (Side) is a rear end side, the outer side in the radial direction when viewed from the axis center C (arrow G side in FIG. 4) is the outer peripheral side, and the opposite side (arrow N side in FIG. 4) is the inner peripheral side.

  As shown in FIG. 4, the nozzle 10 according to the present embodiment has a cylindrical nozzle body in which a tip portion is formed in a taper shape (a shape in which the diameter is gradually reduced from the rear end toward the tip). 12 is provided. A cylindrical nozzle portion 40 having a smaller diameter than the large diameter portion of the nozzle body 12 is formed at the tip of the nozzle body 12. In FIG. 4, the nozzle body 12 is illustrated as an integral unit, but the nozzle body 12 is configured by assembling a plurality of components (members).

  A cylindrical internal space 12 </ b> A is formed in the axial center portion of the nozzle body 12 along the axial direction of the nozzle body 12. The inner space 12A has a tip that is tapered.

  A nozzle hole 22 having a smaller diameter than the large diameter portion of the internal space 12A is formed on the tip side of the internal space 12A in the nozzle body 12. The nozzle portion 40 is provided with a nozzle hole extending portion 38 that communicates with the nozzle hole 22 and extends the nozzle hole 22. That is, the nozzle hole in the nozzle 10 is composed of the nozzle hole 22 and the nozzle hole extension 38. The nozzle hole extension 38 is formed to have a larger diameter than the nozzle hole 22.

  A needle 14 having an outer diameter smaller than the inner diameter of the nozzle body 12 is inserted into the inner space 12A. The tip of the needle 14 is formed in a tapered shape including a larger diameter portion than the nozzle hole 22. A part of the tip reaches the nozzle hole 22. A packing 18 and an O-ring 20 are provided at the rear end portion of the needle 14 as an example of a sealing member that seals the rear end portion of the internal space 12A.

  A through hole 24 is formed in the side wall of the nozzle body 12 on the rear end side of the internal space 12A. A tube body 26 having one end connected to the through hole 24 is provided in the nozzle body 12. The other storage portion 62 (see FIG. 2) is connected to the other end portion of the tube body 26.

  As a result, the coating liquid supplied from the reservoir 62 (see FIG. 2) by the pump 64 (see FIG. 2) reaches the nozzle hole 22 through the pipe 26A, the through hole 24, and the internal space 12A of the pipe body 26. It has become. That is, the coating liquid flow path 16 through which the coating liquid flows is constituted by the pipe interior 26A, the through hole 24, and the internal space 12A of the tubular body 26.

  A cylindrical cylindrical space 30 is formed in the side wall of the nozzle body 12 and on the outer peripheral side of the internal space 12A. The cylindrical space 30 has a tip formed in a tapered shape. The tip of the cylindrical space 30 communicates with the nozzle hole 22.

  On the side wall of the nozzle body 12 on the rear end side of the cylindrical space 30, a through hole 32 that penetrates the nozzle body 12 from the cylindrical space 30 in the outer peripheral direction is formed. A tube body 34 having one end connected to the through hole 32 is provided in the nozzle body 12. The other end of the tube body 34 is connected to an air supply device (not shown) such as a compressor.

  Thereby, the air supplied from the air supply device (not shown) reaches the nozzle hole 22 through the inside 34 </ b> A of the pipe body 34, the through hole 32, and the cylindrical space 30. That is, the air flow path 28 through which air flows is constituted by the pipe interior 34 </ b> A of the pipe body 34, the through hole 32, and the cylindrical space 30.

  In the nozzle 10, the air reaching the nozzle hole 22 through the air flow path 28 causes the coating liquid reaching the nozzle hole 22 through the coating liquid flow path 16 to form a mist (droplet) from the nozzle hole extension 38. It comes to erupt. That is, the nozzle hole 22 and the nozzle hole extension portion 38 constitute an ejection flow path 23 that ejects droplets of the coating liquid onto the workpiece 54. Further, the opening at the tip of the nozzle hole extending portion 38 constitutes a jet outlet 38 </ b> A in the jet flow path 23.

  Here, on the front end side of the nozzle body 12 and on the outer peripheral side, a mist-like coating liquid (hereinafter referred to as a floating coating liquid) that is ejected from the nozzle hole extension 38 and floats without adhering to the coating 54. A plurality of suction flow paths 36 are provided.

