JP2008155449A - Printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing method by which a highly minute pattern can be continuously formed on a flexible base material such as glass base material, plastic film, plastic film in continuous form having especially favorable production efficiency or the like. <P>SOLUTION: This printing method comprises: (1) the provision of an ink liquid film by coating an ink-releasable film base material fed from a take-up roll with an ink liquid by an ink-jetting method, (2) the acquisition of a predried ink film by predrying the ink liquid film, (3) the thrusting of the pattern-formed surface of a relief printing plate equipped with an intagliated part provided with the shape of a pattern desiring to transfer thereon and a relieved part provided with the shape of a pattern not desiring to transfer so as to transferringly remove the portion of the predried ink film corresponding to the relieved part of the relief printing plate and finally (4) the transferring of the portion of the predried ink film remaining on the ink-releasable film base material to the surface of the target base material to be printed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is characterized in that a high-definition pattern can be continuously formed on a flexible substrate such as a glass substrate or a plastic film, in particular, a long plastic film having a high production efficiency. It is about the method.

  In recent years, flat panel displays have been widely used in various forms such as a stationary type, a wall-mounted type, and a portable type in terms of energy saving, space saving, portability, and the like.

  In particular, in the portable type, there is a strong demand for plasticization due to various demands such as ensuring impact resistance that does not break even when dropped when carrying, and reducing the weight and thickness. In addition, the development of a display using a flexible plastic base material is strongly desired from the desire to install it on a columnar column even in a wall-mounted type.

  However, all the conventional flat panel displays are manufactured using a glass substrate, and it is difficult to manufacture using a plastic substrate.

  The reason is that the production of the members of the conventional flat panel display includes a heating process and a photolithography process at a high temperature.

  For example, when manufacturing color filters for liquid crystal displays, there are processes such as development, washing, baking, etc. during patterning of the photosensitive resin, and heat-resistant members such as plastic substrates are not damaged or stretched by heat. Will occur.

  In addition, in the manufacturing process of a thin film transistor that is a driving electrode of a display, the formation of a silicon semiconductor or an insulating film includes a high-temperature processing step of 300 ° C. or more. It has exceeded.

  In addition, since the photolithography process performs film formation, exposure, development, and peeling for each material, the manufacturing equipment is large and the manufacturing cost is high.

  From the above, establishment of a printing method capable of precise patterning on a plastic substrate has been strongly demanded.

  As a printing method on a plastic substrate, use of an ink jet method has been studied. The ink jet method is expected as the simplest patterning method because it can use a predetermined material only in a predetermined portion and can use the material efficiently.

  However, the diameter of ink droplets in the current ink jet method is about several tens of μm, and the landing accuracy is about several μm.

  In addition, in order to perform precise patterning using the ink jet method, barrier ribs must be formed on the substrate in advance by a photolithography process, and a pattern of about 10 μm such as a black matrix of a color filter or a thin film transistor wiring of a printing method. As a method of forming, it cannot be adopted.

  On the other hand, as a method other than the ink jet method, there is a screen printing method. The screen printing method has been put to practical use in the printing of wirings, resistors and dielectrics in electronic parts.

  However, since it is stencil printing, the ink is limited to a paste-like high-viscosity ink. Even if it can be used as a printing method for a thick film of about several tens of μm due to the fineness of the screen mesh, it is still about 10 μm. It cannot be adopted as a method for forming a pattern.

  Therefore, as a method other than the ink jet method and the screen printing method, a dry ink film is provided on the film in advance, a so-called dry film is used to remove the ink film pattern by hot pressure, and then the remaining ink film pattern is changed. A transfer method for transferring to a target base material has been proposed (see Patent Document 1).

  However, since a thermal pressure is applied when transferring a part of the ink film from the film, it involves expansion / contraction of the film base, expansion of the plate, and melting / softening of the ink film. Reproducibility of simple patterns is difficult. In addition, an apparatus for applying the heat pressure uniformly becomes complicated, and transfer in a large area becomes difficult.

  In addition, by applying ink on the blanket wound around the plate cylinder, pre-dried to form an ink film, and then pressing the relief plate on which the convex portions corresponding to the non-image portion pattern are formed, against the ink film, The portion corresponding to the non-image portion pattern is removed from the ink film, and then the image pattern remaining on the blanket is transferred onto the substrate to be printed to form a desired image pattern on the substrate to be printed. A printing method has been tried (see Patent Document 2).

  This method is easy to adjust the ink film thickness. In addition, in this printing method, an image pattern is formed on an ink-peeling blanket, so that ink transfer to a substrate to be printed is good. Further, it is possible to form a fine pattern with a thin film.

  However, this printing method has a problem that the ink wettability and transferability of the blanket surface become unstable when the ink is pre-dried on a blanket made of silicone rubber or silicone resin. This is because drying is performed while the blanket is fixed to the plate cylinder, so that uniform pre-drying is difficult, and the solvent in the coated ink is absorbed into the blanket, causing the blanket to swell and partially transferable. This is because variations in accuracy occur.

