JP2012209040A - Letterpress for forming high definition pattern, method for manufacturing electronic circuit pattern, method for manufacturing organic el element and tabular photosensitive resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a letterpress for forming a high definition pattern by which a printing material for performing successful edge detection is obtained, and stable and high definition management of a press plate is performed by further using a defect inspection machine in combination even in the case of the letterpress using a base material such as a metal base material with high reflectance.SOLUTION: A letterpress has layer structure in which a layer for irregularly reflecting light within a wavelength area of at least 400 nm to 800 nm, a light transmission layer 103 laminated on the layer and for covering the layer so that the end and the end surface of the layer 104 is not exposed from the end and the end surface of the letterpress 100 for printing to the outside and a layer 102 having oil resistance, water resistance, or solvent resistance to which a surface regulator is added are sequentially laminated between a projection pattern 101 which is formed of a resin layer of the letterpress 100 for printing and a base material 105 made of metal for supporting the projection pattern 101.

Description

  The present invention relates to a printing relief plate for forming a high-definition pattern, a plate-like photosensitive resin laminate for the same, and an electronic circuit pattern and an organic EL element manufacturing method using the same.

  In recent years, the development of electronic devices using high-definition processing technology has made rapid progress. Such electronic devices are expected to contribute to the development of the next generation electronics field, biotechnology field, optronics field, and the like.

  One of the electronic devices described above is an organic EL element. In an organic EL element, a light emitting layer made of an organic light emitting material is formed between two opposing electrodes, and light is emitted by passing a current through the light emitting layer. Is important, and a thin film of about 100 nm is required. Further, in order to make this a display, it is necessary to pattern it with high definition.

  Organic light-emitting materials include low-molecular materials and high-molecular materials. In general, low-molecular materials are formed into thin films by resistance heating vapor deposition or the like, and then patterned using a fine pattern mask. There is a problem that the patterning accuracy is less likely to increase as the size increases. Therefore, a low molecular material is not suitable as an organic light emitting material used for a display having a large substrate.

  Therefore, recently, a method of using a polymer material as an organic light emitting material, dissolving the organic light emitting material in a solvent to form a coating liquid, and forming a thin film by a wet coating method has been tried. The wet coating method for forming a thin film includes a spin coating method, a bar coating method, a protruding coating method, a dip coating method, etc., but in order to pattern with high definition or separate into three colors of RGB These wet coating methods are difficult, and it is considered that thin film formation by a printing method, which is good at coating patterning, is most effective.

  Furthermore, among various printing methods, organic EL displays often use a glass substrate as a substrate. Therefore, a method using a hard plate such as a metal printing plate such as a gravure printing method is unsuitable and has elasticity. An offset printing method using a rubber plate and a relief printing method using a photosensitive resin plate mainly composed of rubber or other resin are suitable. Actually, as a trial of these printing methods, a method by offset printing (Patent Document 1), a method by letterpress printing (Patent Document 2) and the like have been proposed.

  By the way, generally, the circuit pattern of an electronic device has a high definition of several millimeters when it is large and a few nanometers when it is small.

  For example, in the case of an organic EL display, in a 2-inch diagonal, 320 pixels × 240 pixels (QVGA), which is becoming mainstream in recent years as a main display for mobile phones, one pixel size is 120 μm, and the display width per color is High-definition pattern formation of about 20 to 40 μm is required.

When an organic EL display is formed by sequentially forming a hole transport layer, a light emitting layer, an electron transport layer, a cathode layer, etc. on a substrate (TFT substrate) having an electronic circuit using a thin film transistor (TFT), it is called an active matrix type. It becomes a high-quality organic EL display. The TFT circuit used here is also formed from a high-definition circuit pattern of about several μm.

  For example, when a high-definition pattern suitable for an organic EL display is to be formed, the pattern accuracy such as total pitch accuracy and line width accuracy required for a circuit pattern is generally targeted within about ± 5%. As an absolute value, an accuracy of about 0.1 μm to 2 μm is required.

  When managing a high-definition pattern belonging to a normal electronic circuit pattern, length measurement is generally performed by a technique called an edge detection method. This method uses various light sources such as reflection, epi-illumination, and transmission, converts the image data obtained by an image input device such as a CCD camera into a digital image, and the edge of the pattern by the difference in contrast. By recognizing it, it is possible to perform management with high accuracy and hardly causing individual differences by the measurer.

  On the other hand, when printing printed matter such as advertisements and magazines, the pattern accuracy of the printing plate varies greatly depending on the pattern to be formed, but is ± 10% or more, and is often about 10 to 100 μm in absolute value.

  Confirmation of the pattern accuracy of printing plates used in these printed materials is often carried out with the naked eye or visually through a microscope. However, in such a method, individual differences may occur depending on the measurer. Many. However, the printing plate management by this method is sufficient in terms of the accuracy of the intended printed matter.

  On the other hand, since the required precision is about 0.1 μm to 2 μm in the printing plate for which high-definition pattern formation such as an organic EL display is required, it is visually observed using a microscope. However, sufficient measurement accuracy cannot be obtained only by measuring the length.