  Each suction channel 36 is formed of a circular hole and has a suction port 36A through which the coating liquid is sucked and a discharge port 36B through which the coating liquid is discharged. As shown in FIG. 5, the suction ports 36 </ b> A are arranged along the circumferential direction of the nozzle hole extension 38 on the outer peripheral side of the nozzle hole extension 38 when viewed from the tip side of the nozzle body 12. As shown in FIG. 4, each discharge port 36 </ b> B communicates with a nozzle hole extension 38.

  The flow direction of each suction flow path 36 proceeds from the suction port 36A to the rear end side of the nozzle body 12, and is folded back to the inner peripheral side at the front end side of the nozzle body 12 to communicate with the nozzle hole extension 38. It goes to the discharge port 36B. That is, the plurality of suction channels 36 are provided radially when viewed from the nozzle hole extension 38. The suction channel 36 has a narrower cross-sectional area on the discharge port 36B side than the suction port 36A.

  In the present embodiment, when the coating liquid is ejected from the nozzle hole extension 38 at a speed that is mist-like by the air from the air channel 28, the nozzle hole extension 38 (the discharge port 36 </ b> B of the suction channel 36). ) Pressure decreases. That is, the flow rate of the ejected fluid at the discharge port 36B of the suction channel 36 is faster than the flow rate of the ejected fluid at the suction port 36A, and the pressure at the discharge port 36B is lower than the pressure at the suction port 36A (Bernoulli's theorem). Thereby, in the suction flow path 36, a flow (airflow) from the suction port 36A to the discharge port 36B is generated, and the floating coating liquid is sucked from the suction port 36A. Then, the floating coating liquid sucked from the suction port 36A is discharged from the discharge port 36B to the nozzle hole extension 38, and becomes a mist (droplet) by the air reaching the nozzle hole 22 through the air flow path 28. The nozzle hole extension 38 is re-spouted.

  Note that the number of the suction channels 36 is not limited to a plurality, and a single suction channel 36 may be used. In addition, the suction flow path 36 is not limited to being formed by a circular hole, and may be, for example, an annular shape.

  A guide member 42 for guiding the floating coating liquid to the suction port 36A is provided on the outer periphery of the suction port 36A of the suction channel 36. As shown in FIG. 5, the guide member 42 surrounds the outer periphery of the nozzle hole extension 38 along the circumferential direction of the nozzle hole extension 38 when viewed from the front end side of the nozzle body 12. Thereby, the guide member 42 comprises the annular | circular shape.

  A guide space 43 for guiding the floating coating liquid is formed on the inner peripheral side of the guide member 42 and on the outer periphery of the nozzle hole extension 38. The guide space 43 is separated from the nozzle hole extending portion 38 by the outer peripheral wall of the nozzle portion 40.

  In addition, the guide member 42 protrudes so that the distal end side is gradually expanded in diameter. As a result, the guide space 43 also expands toward the outer peripheral side on the distal end side. Further, the tip 42A of the guide member 42 protrudes in the ejection direction (tip direction) from the jet outlet 38A of the nozzle hole extension 38.

(Operation according to this embodiment)
Next, a method for producing a coating film will be described as an operation according to the present embodiment.

  In the coating apparatus 50 according to the present embodiment, the nozzle 10 moves the coating liquid to the coating object 54 that is rotationally driven by the driving device 56 while moving in the rotation axis direction of the coating object 54 by the moving mechanism 58. Erupts. Thereby, a coating film is formed on the outer periphery of the workpiece 54.

  Specifically, in the nozzle 10, the coating liquid from the coating liquid flow path 16 is atomized by the air from the air flow path 28, and passes through the nozzle hole 22 and the nozzle hole extension portion 38 to the coating object 54. It is ejected (ejection process).

  The mist-like floating coating liquid that has been ejected to the object 54 through the nozzle hole 22 and the nozzle hole extension 38, but does not adhere to the object 54, has a pressure difference between the discharge port 36B and the suction port 36A. Thus, suction is performed from the suction flow path 36 (suction process).

  The floating coating liquid sucked from the suction flow path 36 is further guided to the nozzle hole extension 38 due to the pressure difference, becomes a mist by the air from the air flow path 28, and is applied through the nozzle hole extension 38. It is ejected again to the object 54 (re-ejecting step).