  Further, since it is necessary to adjust the amount of swelling by cleaning after transfer or drying of the blanket for each transfer, it is not suitable for continuous processing. In addition, since the blanket is fixed to the plate cylinder, the position of the pattern on the blanket and the mark on the substrate, etc., when another pattern is transferred onto the substrate on which a certain pattern is formed in advance. Matching was difficult.

Another problem that cannot be neglected is the low utilization efficiency of the ink material. Since an image pattern is formed from the uniformly applied ink liquid film, a lot of wasted ink is generated without being used for transfer to the substrate. For this reason, the method is particularly unsuitable for printing using an expensive ink material such as an organic EL ink.
JP-A-9-90117 JP 2001-56405 A

The present invention solves the problems of the prior art, and the object of the present invention is to provide a method for producing a printed matter with high use efficiency of an ink material. Another object of the present invention is to provide a printing method that can be applied to a flexible substrate such as a plastic film, particularly a long flexible substrate that is excellent in production efficiency, and that is excellent in reproducibility of high-definition patterns. .

  In order to achieve the above-mentioned object, the invention according to claim 1 is an ink solution in which an ink solution is applied onto an ink peelable film substrate supplied from a take-up roll using an ink jet method. After the film is provided, the ink liquid film is pre-dried to obtain a pre-dried ink film, and thereafter, a concave portion provided in the shape of the pattern to be transferred and a convex portion provided in the shape of the pattern not to be transferred are provided. The pattern forming surface of the relief printing plate is pressed against the pre-dried ink film, and the portion of the preliminary drying ink film corresponding to the convex portion of the relief printing plate is transferred and removed, and then the ink peelable film substrate A portion of the pre-dried ink film remaining on the substrate is transferred to the surface of the target substrate to be printed.

  The invention according to claim 2 is the printing method according to claim 1, wherein the preliminary dried ink film has adhesiveness by preliminary drying of the ink liquid film, and maintains its shape but at room temperature. Only a portion to which an external force is applied by the convex portion of the relief printing plate is in a semi-dry state that can be transferred and removed.

  Still further, the invention according to claim 3 is the printing method according to claim 1 or 2, wherein the ink peelable film base material is continuously fed out from the unwinding portion and is always new. It is characterized by using.

  Furthermore, the invention according to claim 4 is the printing method according to any one of claims 1 to 3, wherein the ink peelable film substrate is formed by laminating a silicone resin layer on the film substrate. It is characterized by being.

Furthermore, the invention according to claim 5 is the printing method according to any one of claims 1 to 3, wherein the ink peelable film substrate is formed of SiO ₂ , TiO ₂ , ZrO ₂ on the film substrate. Either an inorganic oxide film or a composite oxide film of these, and at least one of an alkyl group, a siloxane group, and a fluorine atom is located on the surface through a layer of a silane coupling agent. Features.

  Furthermore, the invention according to claim 6 is the printing method according to any one of claims 1 to 3, wherein the ink peelable film substrate is an oxide film formed on a film substrate by a sol-gel method. Further, at least one of an alkyl group, a siloxane group, and a fluorine atom is located on the surface through a layer of a silane coupling agent.

  Furthermore, the invention according to claim 7 is the printing method according to any one of claims 1 to 6, wherein the ink-peelable film substrate is optically transparent.

  Furthermore, the invention according to claim 8 is the printing method according to any one of claims 1 to 7, wherein the portion comprising the pre-dried ink film left on the ink-peelable film substrate is already provided. When transferring to the surface of the substrate to be printed on which the image pattern is provided, while maintaining the parallel state of the substrate to be printed and the film substrate of the ink releasability, the ink releasability is observed using an observation device. Alignment of the part of the pre-dried ink film left on the film substrate and the image pattern already provided on the surface of the substrate to be printed is performed.

  Furthermore, the invention according to claim 9 is the printing method according to any one of claims 1 to 8, wherein a part of the pre-dried ink film on the ink peelable film substrate is transferred and removed. As the relief plate, a plate made of glass or resin is used.

  Since the printing method of the present invention has the above characteristics, it has the following effects.

  That is, according to the first aspect of the present invention, an ink liquid film is applied on an ink peelable film substrate supplied from a winding roll, the ink liquid film is preliminarily dried, After obtaining the dried ink film, the relief printing plate having the required image portion pattern as a recess is pressed against the preliminary drying ink film, and unnecessary portions of the preliminary drying ink film are transferred to the convex portion of the relief printing plate. The image pattern of the pre-dried ink film remaining on the ink-peeling film substrate is transferred onto the surface of the target substrate to be printed, enabling high-definition printing and only the necessary parts using the ink jet method. By providing an ink liquid film on the printing method, it is possible to obtain a printing method in which the amount of ink used is suppressed.

  Further, according to the invention according to claim 2, the pre-dried ink film has adhesiveness by pre-drying and maintains its shape, but only a portion to which external force is applied by the convex portion of the relief printing plate is transferred at room temperature. Therefore, it is possible to transfer and remove the pre-dried ink film and transfer it to the substrate to be transferred without any heat treatment. There is no shape change due to thermal expansion of the material or the substrate to be transferred and thermal melting of the pattern, and a precise pattern can be printed.