  Therefore, it is necessary to perform highly accurate measurement by an edge detection method or the like. In particular, when a metal plate is used as the base material of the printing plate for the purpose of dimensional stability, the exact edge of the plate's convex part cannot be detected due to the influence of irregular reflection of the measurement light generated on the metal plate, and the finish is finished. It was not possible to quantitatively evaluate the exact line width of the plate pattern in later plates.

  Then, in order to suppress irregular reflection of length measuring light by a metal plate, it has been studied to provide a light reflection suppressing layer between the base material and the convex forming layer (Patent Document 4). However, in the case of the method of Patent Document 4, although the edge detection is easy, the top and side surfaces of the convex pattern are colored black, so that there is no difference in contrast on the surface of the convex pattern. It is difficult to perform plate inspection using a defect inspection machine that inspects unevenness and foreign matter adhesion present on the top.

  In addition, in the plate configuration of the above-mentioned patent document, the adhesion with the base material is lowered by adding a black dye, and the problem is that the adhesiveness is low with respect to the continuous printability in a state where the printing pressure is continuously applied. When the dye is missing from the substrate to be printed during printing, there is a problem of causing defects in electronic circuits, elements, and displays. Moreover, regarding visibility, the improvement was confirmed by mixing an inorganic metal in the layer. However, a pattern due to uneven drying of the resin layer was confirmed as a new problem of the film formability of the resin itself. Due to the unevenness of drying, the defect inspection detects the uneven pattern of the ground in the part other than the pattern surface, and it takes a lot of processing time in the inspection of the original pattern surface and detects the ground pattern. There was a problem that pattern inspection could not be performed accurately.

JP 2001-93668 A JP 2001-155858 A JP 2004-70231 A JP 2008-229947 A

  The present invention has been made in view of the above-described circumstances, and the object thereof is to obtain a plate material capable of detecting a good edge even with a relief plate using a highly reflective substrate such as a metal substrate. Furthermore, a defect inspection machine can be used in combination to provide a relief plate that facilitates quality control of a printing plate. Another object of the present invention is to provide an electronic circuit and an organic EL element free from defects by preventing the loss of additives from the plate during printing.

  According to the first aspect of the present invention, the support base material is coated so as to cover the entire surface including the light irregular reflection layer that irregularly reflects light in the wavelength region of at least 400 nm to 800 nm and the end portion of the light irregular reflection layer. A light transmission layer, a protective layer having any of the properties of oil resistance, water resistance or solvent resistance, and a resin convex portion are laminated in this order, and the protective layer contains a surface conditioner. It is a relief relief for forming a high-definition pattern.

  According to a second aspect of the present invention, an entire surface including a light irregular reflection layer for irregularly reflecting light in a wavelength region of at least 400 nm to 800 nm on the support substrate and two opposite end portions of the light irregular reflection layer. A light-transmitting layer to be covered, a protective layer having any of oil resistance, water resistance or solvent resistance, and a resin convex portion are laminated in this order, and the protective layer is a surface conditioner. Is a relief printing plate for high-definition pattern formation.

  The invention according to claim 3 of the present invention is characterized in that the content of the surface conditioner in the protective layer is in the range of 0.1 to 3% by weight. It is a letterpress for pattern formation.

  The invention according to claim 4 of the present invention is the relief printing plate for high-definition pattern formation according to claim 3, wherein the surface conditioner contains a silicon-based resin.

  The invention according to claim 5 of the present invention is the relief printing plate for high-definition pattern formation according to claim 1 or 2, wherein the light diffuse reflection layer contains a pigment.

  A sixth aspect of the present invention is the relief printing plate for high-definition pattern formation according to the fifth aspect, wherein the pigment has a particle size in the range of 0.2 to 0.8 μm.

  The invention according to claim 7 of the present invention is the relief printing plate for high-definition pattern formation according to claim 5 or 6, wherein the pigment contains titanium oxide.

  The invention according to claim 8 of the present invention is characterized in that the adhesive force between the protective layer and the light transmission layer is 15 N / cm or more, and the high definition according to any one of claims 1 to 7. It is a letterpress for pattern formation.

  According to a ninth aspect of the present invention, the high-definition according to any one of the first to eighth aspects, wherein an adhesive force between the light diffuse reflection layer and the substrate is 10 N / cm or more. It is a letterpress for pattern formation.

  The high-definition device according to any one of claims 1 to 9, wherein an adhesive force between the light transmission layer and the base material is 15 N / cm or more. It is a letterpress for pattern formation.

  The eleventh aspect of the present invention is the relief printing plate for high-definition pattern formation according to any one of the first to tenth aspects, characterized in that the substrate is made of metal. is there.

  According to a twelfth aspect of the present invention, in the relief plate for forming a high-definition pattern according to any one of the first to eleventh aspects, the concave portion made of resin contains at least a photosensitive resin. Is.

  According to a thirteenth aspect of the present invention, an electronic circuit pattern is produced by printing using the relief pattern for forming a high-definition pattern according to any one of the first to twelfth aspects. It is what.

  According to a fourteenth aspect of the present invention, an organic EL element is produced by printing using the high-definition pattern forming relief plate according to any one of the first to twelfth aspects. It is what.

  The invention according to claim 15 of the present invention is characterized in that at least a support substrate, a light diffuse reflection layer, a light transmission layer, a protective layer containing a surface conditioning agent, and a photosensitive resin layer are laminated in this order. It is made into the shape photosensitive resin laminated body.