  As described above, since the floating coating liquid is sucked from the suction flow path 36, the floating coating liquid is suppressed from falling onto the workpiece 54 due to its own weight. In addition, the floating coating liquid sucked from the suction flow path 36 is again ejected to the object 54 to be coated, so that the adhesion efficiency of the coating liquid to the object 54 is improved.

  Further, since the floating coating liquid is sucked and re-spouted by the pressure difference between the discharge port 36B and the suction port 36A, a power source for generating a driving force for performing the suction and re-spout is unnecessary.

  Further, since the floating coating liquid is guided by the guide member 42 and sucked by the suction flow path 36, the floating coating liquid is effectively sucked. Further, since the guide member 42 protrudes in the ejection direction from the ejection port 38A of the nozzle hole extension portion 38, the tip of the guide member 42 is located more than the ejection port 38A of the nozzle hole extension portion 38, as shown in FIG. The floating coating solution is effectively taken in close to the workpiece 54.

  In the present embodiment, the tip 42A of the guide member 42 is configured to protrude in the ejection direction from the ejection port 38A of the nozzle hole extension 38, but the tip 42A of the guide member 42 is ejected from the nozzle hole extension 38. The structure which does not protrude in the ejection direction from the outlet 38A may be used. Specifically, as shown in FIG. 7, the front end 42A of the guide member 42 may be retracted to the rear end side of the nozzle hole extending portion 38A of the nozzle hole extension 38, or as shown in FIG. The positions of the tip 42A of the member 42 and the jet outlet 38A of the nozzle hole extension 38 may coincide with each other.

  Further, as shown in FIG. 9, the nozzle 10 may have a configuration in which the guide member 42 is not provided. In this configuration, the suction port 36 </ b> A of the suction channel 36 is formed on the outer peripheral surface of the side wall of the nozzle body 12.

  Further, as shown in FIGS. 10 and 11, the guide member 42 may have a configuration in which a part in the circumferential direction protrudes greatly toward the outer circumferential side with respect to another part in the circumferential direction. The side of the guide member 42 that protrudes to the outer peripheral side is the downstream side in the movement direction of the movement mechanism 58.

  In the case where the coating liquid is ejected while the nozzle 10 is moved by the moving mechanism 58, the floating coating liquid increases on the downstream side in the moving direction of the nozzle 10. According to the configuration shown in FIGS. It becomes easy to collect.

  When a plurality of nozzles 10 are used, the guide member 42 surrounds the outer circumferences of the plurality of nozzle hole extension portions 38 (nozzle portions 40) as shown in FIGS. It may be configured. Thus, by sharing the guide member 42 for the plurality of nozzles 10, the number of parts is reduced. As shown in FIG. 13, the guide member 42 has a shape surrounded by opposed long sides and opposed curves when viewed from the tip side of the nozzle body 12. May have a quadrilateral shape (for example, a rectangular shape) surrounded by four sides.

  In the present embodiment, the floating coating liquid is sucked and re-spouted by the pressure difference between the discharge port 36B and the suction port 36A. However, as shown in FIG. 14, suction and re-spout are performed using driving force. The structure which performs this may be sufficient. In this configuration, a pump 41 is provided in each suction channel 36. By driving the pump 41, the floating coating liquid is sucked from the suction port 36 </ b> A of the suction channel 36. The sucked floating coating liquid is discharged from the discharge port 36 </ b> B to the nozzle hole extension portion 38, becomes a mist by the air from the air flow path 28, and is jetted again to the object 54 through the nozzle hole extension portion 38. The Further, in this configuration, the discharge port 36 </ b> B may be connected to the tube body 26 so as to be ejected from the nozzle hole extending portion 38 through the coating liquid channel 16.

  In the present embodiment, the floating coating liquid is sucked and re-spouted. However, as shown in FIG. 15, a configuration in which only the floating coating liquid is sucked may be used. In this configuration, the discharge port 36 </ b> B of the suction flow path 36 is not connected to the nozzle hole extension 38 but is connected to the pump 39. By driving the pump 39, the floating coating liquid is sucked from the suction port 36 </ b> A of the suction channel 36. Note that the sucked floating coating solution is stored in, for example, a storage unit.

(Photoreceptor 80 and its manufacture)
Next, the photoreceptor 80 used in the electrophotographic apparatus as a product manufactured by the coating apparatus 50 and its manufacture will be described.