  In addition, according to the invention according to the third aspect, the ink peelable film base material is sequentially fed out from the unwinding device, and printing can be performed using the new ink peelable film base material at all times, and is stable. Continuous printing is possible.

  In addition, according to the invention according to claim 4, the surface of the target printing substrate can be obtained by using an ink peelable film substrate obtained by laminating a silicone resin layer on the film substrate. High transferability can be printed with high reproducibility.

Further, according to the invention of claim 5, the ink-peelable film base is formed on the inorganic film formed of SiO ₂ , TiO ₂ , or ZrO ₂ on the film base, or the composite oxide film thereof. By providing at least one of an alkyl group, a siloxane group, and a fluorine atom on the surface of the provided base material via a silane coupling agent, the wettability of the surface is reduced while maintaining the smoothness of the surface. It is possible to increase the transferability of the pre-dried ink film to the relief printing plate or the surface of the substrate to be printed, and print a high-definition pattern with high reproducibility.

  According to the sixth aspect of the present invention, an ink peelable film base material is alkylated via a silane coupling agent on the base material surface provided with an oxide film by a sol-gel method on the film base material. By having at least one of a group, a siloxane group, and a fluorine atom located on the surface, it is possible to effectively reduce the wettability of the surface while maintaining the smoothness of the surface. The transfer property of the pre-dried ink film onto the material surface can be improved, and high-definition patterns can be printed with high reproducibility.

  According to the invention of claim 7, a part of the pre-dried ink film left on the surface of the ink peelable film base by making the ink peelable film base optically transparent Since it is possible to check other image patterns and alignment marks already provided on the substrate to be printed over (image patterns and alignment marks), it becomes easy to accurately align the transfer position and reproducibility. High-definition patterns can be printed.

Further, according to the invention according to claim 8, an image pattern formed by a pre-dried ink film partially left on an ink-peelable film substrate is already provided with another image pattern. When transferring to the surface, the substrate to be printed and the film substrate of the ink peelability are brought close to each other in parallel, and the substrate to be printed and the ink peelable film of the ink peelable property are Using an observation device such as a camera from between the film substrate and the image portion pattern left on the ink-peeling film substrate, and marks such as image patterns or holes provided on the surface of the substrate to be printed By performing the above positioning, it is possible to print a high-definition pattern with higher reproducibility.

  Further, according to the invention according to claim 9, high-definition pattern printing is performed by using a glass or resin plate as a relief plate for transferring and removing a part of the pre-dried ink film. Can do.

  Therefore, the present invention can continuously and stably print a high-definition pattern on a flexible substrate such as a glass substrate or a plastic film, particularly a long flexible substrate, and becomes a display member. A black matrix, a white matrix, a color pattern, a spacer, and the like of a color filter can be accurately produced by this printing method. Further, a solution type semiconductor pattern such as a gate electrode, a source / drain electrode, a gate insulating film, and an organic semiconductor of a printing transistor can be accurately produced by this printing method. Furthermore, the patterning of the light emitting layer of the polymer type organic EL can be efficiently produced by such a printing method.

  Hereinafter, embodiments of the printing method according to the present invention will be described.

  In the printing method of the present invention, an ink liquid film is applied on an ink peelable film substrate supplied from a winding roll using an ink jet method to form an ink liquid film, and then the ink liquid film is formed. Preliminarily dried to obtain a pre-dried ink film, and then the pre-dried pattern forming surface of the relief printing plate having concave portions provided in the shape of the pattern to be transferred and convex portions provided in the shape of the pattern not to be transferred. Press against the ink film to transfer and remove the part of the pre-dried ink film corresponding to the convex part of the relief printing, and then remove the part of the pre-dried ink film remaining on the ink peelable film substrate. It is the printing method characterized by making it transfer to the surface of the target to-be-printed base material.

  Hereinafter, the printing method of the present invention will be described in more detail with reference to a specific example using a printing apparatus whose schematic configuration is shown in FIG.

  The printing apparatus shown in FIG. 1 generally includes an ink peelable film base unwinding portion 101, an ink peelable film base unwinding portion 107, a substrate to be printed unwinding portion 108, Conveying part related to the conveyance of the ink-peelable film substrate and the substrate to be printed such as the winding part 110 of the printing substrate, the coating part 102 of the ink liquid, the preliminary drying part 103 of the ink liquid film, the preliminary drying ink A removal unit 104 for transferring / removing a portion where the film is not transferred into a pattern, an alignment unit 105 for transferring a portion where the pre-dried ink film is to be transferred, in register with the substrate to be printed, and The laminating unit 106 includes a drying unit 109 for drying the pre-dried ink film transferred onto the substrate to be printed.