  According to the present invention, it is possible to obtain a plate material capable of good edge detection and plate defect inspection even with a relief plate using a highly reflective substrate such as a metal substrate, and a stable and highly accurate printing press. It became possible to perform quality control of the plate. Furthermore, by covering the light reflecting layer, it is possible to obtain a defect-free electronic circuit or organic EL element by preventing the addition of additives in the plate during printing and eliminating the contamination of the printed material. It was.

It is sectional drawing which shows the example of the relief printing plate in embodiment of this invention. It is the schematic which shows the shaping | molding method of the plate-shaped photosensitive resin laminated body which shape | molds the convex part pattern in embodiment of this invention. It is sectional drawing which shows the platemaking process of the photosensitive resin plate in embodiment of this invention. It is the schematic which shows the example of the flexographic printing machine in embodiment of this invention. It is the schematic which shows the example of the organic EL element in embodiment of this invention. It is the schematic which shows the board | substrate example of the active matrix system of the organic EL element in embodiment of this invention. It is a figure which shows the plate which coated the surface additive which concerns on the Example of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to this.

FIG. 1 shows a cross-sectional view of an example of a high-definition pattern forming relief according to the present invention. As shown in FIG. 1, a high-definition pattern forming relief plate 100 of the present embodiment (hereinafter simply referred to as a printing relief plate 100) has a light irregular reflection layer 104 formed on a base material 105, and further the light irregular reflection. The light irregular reflection layer 104 is covered with the light transmission layer 103 so that the end and end face of the layer 104 are not exposed to the outside from the end of the printing relief plate 100. A layer 102 is laminated on the light transmission layer 103, and a plurality of convex patterns 101 formed of a resin layer are formed on the layer 102. In the present embodiment, each convex pattern 101 is arranged at an interval from the adjacent convex pattern 101, and each convex pattern 101 is independent of other convex patterns 101. However, the convex pattern 101 may be formed so as to be continuously connected to the adjacent convex pattern 101.

  As described above, in the present embodiment, the end portion and the end surface of the light irregular reflection layer 104 are arranged on the inner side of the end portion of the printing relief plate 100 so as not to be exposed to the outside of the printing relief plate 100. When the end portion and the end face of the light irregular reflection layer 104 are exposed to the outside at the end portion of the printing relief plate 100, the diffuse reflection of light from the end portion and the end face portion of the light irregular reflection layer 104 exposed from the end portion when the printing relief plate 100 is used. A part of the layer 104 is missing, which is not preferable because it adheres to the substrate and causes defects. In principle, there is no problem as long as the light irregular reflection layer 104 is positioned inside the end portion of the printing relief plate 100. However, just in case, the light irregular reflection layer 104 is not exposed to the outside of the printing relief plate 100. In addition, a light transmission layer 103 covering the diffused reflection layer 104 is provided. The light transmission layer 103 may also serve as the layer 102 having oil resistance, water resistance, and solvent resistance.

  Note that the coating of the end portion, particularly the end face, of the light irregular reflection layer 104 depends on the method of manufacturing the relief printing plate 100, but it may be difficult to completely cover the light transmission layer 103 in a specific direction. In general, if the relief printing plate has a long shape, the light diffuse reflection layer is also formed in a long shape on the inside thereof. However, the entire surface of the light transmission layer 103 is only covered so as to cover only the opposite ends of the light diffuse reflection layer. It may not be possible to coat with. Specifically, the light diffuse reflection layer 104 is inevitably exposed at the two end faces in the direction perpendicular to the extending direction as shown in the sectional views of FIGS. 1 to 3. That's what it means.

  In the plate material used for the printing relief plate 100 of this embodiment, the base material 105 on which the convex pattern 101 is formed via the layer 102, the light transmission layer 103, and the light irregular reflection layer 104 is a mechanical component for printing. Any material having strength may be used, such as polyethylene, polystyrene, polybutadiene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyamide, polyethersulfone, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, and polyvinyl alcohol. A known resin such as a synthetic resin, iron, copper, or aluminum, or a laminate thereof can be used.

  In particular, as the base material 105 constituting the printing relief plate 100 of the present embodiment, one that maintains high dimensional stability is desirable. Therefore, a metal is more preferable as a material used as the base material 105. Examples of the metal used as the base material 105 include iron, aluminum, copper, zinc, nickel, titanium, chromium, gold, silver, alloys thereof, and laminates. In particular, iron is mainly used from the viewpoint of workability and economy. A steel base material or aluminum base material as a component can be suitably used.

  Polymers that are one component of the resin used for the material of the convex pattern 101 of the printing relief plate 100 are nitrile rubber, silicone rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, butyl rubber, acrylonitrile rubber, ethylene propylene rubber, In addition to rubber such as urethane rubber, polyethylene, polystyrene, polybutadiene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyamide, polyurethane, polyethersulfone, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyvinyl alcohol, etc. One or more types can be selected from synthetic resins, their copolymers, natural polymers such as cellulose, etc., but when applying coating liquids such as organic light emitting materials, organic From the viewpoint of solvent resistance, polyamide or fluorine-based elastomer and polytetrafluoroethylene, polyvinylidene fluoride, a resin such as poly hexafluoride vinylidene and copolymers thereof it is preferred for agents.