  As shown in FIG. 16, the photoreceptor 80 includes a base 82 and a photosensitive layer 84 formed on the outer peripheral surface thereof. The substrate 82 corresponds to the above-described object 54 to be coated, and the photosensitive layer 84 corresponds to a coating film formed on the substrate 82 by applying a coating solution to the substrate 82.

  As the base 82 of the photoreceptor 80, for example, aluminum, copper, gold, silver, platinum, palladium, titanium, nickel on a drum or sheet of metal such as aluminum, copper, iron, zinc, nickel, paper, plastic, or glass. -Deposit metal such as chromium, stainless steel, copper-indium, deposit conductive metal oxide such as indium oxide and tin oxide, laminate metal foil, or carbon black, indium oxide, tin oxide- Known materials such as drum-like, sheet-like, and plate-like ones that are conductively treated by dispersing and coating antimony oxide powder, metal powder, copper iodide, etc. in a binder resin are used. It is not limited.

  As the photosensitive layer 84, as shown in FIG. 16, for example, there is a function separation type laminated structure including a charge generation layer 84A formed of a charge generation material and a charge transport layer 84B formed of a charge transport material. . The photosensitive layer 84 may have a single layer structure containing the charge transport material and the charge generation material in the same layer.

  The charge generation material is not particularly limited, and for example, conventionally known materials are used. Specific examples of such a charge generation material include selenium compounds such as amorphous selenium, crystalline selenium-tellurium alloy, selenium-arsenic alloy, or inorganic photoconductive materials such as selenium alloy, zinc oxide, and titanium oxide. Materials: Organic pigments or dyes such as phthalocyanine compounds, squalium compounds, anthanthrone compounds, perylene compounds, azo compounds, anthraquinone compounds, pyrene compounds, pyrylium salts, thiapyrylium salts, and the like.

  Moreover, there is no restriction | limiting in particular as a charge transport material, For example, a conventionally well-known thing is used. Such charge transport materials include oxadiazole derivatives, pyrazoline derivatives, aromatic tertiary amino compounds, aromatic tertiary diamino compounds, 1,2,4-triazine derivatives, hydrazone derivatives, quinazoline derivatives, benzofuran derivatives. Hole transport materials such as α-stilbene derivatives, enamine derivatives, carbazole derivatives, poly-N-vinylcarbazole and derivatives thereof; quinone compounds, tetracyanoquinodimethane compounds, fluorenone compounds, oxadiazole compounds, Examples thereof include electron transport materials such as xanthone compounds, thiophene compounds, and diphenoquinone compounds.

  Furthermore, there is no restriction | limiting in particular as binder resin used for the photosensitive layer 84, A conventionally well-known thing is used. Specific examples of such binder resins include polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal resin, polycarbonate resin, polyester resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, vinyl chloride. -Vinyl acetate copolymer, silicone resin, phenol resin, poly-N-vinyl carbazole resin and the like.

  Furthermore, the surface layer of the photosensitive layer 84 is composed of inorganic filler, polyethylene powder, fluorine atom-containing resin fine particles, spherical resin fine powder made of curable resin or silicone resin, melamine-formaldehyde condensate or benzoguanamine-formaldehyde condensate fine particles. It is preferable to contain fine particles such as. When the surface layer contains such fine particles, the wear resistance and lubricity of the electrophotographic photosensitive member tend to be improved.

  As shown in FIG. 17, an undercoat layer 86 may be provided between the photosensitive layer 84 and the substrate 82. The undercoat layer 86 prevents the charge from flowing from the substrate 82 to the photosensitive layer 84 when the photosensitive layer having a laminated structure is charged, and also integrally holds the photosensitive layer 84 to the substrate 82. It means a layer that functions as an adhesive layer and prevents light reflection of the base 82 depending on the material. Here, as the binder resin used for the undercoat layer 86, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, Vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide , Zirconium chelate compounds, titanyl chelate compounds, titanyl alkoxide compounds, organic titanyl compounds, silane coupling agents, etc., and these binder resins are used alone. May be use, it may be used as a mixture of two or more. Further, these binder resins may be used by mixing with fine particles such as titanium oxide, silicon oxide, zirconium oxide, barium titanate, and silicone resin.