  Conveying parts such as the unwinding part 101 of the ink peelable film base, the winding part 107 of the ink peelable film base, the unwinding part 108 of the substrate to be printed, and the winding part 110 of the substrate to be printed are In order to install or wind up the raw material supplied by each take-up roll, a cylinder (not shown) equipped with a mounter capable of mounting a core having a diameter of about 3 to 30 inches, and rotation and tension are controlled. A motor (not shown) for transporting the film substrate and the substrate to be printed is provided. The width of the film substrate or substrate to be printed mounted on the take-up roll can be selected from about 100 mm to 1000 mm, but the width of the substrate is about 300 mm in consideration of the practicality of the pattern and the transfer position accuracy. Is preferably used.

  Further, the tension applied to the film substrate or the substrate to be printed may be adjusted by using a nip portion in the transport system and holding the substrate there in addition to those caused by these apparatuses. For this nip portion, an adsorption nip mainly composed of air adsorption holes provided in the transport roll is used.

  The transport of the base material can be continuously transported at a transport speed of about 5 m / sec to 10 m / sec when the time difference required in each step is eased and a buffer for continuously transporting the base material is provided. However, it is preferable to use a method in which an ink-peelable film substrate or a substrate to be printed is fed out for a required length for each process.

  The coating unit 102 is provided with a movable stage 112 and an ink jet device 111 for applying an ink liquid to an ink-peeling film substrate conveyed on the movable stage 112. The movable stage 112 is made of metal or stone, and can be driven by a ball screw, a linear motor, or the like, and can reciprocate in the horizontal direction while maintaining at least the level. It is possible to temporarily adsorb an adhesive film substrate. When adsorbing, the surface of the film substrate can be adsorbed by adsorption holes provided near the edge of the film substrate so that the film substrate does not become uneven. It is possible to adopt a configuration that allows the film base material to be uniformly adsorbed over a wide area.

  On the other hand, for example, the ink jet device 111 uses a single ink jet head, and drives the stage and the ink jet head a plurality of times so that a patterned ink liquid film made of an ink liquid can be applied. Or a head array having a plurality of ink jet heads arranged in accordance with the width of the ink-peelable film substrate. In such an ink jet apparatus, a predetermined amount of ink can be supplied from a separately prepared ink supply tank (not shown). The gap between the ink jet head and the ink releasable film substrate may be set before the start of ink liquid coating, and is adjusted by moving the ink jet head up and down according to the conveyance of the movable stage 112.・ It may be set.

  The pre-drying unit 103 is installed to pre-dry the ink liquid film that has been applied on the ink-peelable film substrate by the coating unit 102, and there is a hot plate, oven, The ink liquid film on the film substrate is preliminarily dried using wind, a vacuum dryer, an ultraviolet irradiator or the like.

  In the removing unit 104 for transferring and removing the portion of the pre-dried ink film that is not transferred, for example, a relief plate made of resin or glass is attached to the movable stage by adsorption, and the ink peelable film substrate After bringing the relief plate close to the pre-drying ink film, the load is applied by the impression cylinder along with the movement of the movable stage, and the portion of the pre-drying ink film in contact with the convex portion of the relief plate is transferred to the relief plate side. Remove from substrate.

  The alignment unit 105 includes a movable stage and a plurality of microscope cameras and the like. The pre-dried ink remaining on the ink-peelable film substrate on the substrate to be printed adsorbed on the movable stage. After bringing the surface of the membrane close to about 100 to 250 μm, utilizing the transparency of the ink-releasable film substrate, part of the pre-dried ink film remaining on the ink-removable film substrate and alignment A pattern such as a mark pattern for printing and a pattern already printed on the substrate to be printed are recognized by a transmission image, and the movable stage is operated based on the recognition image of the pattern on each substrate to determine the transfer position. Make corrections.

  A method of inserting a microscope camera between the ink-peelable film substrate and the substrate to be printed and correcting the position based on the recognized image of the pattern on each substrate can also be selected.

  As the microscope camera, an optical microscope, a CCD (Charge Coupled Device) microscope, or the like can be applied. However, the microscope camera requires either an autofocus function, an electrically controllable manual focus control mechanism, or both functions. Therefore, it is recommended to have an external monitor or an interface to an image processing device for position correction.

  The laminating unit 106 is provided with a laminating roller such as a metal roller or a rubber roller on a movable stage installed in the alignment unit 105.

  In this laminating portion 106, a roller is pressed against this substrate against the substrate to be printed fixed to the movable stage and the ink-peeling film substrate that has been transported while maintaining a slight gap therewith, A pre-dried ink film left on the film substrate by moving the movable stage and applying the printing pressure while rotating the roller to overlap, and then peeling the ink-removable film substrate from the substrate to be printed. Is transferred onto the substrate to be printed.

  The drying unit 109 is installed to dry the pre-dried ink film transferred onto the substrate to be printed, and is predetermined by a drying device using a hot plate, oven, hot air, reduced pressure drying, ultraviolet irradiation, or the like. It is a part which performs drying. Here, it is sufficient that drying necessary to prevent blocking at the time of winding the substrate to be printed is performed, and specifically, thermal drying is performed at 120 ° C. for about 3 to 5 minutes.