  Further, polyether amide, polyether ester amide, tertiary nitrogen-containing polyamide, ammonium salt type tertiary nitrogen atom-containing polyamide, addition polymer of amide compound having at least one amide bond and organic diisocyanate compound, polyvinyl alcohol, polyurethane, Solvent resistance can also be imparted by containing at least one kind soluble in water-soluble solvents such as cellulose acetate succinate, partially saponified polyvinyl acetate, cationic piperazine-containing polyamide and derivatives thereof. Furthermore, since development using alcohol or water becomes possible, it is desirable to select one or more of these and use them as a polymer that is a component of the resin used for the material of the convex pattern 101. Of these, tertiary nitrogen atom-containing polyamides and ammonium salt type tertiary nitrogen atom-containing polyamides are preferred.

  The photosensitive resin layer used for the convex pattern 101 of this embodiment contains a crosslinking agent (also referred to as an ethylenically unsaturated compound), a photoinitiator composition, and a polymerization inhibitor in addition to the resin. Still other additives such as thermal polymerization inhibitors, dyes, pigments or antioxidants may be included.

  Suitable crosslinking agents (ethylenically unsaturated compounds) include dipentaerythritol, pentaerythritol, trimethylolpropane, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, phthalic acid, ethylene oxide adduct, bisphenol A, Diglycidyl ether acrylic acid adduct of bisphenol F, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) Addition reaction product of poly (glycidyl ether) such as acrylate and dipentaerythritol penta (meth) acrylate and (meth) acrylic acid, such as adipic acid Examples include, but are not limited to, polyunsaturated compounds such as a reaction adduct of a polyvalent carboxylic acid and glycidyl (meth) acrylate, an addition reaction product of a polyvalent amine such as propylenediamine and glycidyl (meth) acrylate, and the like. In addition, two or more of these compounds can be mixed and used.

  Examples of the photoinitiator composition used in the photosensitive resin layer of the convex pattern 101 of this embodiment include benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals, anthraquinones And thioxanthones. Specifically, benzophenone, chlorobenzophenone, benzoin, acetophenone, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl diisopropyl ketal, anthraquinone, 2-ethylanthraquinone , 2-methylanthraquinone, 2-allylanthraquinone, 2-chloroanthraquinone, thioxanthone, 2-chlorothioxanthone and the like.

In the photosensitive resin layer of the convex pattern 101 of this embodiment, the polymerization inhibitor is used to make the edge of the convex pattern 101 an acute angle. As this polymerization inhibitor, those commercially available can be used. Examples include benzophenones, benzotriazoles, and cyanoacrylates. Specifically, p-benzoquinone, oxybenzone, 4-tert-butyl-4-methoxy-benzoylmethane, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′- Tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4′-benzophenone dimethoxy, 1,4-bis (4-benzoyl-3-hydroxy) Among them, benzophenones are preferable.

The diffuse light reflection layer 104 may be any layer that diffuses light with respect to light having a wavelength range of 400 nm to 800 nm, which is general observation light of a measuring apparatus. Although the light after irregular reflection may exhibit various colors such as deep blue, deep green, deep red, and deep orange depending on the absorption spectrum, it is desirable that the light is white. As the material of the light diffuse reflection layer 104, zinc oxide, titanium oxide, zirconium oxide, or the like is used. Among these, titanium oxide is more preferable because it has excellent concealability and whiteness. In the case of mainly white pigments, the hiding power is considered to be the same as light scattering, and the optimum titanium oxide particle size is calculated from the following equation.
D = 2λ / {π (n1−n2)} (1)
Where D: particle diameter λ: wavelength of light n1: refractive index of pigment, n2: refractive index of resin.
Here, when the refractive index of titanium oxide is n1 = 2.5 to 2.7, the refractive index n2 of the resin is 1.5 to 1.6, and the wavelength of light λ is 400 to 800 nm, the optimum titanium oxide is obtained. The particle size is 0.2 to 0.8 μm. Therefore, when the refractive indexes n1 and n2 of the titanium oxide and the resin and the light wavelength λ are in the above-described ranges, it is more preferable to use titanium oxide having a particle size in the range of 0.2 to 0.8 μm. desirable. However, although the pigment described above may be used, it is necessary to make the calculated particle diameter according to the formula (1).

  Further, the light irregular reflection layer 104 and the light transmission layer 103 are required to firmly bond the base material 105 to the oil-resistant / water-resistant / solvent-resistant layer 102 or the photosensitive resin layer (layer constituting the convex pattern 101). Therefore, for these layers 103 and 104, it is preferable to use a polyester urethane adhesive, an epoxy adhesive, or the like obtained by curing a soluble polyester with a polyvalent isocyanate. Among them, polyester urethane adhesives are preferable because they are excellent in both adhesion, and among polyester urethane adhesives, an adhesive composed of polyester and isocyanurate type polyisocyanate is particularly desirable.

  In the present embodiment, the polyester urethane adhesive added with titanium oxide is used as the light diffuse reflection layer 104, and the one not added with titanium oxide is used as the light transmission layer 103. However, the light diffuse reflection layer is not particularly limited. The adhesive force between 104 and the substrate 105 may be 10 N / cm or more, and the adhesive force between the light transmission layer 103 and the substrate 105 may be 15 N / cm or more. If it is less than this value, the substrate 105 and the layers 103 and 104 are peeled off or missing during printing or handling, which is not preferable.