  The photosensitive layer 84 may contain additives such as an antioxidant, a light stabilizer, and a heat stabilizer. Here, as the antioxidant, hindered phenol, hindered amine, p-phenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compound, organic phosphorus compound, etc .; benzophenone as light stabilizer , Benzotriazole, dithiocarbamate, tetramethylpiperidine and derivatives thereof.

  When the photosensitive layer 84 has a function-separated layered structure including the charge generation layer 84A and the charge transport layer 84B, first, a solution containing the charge generation material and the binder resin is ejected from the nozzle 10 onto the substrate 82. Then, a charge generation layer 84A is formed. Next, a solution containing the charge transport material is further ejected from the nozzle 10 onto the charge generation layer 84A and applied to form the charge transport layer 84B. Thereby, the photoreceptor 80 is manufactured.

  Note that the coating apparatus 50 may be used in at least one of the film formation of the charge generation layer 84A and the charge transport layer 84B. Further, the photoreceptor 80 may have a functional layer other than the charge generation layer 84A, the charge transport layer 84B, and the undercoat layer 86. In that case, the coating apparatus 50 is used in forming the functional layer. May be.

  Here, as a solvent for dissolving the charge generation material and the charge transport material, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; ketones such as acetone and 2-butanone; methylene chloride, chloroform, ethylene chloride and the like Halogenated aliphatic hydrocarbons; cyclic or straight chain ethers such as tetrahydrofuran and ethyl ether, and the like. These solvents may be used alone or as a mixture of two or more. May be. As a method for dispersing the charge generation material and the charge transport material in a solvent, a conventionally known method using, for example, a ball mill, a sand mill, an attritor, a dyno meal or the like is used.

  Further, the film thickness of the charge generation layer 84A and the charge transport layer 84B is not particularly limited, but the film thickness of the charge generation layer 84A is usually 0.01 to 5 μm, preferably 0.05 to 2 μm. The thickness of 84B is usually 5 to 50 μm, preferably 10 to 40 μm.

  When the photosensitive layer 84 has a single layer structure containing the charge transport material and the charge generation material in the same layer, a solution in which the charge transport material and the charge generation material are dispersed is ejected from the nozzle 10 onto the substrate 82. Apply. Thereby, the photoreceptor 80 is manufactured. Here, as the solvent to be used and the method of dispersing in the solvent, for example, the same method as in the case of the above-mentioned laminated photosensitive layer is used. The film thickness of the photosensitive layer 84 is not particularly limited, but is usually 5 to 100 μm, preferably 10 to 40 μm.

(Organic electroluminescent device 90 and its manufacture)
Next, an organic electroluminescent element (organic EL element) 90 as a product manufactured by the coating apparatus 50 and its manufacture will be described.

  As shown in FIG. 18, the organic electroluminescent device 90 includes, for example, a transparent electrode (anode) 92, a hole injection layer 93, a hole transport layer 94, a light emitting layer 95, an electron transport layer 96, and a transparent substrate 91. A back electrode 97 (cathode) is sequentially stacked.

  The transparent substrate 91 is preferably transparent in order to extract emitted light, and a glass substrate, a plastic film substrate, or the like is used.

  The transparent electrode 92 is transparent in order to extract emitted light in the same manner as the transparent substrate 91 and has a high work function in order to inject holes. For example, an oxide film (for example, indium tin oxide (ITO), oxide) Tin (NESA), indium oxide, zinc oxide or the like) or a metal film (for example, gold, platinum, palladium, or the like) is preferably used. The transparent electrode 92 is formed on the transparent substrate 91 by, for example, vapor deposition or sputtering.

  As a hole injection material constituting the hole injection layer 93, for example, MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine), copper phthalocyanine, polyaniline, PEDOT / PSS ( Polyethylene dioxythiophene / polystyrene sulfonate) or mixtures thereof are preferably used.

  The hole injection layer 93 is formed on the transparent electrode 92 by spraying and applying a solution containing a hole injection material from the nozzle 10 onto the transparent electrode 92.

  The solvent of the coating solution to be used is preferably one that dissolves the raw material organic material (such as a light-emitting material or a charge transport material), and is preferably a volatile organic solvent. Typical examples of the organic solvent include 2-methyl-1-propanol, benzene, toluene, tetrahydrofuran and the like.