  Examples of the ink peelable film substrate used in the present invention include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, cycloolefin polymer, polyimide, nylon, aramid, polycarbonate, polymethyl methacrylate, polyvinyl chloride, and triacetyl. A flexible film or sheet made of cellulose or the like can be used. Furthermore, by using a light-transmitting film base material, alignment can be facilitated during pattern superposition. These flexible substrates are supplied by a long winding roll.

  The ink releasable film base material used in the present invention may be coated with a release agent represented by silicone oil or silicone varnish on the base material, or a thin film layer of silicone rubber may be formed. Good. For the same purpose, fluorine-based resin, fluorine-based rubber or the like can be used, or the fluororesin fine powder can be mixed with silicone rubber or ordinary rubber to give peelability. These silicone-based coatings are generally weakly adhered to the film substrate, but are thermosetting or ultraviolet curable acrylic resins, epoxy resins, and resins having high adhesion to the silicone layer provided on the outermost surface. A layer composed of the above or the like may be provided on the film substrate in advance as an anchor layer.

  Regardless of the configuration, the ink-peelable film substrate needs to have an appropriate ink receptivity and at the same time have the complete ink-release property of the pre-dried ink film once received.

  Specific examples of the silicone include dimethylpolysiloxanes having various molecular weights, other methylhydrogenpolysiloxanes, methylphenylsilicone oils, methylchlorinated phenylsilicone oils, or a copolymer of these polysiloxanes and organic compounds. A coalescence or the like can be used.

  As the silicone rubber, a two-component diorganopolysiloxane and a trifunctional or higher functional silane as a crosslinking agent, or a combination of siloxane and a curing catalyst, or a one-component diorganopolysiloxane and acetone oxime, A combination of various methoxysilanes, methyltriacetoxysilanes, or the like is used. In addition, polysiloxane or the like for adjusting rubber hardness is also used as appropriate.

  Moreover, after providing an inorganic substance film | membrane to the said base material as an ink peelable film base material used for this invention, what surface-treated with the silane coupling agent can also be used.

  As the silane coupling agent, trimethoxysilanes, triethoxysilanes, and the like can be used. One part of this silane coupling agent can be selected from those having a reactive group with an organic compound such as a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an alkyl group or a part thereof. Those in which fluorine atoms are substituted or those in which siloxane is bonded to each other and bonded to a substituent capable of forming a surface having a small surface free energy can be used. When the former silane coupling agent having a reactive group is used, the surface of the substrate is treated with the silane coupling agent, and then another monomer component is applied so as to obtain a predetermined surface free energy. Can be made. Examples of the silane coupling agent having a reactive group include vinyl methoxy silane, vinyl ethoxy silane, p-styryl trimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 2- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane. , 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, etc., and monomers include styrene, ethylene glycol diglycidyl ether, trimethylpropane triglycidyl ether, lauryl acrylate, dipentaerythritol Hexaacrylate or the like can be used. As the silane coupling agent having no reactive group, methyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane, or the like can be used. However, it is not limited to an alkyl group.

  As a method for fixing the silane coupling agent to the substrate, a known surface treatment method using a silane coupling agent can be used. For example, a solution in which a silane coupling agent is diluted with water, an acetic acid aqueous solution, a water-alcohol mixed solution, or an alcohol solution is prepared, and then the prepared solution is a known coating method such as a gravure coater, a roll coater, The silane coupling agent can be fixed by coating on the surface of the substrate using a die coater or the like and then drying. When a silane coupling agent having a reactive group is used, other monomer components can then be applied and bonded in the same manner.

In order to immobilize the silane coupling agent on the substrate, it is preferable that a thin film made of SiO ₂ , TiO ₂ , or ZrO ₂ or a composite film thereof is provided on the substrate in advance. As these inorganic oxide films, those provided by using a known vapor deposition method or sputtering method can be used.

In order to provide the inorganic oxide film, a metal alkoxide represented by the general formula M (OR) n (M is a metal such as Si, Ti, Al, Zr, R is CH ₃ , C ₂ H _5, etc.) Use a so-called sol-gel method in which an inorganic oxide film is formed by coating a gel solution obtained by subjecting an alkyl group) to hydrolysis and polycondensation reaction in the presence of water and alcohol on the surface and then heating. Can do.

Furthermore, the silane coupling agent can be added in advance to the metal alkoxide solution used in the sol-gel method. In this case, an effect is particularly obtained for surface property modification.

  The ink releasability for the ink releasable film substrate thus obtained is preferably such that the contact angle when the ink liquid is dropped onto the treated surface is about 10 ° or more and 90 ° or less, and 20 ° or more. More preferably, it is 70 ° or less. If the contact angle is small, the predetermined ink peelability cannot be ensured in the subsequent process, and defects in the transfer pattern of the pre-dried ink film to be transferred (reproducibility defects, etc.) are likely to occur. When forming the liquid film, repelling occurs, making it difficult to form a uniform ink liquid film.

  As a method of forming an ink liquid film on the above-described ink peelable film substrate, an ink jet device is used. The ink jet head method of this ink jet device is a thermal method, a bubble method, an electrostatic actuator method, A conventionally known method such as a piezo method can be employed.