  Further, the layer 102 to which the surface adjusting agent in the layer is applied so as not to be exposed outward from the end and end face of the relief printing plate of the present invention is 0.1% to 3% surface adjustment in the resin. It is desirable to add an agent, and typical surface conditioning agents include acrylic, vinyl, silicon, and fluorine. In the present invention, silicon results show good results from matching with the resin used. However, the present invention is not limited to this. It is preferable to add the same resin as that used in the light transmission layer 103. It is preferable to take a form that prevents a decrease in adhesion, and in the case of multiple laminations, a force is applied due to the resin in the lower layer part being different from this, and this lamination part is prevented from being easily peeled off. Alternatively, a polymerization initiator or a polymerizable monomer may be used for the resin, and the polymerizable monomer may be cross-linked by photopolymerization or thermal polymerization to have adhesiveness. Examples of the polymerizable monomer include dipentaerythritol, pentaerythritol, trimethylolpropane, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, diglycidyl ether acrylic acid adduct of bisphenol A and bisphenol F, and ethylene glycol di (meth) acrylate. , Polyvalent glycidyl ethers such as neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate and (Meth) acrylic acid addition reaction product, reaction addition product of polycarboxylic acid such as adipic acid and glycidyl (meth) acrylate, propylene Examples include, but are not limited to, polyunsaturated compounds such as an addition reaction product of a polyvalent amine such as range amine and glycidyl (meth) acrylate. The solvent resistant layer used as the layer 102 is desirably as flat as possible. This is because the presence of irregularities, bubbles, etc. is not preferable because irregularities, bubbles, etc. are detected in addition to the defects of the resin convex portion during defect inspection. When the addition rate is less than 0.1%, uneven drying is observed on the surface, and the surface becomes uneven. When the addition rate is more than 3%, aggregates are confirmed in the resin. Precision version control was not possible. Further, the adhesive strength between the oil-resistant or water-resistant, solvent-resistant layer and the light transmission layer is preferably 15 N / cm or more, and when it is less than 15 N / cm, the substrate 103 and the layer 102 are not peeled or printed during printing or handling. It is not preferable because it is missing and becomes a foreign matter.

  The convex pattern 101 by the photosensitive resin layer in this embodiment is a photolithography method using a positive photosensitive resin, a photolithography method using a negative photosensitive resin, injection molding, a relief printing method, an intaglio printing method, Various pattern molding methods such as lithographic printing method, stencil printing method, laser ablation method can be used, but from the viewpoint of high definition of pattern, photolithography method using photosensitive resin is desirable and required accuracy A photolithography method using a negative photosensitive resin capable of forming a relief printing plate is most desirable.

  When a photolithography method using a photosensitive resin is applied as a method for forming the convex pattern 101, the base material 105, the light irregular reflection layer 104, the light transmission layer 103, and an oil or water resistance and solvent resistance to which a surface conditioner is added. It is most desirable to form the convex pattern 101 of the printing relief plate 100 from a plate-like photosensitive resin laminate in which the photosensitive resin layers constituting the layer 102 and the convex pattern 101 are sequentially laminated. As a method for molding the photosensitive resin layer, a known method such as an injection molding method, a protruding molding method, a laminating method, a bar coating method, a slit coating method, or a comma coating method can be used.

  FIG. 2 shows a method for molding the plate-like photosensitive resin laminate constituting the convex pattern 101 in the present embodiment.

  First, as shown in FIGS. 2A to 2C, the light irregular reflection layer 104 and light transmission are applied to the base material 105 by wet coating methods such as bar coating, slit coating, spray coating, flexographic printing, and gravure printing. A layer 103 and an oil-resistant or water-resistant and solvent-resistant layer 102 to which a surface conditioner is added are sequentially formed to form a laminate 106.

  Next, as shown in FIG. 2D, a known method such as injection molding, protruding molding, laminating, bar coating, slit coating, or comma coating is applied to the laminate 106 with the photosensitive resin layer 107. To form a plate-like photosensitive resin laminate 108.

  Next, when the convex pattern 101 is formed on the plate-shaped photosensitive resin laminate 108 by a photolithography method, a water-developable negative photosensitive resin is used as an example of the printing relief plate 100 of this embodiment. The case where it uses for the material of the plate-shaped photosensitive resin laminated body 108 is demonstrated.

  FIG. 3 shows a cross-sectional view of the plate making process of the convex pattern 101 in the printing relief plate 100. First, as shown in FIG. 3A, a plate-like photosensitive resin laminate 108 is prepared.

  Next, as shown in FIG. 3B, a photomask 303 is placed on the photosensitive resin. The photomask 303 is configured by forming a pattern made of, for example, a chromium thin film on a light-transmitting glass 304, and the light shielding portion 301 formed with the chromium thin film and the glass 304 are exposed without forming the chromium thin film. A translucent portion 302. In the photomask 303, light is blocked by the light shielding portion 301 and light is transmitted by the light transmitting portion 302.