  As the hole transport material constituting the hole transport layer 94, for example, a tetraphenylenediamine derivative, a triphenylamine derivative, a carbazole derivative, a stilbene derivative, an arylhydrazone derivative, a porphyrin-based compound, or the like is desirably used.

  The hole transport layer 94 is formed on the hole injection layer 93 by applying and spraying a solution containing a hole transport material from the nozzle 10 onto the hole injection layer 93. As the solvent of the coating liquid to be used, for example, the above organic solvent is used.

  Examples of the light-emitting material constituting the light-emitting layer 95 include compounds that exhibit a higher fluorescence quantum yield in the solid state than other states, such as a low-molecular light-emitting material or a polymer light-emitting material. Examples of the low-molecular light-emitting material include chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, coumarin derivatives, styrylarylene derivatives, silole derivatives, oxazole derivatives, oxathiazole derivatives, and oxadiazole derivatives. Examples of the polymer light emitting material include polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyacetylene derivatives.

  The light emitting layer 95 is formed on the hole transport layer 94 by applying a solution containing a light emitting material by ejecting the solution from the nozzle 10 onto the hole transport layer 94. As the solvent of the coating liquid to be used, for example, the above organic solvent is used.

  As an electron transport material constituting the electron transport layer 96, an oxadiazole derivative, a nitro-substituted fluorenone derivative, a diphenoquinone derivative, a thiopyrandioxide derivative, a fluorenylidenemethane derivative, or the like is preferably used.

  The electron transport layer 96 is formed on the light emitting layer 95 by spraying a solution containing an electron transport material from the nozzle 10 onto the light emitting layer 95 and applying it. As the solvent of the coating liquid to be used, for example, the above organic solvent is used.

  The back electrode 97 is made of a metal having a small work function in order to inject electrons, and particularly preferably magnesium, aluminum, silver, indium, or an alloy thereof. The back electrode 97 is formed on the electron transport layer 96 by, for example, vapor deposition or sputtering.

  Note that the coating apparatus 50 may be used in at least one of the film formation of the hole injection layer 93, the hole transport layer 94, the light emitting layer 95, and the electron transport layer 96. The organic electroluminescent device 90 may have a functional layer other than the hole injection layer 93, the hole transport layer 94, the light emitting layer 95, and the electron transport layer 96. In the film formation, a coating apparatus 50 may be used. Further, the organic electroluminescent device 90 may have a configuration in which the hole injection layer 93, the hole transport layer 94, and the electron transport layer 96 are not included as long as the light emitting layer 95 is included.

[Example]
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, it is not limited to these. For the photoconductors manufactured in the examples and comparative examples, a digital copier (Apeos Port III C4400) manufactured by Fuji Xerox Co., Ltd. was used, and “image quality” and “film defect / foreign matter adhesion” were determined according to the following criteria. evaluated.

  “Image quality” was determined by visually observing that the output image had no shading unevenness, no image defect, and no image smearing as ◯, slight occurrence Δ, and occurrence x. “Coating film defect / foreign matter adhesion” was determined by visually observing the surface of the coated photoconductor, with no occurrence, o slightly occurrence, and occurrence x.

Example 1
In Example 1, a photoreceptor substrate was prepared as follows. First, an aluminum pipe having a diameter of 84 mm, a length of 340 mm, and a thickness of 1 mm is mirror-cut by a mirror lathe using a diamond tool to obtain a surface roughness Ra (the arithmetic average roughness specified in JIS B0601 (2001)). ) Was finished to a smooth surface having a thickness of 0.04 μm. Next, this substrate was subjected to a surface roughening treatment using wet blasting.

  Next, after the substrate held on the support is moved to the cleaning tank by the robot, it is arranged so that the axis of the support and the center of the ring nozzle coincide with each other, and the cleaning process is performed using ion-exchanged water. went.

  Using the substrate that had been roughened by the above method, a photoreceptor was produced according to the following procedure.

  First, 100 parts by weight of an organozirconium compound (trade name: Olgatyx ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by weight of a silane coupling agent (trade name: A1100, manufactured by Nihon Unicar Co., Ltd.), polyvinyl butyral resin (commodity) (Name: BM-S, manufactured by Sekisui Chemical Co., Ltd.) 10 parts by weight and n-butyl alcohol 130 parts by weight were mixed to prepare a coating solution. The obtained coating solution was applied to the substrate surface by a dip coating method and heated at 140 ° C. for 15 minutes to form a subbing layer having a thickness of 1.0 μm.