  Compared to the case where a uniform ink liquid film is applied to the entire surface of the ink-removable film substrate using a spin coating method, a die coating method, etc., the pattern including the pattern to be transferred to the substrate to be printed is slightly larger. If an ink liquid film is provided in a predetermined area on a flexible ink-removable film substrate by using the ink jet method, the amount of wasted ink that is unnecessary in the subsequent process can be suppressed. Printing with high use efficiency of the ink material can be achieved.

  After the ink liquid film is formed by the above method on a predetermined region on the ink-peelable film substrate, the ink liquid film is preliminarily dried. This predrying includes natural drying, cold / hot air drying, microwave drying, Various drying methods such as vacuum drying can be used. Moreover, you may make it dry using radiation, such as an ultraviolet-ray and an electron beam.

  The purpose of this preliminary drying is to increase the viscosity, thixotropy and brittleness of the ink liquid film. When drying by preliminary drying is insufficient, when the convex part of the relief printing plate is pressed and peeled off in a later step, the preliminary drying ink film is torn at an unnecessary part. On the other hand, when the drying is excessive, tackiness on the surface of the pre-dried ink film is lost, and the pre-dried ink film is not transferred to the convex portions of the relief printing plate. Therefore, although the drying state is adjusted by the drying time and the atmospheric temperature depending on the composition of the ink to be used, it is preferable that a solvent residue of about 0.5% to 4.0% is observed in the predried ink film.

  The so-called dry film has a residual amount of solvent on the order of ppm, which causes excessive drying and causes a problem that a part of the pre-dried ink film is not transferred, or a part of the pre-dried ink film is peeled off due to pressing of the relief printing plate, resulting in dust. This is not suitable as a pre-dried ink film condition.

  The relief pattern used to transfer the desired portion of the pre-dried ink film on the ink-peelable film substrate to the substrate to be printed is a mask pattern using a photosensitive resin on the surface of low expansion glass such as alkali-free glass. After forming the film, an existing dry etching process, wet etching process, or sand blasting process can be used to provide a plate depth convex part and concave part of about 2 μm to 30 μm.

Moreover, what consists of nylon, an acryl, a silicone resin, a styrene-diene copolymer etc. can also be used for a letterpress. In addition, a relief printing plate made of rubber such as ethylene-propylene, butyl, or urethane rubber can be used. Such resin-made relief plates have already been used for general relief printing and flexographic printing, and can be obtained by pouring a predetermined resin into a previously produced mold or by engraving. However, a method using a photosensitive resin is preferably used because a method with higher accuracy can be produced.

  Examples of the substrate to be printed include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone, cycloolefin polymer, polyimide, nylon, aramid, polycarbonate, polymethyl methacrylate, polyvinyl chloride, triacetyl cellulose. It is also possible to use a film or sheet made of the same. From these, an appropriate one may be selected according to the drying conditions of the ink liquid film applied to the printing, but the heat resistant material is composed of polyethylene naphthalate, polyethersulfone, cycloolefin polymer, polyimide, etc. A flexible film or sheet is preferred. Moreover, the base material which consists of material which added the inorganic filler to resin and improved heat resistance may be sufficient. The film and sheet may be stretched or unstretched, and a gas barrier layer, a smoothing layer, an ink image-receiving layer, or the like may be laminated on the printing surface or other surface as necessary. .

  As the material of the ink liquid, an image pattern forming material in which a solvent is dissolved or dispersed can be used. For example, when a color pattern (colored layer) consisting of red, green and blue or a black matrix is provided by a printing method of the present invention in a color filter, an ink obtained by dissolving and dispersing a pigment component and a resin component in a solvent is used. Can be used.

  Examples of pigments that can be used in red, green, and blue colors include the following. The type of pigment is a color index (CI) No. It shows with. First, 97, 122, 123, 149, 168, 177, 180, 192, 208, 209, 215, etc. as red pigments, 7, 36, etc. as green pigments, 15, 15: 1, 15 as blue pigments. : 3, 15: 6, 22, 60, 64 and the like. Examples of black pigments include carbon black and titanium black. Furthermore, in order to improve the color adjustment of these red, green and blue pigments and the fluidity of the ink, the following pigments can be added in necessary amounts.

  That is, yellow pigments 17, 83, 109, 110, 128, etc., purple pigments, 19, 23, etc., white pigments, 18, 21, 27, 28, etc., orange pigments, 38, 43, etc. Is mentioned. In addition to the simple substance, these pigments may be a pigment dispersion in which the pigment is previously dispersed in a dispersant or an organic solvent.

  Moreover, as a black pigment used for formation of a black matrix, carbon black and titanium black are used individually or in mixture.

  As the resin component, for example, at least one selected from the group consisting of a polyester resin, an acrylic resin, an epoxy resin, a melamine resin, and a benzoguanamine resin is used. As the solvent, ester solvents, alcohol solvents, ether solvents, hydrocarbon solvents and the like are used. Examples of the ester solvent include propylene glycol monomethyl ether acetate and ethoxyethyl propionate. Examples of the alcohol solvent include 1-butanol, 3methoxy-3methyl-1butanol, 1-hexanol, 1,3 butanediol, -Pentanol, 2-methyl 1-butanol, 4-methyl-2-pentanol, ether solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene Glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether Le, the hydrocarbon-based solvent, Solvesso 100, Solvesso 150 (trade name, manufactured by Exxon Chemical Co., Ltd.).