  Next, as shown in FIG. 3C, the plate-shaped photosensitive resin laminate 108 is irradiated with an actinic ray 305 typified by ultraviolet light through a photomask 303, and the photosensitive resin layer 107 is exposed to the photomask. Exposure is performed according to the pattern 303. At this time, the portion of the photosensitive resin layer 107 irradiated with actinic rays through the light-transmitting portion 302 of the photomask 303 is cured, but desired patterning can be obtained even if the irradiation amount is too large or too small. I can't.

  Next, the photomask 303 is removed from the plate-like photosensitive resin laminate 108, and development is performed. By this development, the uncured portion that was not irradiated with light by the previous exposure is removed, and the relief printing plate 100 is obtained. At this time, when the water developing type photosensitive resin layer 107 in which the uncured portion can be dissolved and removed by water is used, water is used as the developing solution.

  Next, an apparatus for manufacturing an organic EL element will be described as an example of a circuit pattern manufacturing apparatus using the printing relief plate 100 on which the convex pattern 101 is formed by the plate making process of the present embodiment. In addition, the circuit pattern which can be produced with the manufacturing apparatus using the relief printing plate according to the present invention is not limited to the organic EL element.

  FIG. 4 shows a schematic diagram of an example of a flexographic printing machine according to an embodiment of the manufacturing apparatus of the present invention. A printing substrate 406 is fixed to the stage 407. The printing relief plate 100 on which the convex pattern 101 is formed by the plate making process of this embodiment is fixed to the plate cylinder 405. The printing relief plate 100 is an ink supply. The anilox roll 408 is in contact with a certain anilox roll 408, and includes an ink replenishing device 401, an ink chamber 402, and a doctor 403.

  First, ink is replenished from the ink replenishing device 401 to the anilox roll 408 via the ink chamber 402, and excess ink out of the ink supplied to the anilox roll 408 is removed by the doctor 403. The ink replenishing device 401 may be a dripping type ink replenishing device, a fountain roll, a slit coater, a die coater, a coater such as a cap coater, or a combination thereof. For the doctor 403, a known object such as a doctor roll can be used in addition to the doctor blade. The anilox roll 408 can be made of chromium or ceramics. Further, instead of the cylindrical anilox roll 408, a flat anilox plate can be used as an ink supply to the printing relief plate 100. The flat anilox plate is disposed, for example, at the position of the printing substrate 406 in FIG. 4. After the ink is replenished to the entire surface of the anilox plate by an ink replenishing device, the plate cylinder 405 is rotated to apply ink to the printing substrate. Supply can be made.

  The ink uniformly held by the doctor 403 on the surface of the anilox roll 408 which is an ink supply body to the printing relief plate 100 is transferred and supplied to the projection pattern 101 of the printing relief plate 100 attached to the plate cylinder 405. . Then, as the plate cylinder 405 rotates, the convex pattern 101 of the printing relief plate 100 and the printing substrate 406 move relatively in contact with each other, and the ink is transferred to a predetermined position on the printing substrate 406 on the stage 407. An ink pattern is formed on the substrate to be printed 406. After the ink pattern is provided on the substrate to be printed 406, a drying process using an oven or the like can be provided as necessary.

The method of printing the ink on the printing relief plate 100 on the printing substrate 406 may be a method of moving the stage 407 on which the printing substrate 406 is fixed in accordance with the rotation of the plate cylinder 405. Even if the printing substrate 405 is kept stationary, a printing unit including the plate cylinder 405, the printing relief plate 100, the anilox roll 408, and the ink replenishing device 401 in the upper part of FIG. 4 is moved according to the rotation of the plate cylinder 405. Good. Further, the printing relief plate 100 used in the flexographic printing machine (letter printing apparatus) of the present embodiment is not limited to the one attached on the plate cylinder 405 after the formation of the projection pattern 101. For example, the printing relief plate 100 in which the convex portion pattern 101 is formed by directly forming the resin layer on the plate cylinder 405 and directly making the resin layer may be used.

  FIG. 4 shows a sheet-fed relief printing apparatus that forms an ink pattern on a substrate to be printed one by one. However, when the substrate to be printed 405 can be wound in a web shape, roll-to- A roll type letterpress printing apparatus can also be used. When a roll-to-roll type letterpress printing apparatus is used, it is possible to continuously form an ink pattern and to reduce the manufacturing cost.

  Next, an organic EL element is demonstrated as an example of the printed matter which can be manufactured using the relief printing apparatus of FIG. In addition, the printed matter which can be manufactured using the relief printing apparatus of FIG. 4 is not restricted to this. The relief printing apparatus shown in FIG. 4 can also be used to manufacture general-purpose electronic circuit patterns such as TFTs. FIG. 5 shows a cross-sectional view of the organic EL element. As a driving method of the organic EL element, there are a passive matrix type and an active matrix type. The relief printing apparatus shown in FIG. 4 can be used for manufacturing either a passive matrix type organic EL element or an active matrix type organic EL element. Applicable.

  The passive matrix method is a method in which stripe-shaped electrodes are opposed to each other so as to be orthogonal to each other, and light is emitted at the intersection, whereas the active matrix method uses a so-called thin film transistor (TFT) substrate in which a transistor is formed for each pixel. Thus, the light is emitted independently for each pixel.