  Next, a 2 wt% cyclohexanone solution of polyvinyl butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and a hydroxygallium phthalocyanone pigment (described in JP-A-5-263007) are used. Then, the pigment and the resin were mixed so that the ratio was 2: 1 and dispersed for 3 hours by a sand mill. The obtained dispersion was further diluted with n-butyl acetate and dip-coated on the undercoat layer to form a charge generation layer having a thickness of 0.15 μm.

  Next, 4 parts by weight of N, N′-diphenyl-N, N′-bis (m-tolyl) benzidine and 6 parts by weight of polycarbonate Z resin are dissolved in 36 parts of monochlorobenzene, and the resulting solution is placed on the charge generation layer. Then, coating was performed by a coating apparatus 50, and 500 continuous spray coatings were performed. Thereafter, the film was dried at 115 ° C. for 40 minutes, and a charge transport layer having a thickness of 24 μm was formed to obtain a photoreceptor.

  In Example 1, the nozzle 10 was used (see FIG. 8) in which the positions of the tip 42A of the guide member 42 and the jet outlet 38A of the coating liquid flow channel 16 coincided (gap g (see FIG. 4) is 0 mm).

(Example 2)
In the second embodiment, the tip 42A of the guide member 42 is retracted 5 mm from the jet outlet 38A of the coating liquid flow path 16 (gap g (see FIG. 4) is −5 mm), using the nozzle 10 (see FIG. 7). Application was carried out in the same manner as in Example 1.

(Example 3)
In the third embodiment, the tip 42A of the guide member 42 protrudes 5 mm from the ejection port 38A of the coating liquid channel 16 (gap g (see FIG. 4) is +5 mm), and the nozzle 10 is used (see FIG. 4). Application was performed in the same manner as in Example 1.

Example 4
In Example 4, application was performed in the same manner as in Example 1 using the nozzle 10 not provided with the guide member 42 (see FIG. 9).

(Comparative example)
In the comparative example, application was performed in the same manner as in Example 1 using the nozzle 100 in which the suction channel 36 was not provided (see FIG. 19).

  As a result, as shown in the result table of FIG. 20, “film defect / foreign matter adhesion” occurred slightly in Examples 1, 2, and 4, but did not occur in Example 3, but occurred in the comparative example. As for “image quality”, in Examples 1 and 3, there were no shading unevenness, image defects, and image stains, and in Example 2, slight shading unevenness, image defects, and image stains were generated.

  The present invention is not limited to the above-described embodiment, and various modifications, changes, and improvements can be made.

DESCRIPTION OF SYMBOLS 10 Nozzle 23 Ejection flow path 36 Suction flow path 36A Suction port 36B Ejection port 38A Ejection port 42 Guide member 54 Coating object

Claims (8)

An ejection flow path for ejecting liquid droplets on an object to be coated;
A suction flow path for sucking a liquid droplet ejected from the ejection flow path from the suction port;
Nozzle with.   The nozzle according to claim 1, wherein the suction channel has a discharge port provided downstream of the suction port and communicates with the ejection channel.   The nozzle according to claim 2, wherein the suction flow path has a smaller cross-sectional area of a discharge port provided downstream of the suction port than a cross-sectional area of the suction port. The suction channel has a discharge port provided downstream of the suction port and communicates with the ejection channel,
The nozzle according to claim 1, wherein the liquid droplet sucked in the suction flow channel is re-ejected from the ejection flow channel.   The nozzle according to claim 4, wherein the suction channel sucks the liquid droplets by a pressure difference between the suction port and the discharge port that is generated along with the ejection in the ejection channel.   The nozzle of any one of Claims 1-5 provided with the guide member provided in the outer periphery of the said suction opening, and guiding the said droplet to the said suction opening.   The nozzle according to claim 6, wherein a leading end of the guide member protrudes in a jet direction from a jet port of the jet channel. An ejection process for ejecting liquid droplets onto an object to be coated;
A suction step for sucking and floating droplets ejected in the ejection step;
A re-ejecting step of re-ejecting the liquid droplets sucked in the suction step to the object to be coated;
The manufacturing method of a coating film provided with.

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