In the case of forming an organic light emitting layer of an organic EL element, for example, an ink obtained by dissolving and dispersing a polymer light emitting material such as polyphenylene vinylene (PPV) in an aromatic organic solvent such as toluene or xylene as a solvent. Is used. In addition, when forming the wiring of the circuit substrate, it is obtained by dissolving and dispersing a metal fine particle dispersion such as gold, silver, copper, nickel, platinum, palladium, rhodium in water, alcohol, or glycol solvent. Ink is used. Moreover, various additives, such as surfactant, antioxidant, a viscosity modifier, a ultraviolet absorber, a leveling agent, may be added to these inks as needed. The ink used in the present invention is not limited to these.

  Examples of the present invention will be described below.

  A red colored ink for a color filter was prepared as follows.

(Composition of red coloring ink)
First, 20 parts by weight of methacrylic acid, 10 parts by weight of methyl methacrylate, 55 parts by weight of butyl methacrylate and 15 parts by weight of hydroxyethyl methacrylate are dissolved in 300 g of butyl lactate, and 0.75% by weight of azobisisobutylnitrile in a nitrogen atmosphere. Part was added and reacted at 70 ° C. for 5 hours to obtain an acrylic copolymer resin. Next, the obtained acrylic copolymer resin was diluted with propylene glycol monomethyl ether acetate so that the resin concentration was 10% by weight to obtain a diluted solution of the acrylic copolymer resin.

  18.0 g of red pigment and 0.9 g of polyoxyethylene alkyl ether as a dispersant were added to 80.1 g of this diluted solution, and kneaded with three rolls to obtain a red colored varnish. In addition, Pigment Red 177 was used as a red pigment.

  To each colored varnish obtained, propylene glycol monomethyl ether acetate was added by adjusting the pigment concentration to 11 to 15% by weight and the viscosity to 15 mPa · s (25 ° C.). The mixture was stirred and mixed, and further filtered through a 5 μm filter to obtain a red colored ink.

  Subsequently, a silicone-based release polyester film K1504 (manufactured by Toyobo Co., Ltd.) having a substrate thickness of about 120 μm was prepared as a 300-mm width and 500-m roll as an ink-peelable film substrate.

  Further, as a pattern removal plate (letter plate), a resin flexo plate (manufactured by Toyobo Co., Ltd.) having a width of 200 mm (pattern effective width is 150 mm) was prepared. This flexographic plate has four 50 mm × 50 mm patterns within the effective width. Each pattern is a continuous stripe pattern with a convex portion of 20 μm width and a concave portion of 80 μm width, and is positioned at four corners. An alignment mark is provided in a 200 μm square region.

  Further, a light-transmissive PET substrate having a film thickness of 120 μm was prepared as a substrate to be printed in a roll shape having a width of 300 mm and 20 m.

  And the printing process was performed as follows using the apparatus as shown in FIG. 1 using the said member. The ink jet apparatus used was a head equipped with a head of 12 pl and 180 dpi for one shot.

  First, an ink-peeling film substrate is drawn out so that a new film surface comes on the coating part stage, and a red colored ink having a coating width of 150 mm and a coating length of 150 mm, and 52 mm × 52 mm red ink by an inkjet device. Four ink liquid films consisting of were coated. In addition, a square pattern about 10% larger than the mark was also applied at the alignment mark position. The thickness of the ink liquid film was set such that the ejection amount of the ink jet apparatus was set so that the ink film thickness was 0.8 μm in the subsequent preliminary drying.

  Next, preliminary drying was performed for 30 seconds on a 40 ° C. hot plate installed in the drying unit to obtain a preliminary drying ink film, and then transported until the portion was positioned on the stage of the pattern removal unit. After that, it was kept waiting for 120 seconds there.

  Then, a pre-dried ink film is pressed against the flexographic plate installed in the pattern removal unit in advance with a rubber roller to remove the non-image area (pattern-shaped part that is not transferred), and then the silicone-based separation is performed on the alignment unit stage. It was conveyed so that the pattern of the pre-dried ink film remained on the shaped polyester film (peelable film substrate) was obtained. After confirming diagonal alignment marks with two alignment cameras, and then overlaying the ink peelable film substrate and the printing substrate with a rubber roller, the ink peelable film is moved from the stage. The image pattern was transferred to the substrate to be printed by peeling the substrate from the substrate to be printed.

  Finally, the substrate to be printed on which the image pattern was transferred was conveyed to a drying section, and dried for 120 seconds with a hot plate to obtain a printed pattern.

  In the same manner as in Example 1, processing was performed using an apparatus as shown in FIG.

  As the ink, an aqueous dispersion of silver particles (average particle size 20 nm), which is a conductive ink, was used in which the viscosity was adjusted to 12.0 mPa · s (25 ° C.) with ethylene glycol.