  As shown in FIG. 5, the organic EL element of this embodiment has a first electrode 502 in a stripe shape as an anode on a substrate 501. The partition wall 505 is provided between the first electrodes 502 and preferably covers the end portion of the first electrode 502 for the purpose of preventing a short circuit due to burrs at the end portion of the first electrode 502.

  The organic EL element of the present embodiment has an organic EL layer composed of an organic light emitting layer and a light emission auxiliary layer in a region (light emitting region, pixel portion) partitioned by the partition 505 on the first electrode 502. ing. The organic EL layer sandwiched between the electrodes may be composed of an organic light emitting layer alone, or may be composed of a laminated structure of an organic light emitting layer and a light emission auxiliary layer. Examples of the light emission auxiliary layer include a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and a charge generation layer. FIG. 5 shows a structure having a laminated structure of a hole transport layer 503 which is a light emission auxiliary layer and organic light emitting layers (508, 509, 510). A hole transport layer 503 is provided on the first electrode 502, and a red (R) organic light emitting layer 508, a green (G) organic light emitting layer 509, and a blue (B) organic light emitting layer 510 are provided on the hole transport layer 503, respectively. Is provided.

  Next, the second electrode 504 is disposed as a cathode on the organic light emitting layer (508, 509, 510) so as to face the first electrode 502 as the anode. In the case of the passive matrix system, the second electrode 504 is provided in a stripe shape so as to be orthogonal to the first electrode 502 having a stripe shape. In the case of the active matrix method, the second electrode 504 is formed on the entire surface of the organic EL element. Further, in order to prevent intrusion of moisture and oxygen in the environment to the first electrode 502, the organic light emitting layer (508, 509, 510), the light emission auxiliary layer (hole transport layer 503), and the second electrode 504, the effective pixel entire surface is prevented. On the other hand, a sealing body such as a glass cap 506 is provided, and is attached to the substrate 501 through an adhesive 507.

The organic EL element of this embodiment includes at least a substrate 501, a patterned first electrode 502 supported on the substrate 501, organic light emitting layers (508, 509, 510), and a second electrode 5.
04. The organic EL element of the present invention may have a structure in which the first electrode 502 is a cathode and the second electrode 504 is an anode, contrary to FIG. In addition, in order to protect the organic optical medium layer and the electrode from the ingress of external oxygen and moisture in place of the sealing body such as the glass cap 506, the function of the passivation layer, the protective layer protecting from the external stress, or both functions You may provide the sealing base material provided with.

  Next, the manufacturing method of an organic EL element is demonstrated. As the substrate according to the present invention, any substrate can be used as long as it has an insulating property. In the case of a bottom emission type organic EL element that extracts light from the substrate side, it is necessary to use a transparent substrate.

  For example, a glass substrate or a quartz substrate can be used as the substrate. Further, it may be a plastic film or sheet such as polypropylene, polyethersulfone, polycarbonate, cycloolefin polymer, polyacrylate, polyamide, polymethyl methacrylate, polyethylene terephthalate, or polyethylene naphthalate. Metal oxide thin film, metal fluoride thin film, metal nitride thin film, metal oxynitride thin film, or polymer resin film for the purpose of preventing moisture from entering the organic light emitting medium layer in these plastic films and sheets You may utilize what laminated | stacked these as a board | substrate.

  In addition, it is more preferable to reduce the moisture adsorbed on the inside or the surface of the substrate as much as possible by performing a heat treatment on these substrates in advance. Further, in order to improve the adhesion depending on the material to be laminated on the substrate, it is preferable to use after performing surface treatment such as ultrasonic cleaning treatment, corona discharge treatment, plasma treatment, UV ozone treatment.

  Further, a thin film transistor (TFT) can be formed on these to form a substrate for an active matrix organic EL element. FIG. 6 shows an explanatory cross-sectional view of an example of the active matrix substrate of the present invention. In the case of the organic EL element substrate 601 of the present invention, the planarization layer 610 is formed on the TFT 613, and the lower electrode (first electrode 602) of the organic EL element is provided on the planarization layer 610. The TFT 613 and the lower electrode (first electrode 602) are preferably electrically connected through a contact hole 611 provided in the planarization layer 610. With this configuration, excellent electrical insulation can be obtained between the TFT 613 and the organic EL element.

  The TFT 613 and the organic EL element formed above the TFT 613 are supported by a support 604. The support 604 is preferably excellent in mechanical strength and dimensional stability. Specifically, the materials described above as the substrate 601 can be used.

  As the TFT 613 provided over the support 604, a known thin film transistor can be used. Specifically, a thin film transistor (TFT) 613 composed mainly of an active layer 605 in which a source / drain region and a channel region are formed, a gate insulating film 606, and a gate electrode 607 can be given. The structure of the thin film transistor (TFT) 613 is not particularly limited, and examples thereof include a staggered type, an inverted staggered type, a top gate type, and a coplanar type.