As an ink peelable film substrate, 0.1% hydrochloric acid 4.0 g and tetraethyl silicate 170 g (Si (OC ₂ H ₅ ) ₄ , Nippon Colcoat Chemical Co., Ltd., product name ethyl silicate 28) are dissolved in 1200 ml of isopropanol. A solution obtained by hydrolyzing the solution while stirring at room temperature for about 2 hours was coated on a PET substrate having a thickness of 120 μm and a width of 300 mm using a gravure coater to prepare a solution having a thickness of 0.5 μm.

  Moreover, as a pattern removal plate (letter plate), a glass plate produced by dry etching with a width of 200 mm (pattern effective width is 150 mm) and a plate depth of 25 μm was used. As in Example 1, the removal plate has four 50 mm × 50 mm patterns within the effective width, and each pattern is a continuous stripe pattern with a convex portion having a width of 20 μm and a concave portion having a width of 80 μm. In addition, an alignment mark provided in 200 μm square regions located at four corners was used.

  Then, the conductive ink was applied using an inkjet apparatus so that four patterns of 52 mm × 52 mm were arranged in a coating width of 150 mm and a coating length of 150 mm. In addition, a square pattern that was about 10% larger than the mark was applied to the alignment mark position. After coating, preliminary printing at 60 ° C. was performed, and pattern printing was performed on a PET substrate, which is a substrate to be printed, by the same process as in Example 1 except that a preliminary drying ink film was obtained.

  In Example 1 or Example 2, a high-definition pattern having excellent reproducibility can be printed stably, and the amount of ink used can be suppressed.

The printing method of the present invention is capable of continuously and stably performing thin film printing of a high-definition pattern on a flexible substrate such as a glass substrate or a plastic film, particularly a long flexible substrate, In addition, since the amount of ink used can be reduced, color filter members such as color patterns, black matrix, white matrix, spacers, gate electrodes, source electrodes, drain electrodes, gate insulating films, transistor members such as organic semiconductor materials, organic It can utilize for printing formation of organic EL elements, such as a light emitting layer.

It is explanatory drawing which shows an example of the printing method and printing apparatus which concern on one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 ... Unwinding part 102 of an ink peelable film base ... Coating part 103 ... Drying part 104 ... Letterpress bonding / pattern removal part 105 ... Alignment part 106 ... Adsorption Stage / bonding part 107 ... winding part 108 of the ink peelable film base material ... unwinding part 109 of the base material to be printed ... drying part 110 of the base material to be printed ... base material to be printed Winding part 111 of ink jet device 112 ... movable stage

Claims (9)

  An ink liquid film is applied on an ink peelable film substrate supplied from a take-up roll using an ink jet method to form an ink liquid film, and then the ink liquid film is preliminarily dried to prepare a predrying ink. A film is formed and pressed against the pre-dried ink film with a pattern forming surface of a relief printing plate having a concave portion provided in the shape of the pattern to be transferred and a convex portion provided in the shape of the pattern not to be transferred. The portion of the pre-dried ink film corresponding to the convex portion of the relief printing plate is transferred and removed, and then the portion of the pre-dried ink film remaining on the ink-removable film substrate is removed from the target substrate to be printed. A printing method characterized by transferring to a surface.   The pre-dried ink film has adhesiveness by pre-drying of the ink liquid film and maintains its shape, but at room temperature, only the part to which external force is applied by the convex part of the relief printing plate can be transferred and removed. The printing method according to claim 1, wherein the printing method is in a state.   The printing method according to claim 1 or 2, wherein the ink-peeling film base material is successively fed out from an unwinding portion and the new ink-peeling film base material is always used.   The printing method according to any one of claims 1 to 3, wherein the ink-peelable film substrate is formed by laminating a silicone resin layer on a film substrate. The ink releasable film base material is provided with either an inorganic oxide film of SiO ₂ , TiO ₂ , or ZrO ₂ on a film base material, or a composite oxide film thereof, and a layer of a silane coupling agent The printing method according to claim 1, wherein at least one of an alkyl group, a siloxane group, and a fluorine atom is located on the surface via   The ink-peelable film base material is provided with an oxide film on the film base material by a sol-gel method, and at least one of an alkyl group, a siloxane group, and a fluorine atom is surfaced through a layer of a silane coupling agent. The printing method according to any one of claims 1 to 3, wherein the printing method is located in the position.   The printing method according to claim 1, wherein the ink-peelable film substrate is optically transparent.   When transferring the portion consisting of the pre-dried ink film left on the ink-peelable film substrate to the surface of the substrate to be printed on which an image pattern is already provided, the substrate to be printed and the ink-peelable property are transferred. An image already provided on the surface of the substrate to be printed and the portion of the pre-dried ink film left on the film substrate of the ink peelability using an observation instrument while maintaining the parallel state with the film substrate of The printing method according to claim 1, wherein alignment with a pattern is performed.   9. A plate made of glass or resin is used as a relief plate for transferring and removing a part of the pre-dried ink film on the ink-peeling film substrate. The printing method described.

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