The active layer 605 is not particularly limited, and examples thereof include inorganic semiconductor materials such as amorphous silicon, polycrystalline silicon, microcrystalline silicon, and cadmium selenide, thiophene oligomers, and organic materials such as poly (p-ferylene vinylene). It can be formed of a semiconductor material. These active layers are formed by, for example, laminating amorphous silicon by plasma CVD, ion doping, forming amorphous silicon by LPCVD using SiH ₄ gas, and crystallizing amorphous silicon by solid phase growth. After obtaining silicon, ion doping is performed by ion implantation, LPCVD using Si ₂ H ₆ gas, and amorphous silicon is formed by PECVD using SiH ₄ gas, and laser such as excimer laser is used. After annealing and crystallizing amorphous silicon to obtain polysilicon, polysilicon is laminated by ion doping (low temperature process), low pressure CVD or LPCVD, and thermally oxidized at 1000 ° C. or higher. Gate break Film is formed, a gate electrode 607 of the n + polysilicon is formed thereon, then, a method of ion doping (high temperature process), and the like by an ion implantation method.

As the gate insulating film 606, a film normally used as a gate insulating film can be used. For example, SiO ₂ formed by PECVD, LPCVD, etc., SiO obtained by thermally oxidizing a polysilicon film ₂ etc. can be used.

  As the gate electrode 607, a material usually used as a gate electrode can be used. For example, a metal such as aluminum or copper, a refractory metal such as titanium, tantalum, or tungsten, polysilicon, or a silicide of a refractory metal. And polycide.

  The TFT 613 may have a single gate structure, a double gate structure, or a multi-gate structure having three or more gate electrodes. Moreover, you may have a LDD structure and an offset structure. Further, two or more thin film transistors may be arranged in one pixel.

  A display using an organic EL element needs to be connected so that the thin film transistor (TFT) 613 functions as a switching element of the organic EL element. The drain electrode 609 of the thin film transistor (TFT) 613 and the pixel electrode (first electrode) of the organic EL element One electrode 602) is electrically connected. Furthermore, it is generally necessary to use a metal that reflects light for the pixel electrode (first electrode 602) for adopting a top emission structure.

  The TFT 613, the drain electrode 609, and the pixel electrode (first electrode 602) of the organic EL element are connected via a connection wiring formed in a contact hole 611 that penetrates the planarization film 610.

As for the material of the planarizing film 610, inorganic materials such as SiO ₂ , spin-on glass, SiN (Si ₃ N ₄ ), TaO (Ta ₂ O ₅ ), organic materials such as polyimide resin, acrylic resin, photoresist material, and black matrix material are used. Materials and the like can be used. According to these materials, a spin coating, a CVD, a vapor deposition method or the like can be selected as the lamination method. If necessary, a contact hole is formed by dry etching, wet etching, or the like at a position corresponding to the lower TFT 613 after photolithography using a photosensitive resin as the planarizing layer 610 or by forming the planarizing layer 610 once on the entire surface. 611 is formed. The contact hole 611 is then filled with a conductive material to be electrically connected to the pixel electrode (first electrode 602) formed on the planarization layer 610. The thickness of the planarization layer 610 only needs to cover the lower TFT 613, the capacitor, the wiring, and the like, and the thickness may be several μm, for example, about 3 μm.

  A first electrode 602 is provided on the substrate. When the first electrode 602 is used as an anode, the material is a metal such as ITO (indium tin composite oxide), IZO (indium zinc composite oxide), tin oxide, zinc oxide, indium oxide, and zinc aluminum composite oxide. A single layer or laminated layer of metal materials such as composite oxide, gold, platinum, and chromium can be used. As a method for forming the first electrode 602, a dry film forming method such as a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used depending on the material.

  In addition, ITO is preferably used because of its low resistance, solvent resistance, and high transparency when the bottom mission method is adopted. ITO is formed on the glass substrate by a sputtering method and patterned by a photolithography method to form the first electrode 602.

  After forming the first electrode 602, the partition wall 603 is formed so as to cover the edge of the first electrode. The partition wall 603 needs to have insulating properties, and a photosensitive material or the like can be used. The photosensitive material may be a positive type or a negative type, a photo-curing resin of a photo radical polymerization system, a photo cationic polymerization system, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol. , Novolac resin, polyimide resin, cyanoethyl pullulan, and the like can be used. In addition, as a material for forming the partition wall 603, SiO2, TiO2, or the like can be used.

  When the forming material of the partition wall 603 is a photosensitive material, the forming material solution is coated on the entire surface by a slit coating method or a spin coating method, and then patterned by a photolithography method such as exposure and development. In the case of the spin coating method, the height of the partition wall 603 can be controlled by conditions such as the number of rotations when spin coating is performed, but there is a limit height in one coating, and when it is further increased, the spin coating is performed multiple times. Is used.

  When the partition 603 is formed by a photolithography method using a photosensitive material, the shape of the partition 603 can be controlled by exposure conditions and development conditions. For example, when a negative photosensitive resin is applied, exposed / developed, and post-baked to obtain the partition wall 603, the end portion of the partition wall 603 has a forward tapered shape. The type, concentration, temperature, or development time of the developer may be controlled. If the development condition is mild, the end of the partition wall 603 has a forward tapered shape, and if the development condition is severe, the end of the partition wall 603 has a reverse tapered shape.

Further, when the material for forming the partition wall 603 is SiO ₂ or TiO ₂ , the partition wall 603 can be formed by a dry film formation method such as a sputtering method or a CVD method. In this case, patterning of the partition wall 603 can be performed by a mask or a photolithography method.

  Next, an organic EL layer composed of an organic light emitting layer and a light emission auxiliary layer is formed. The organic EL layer sandwiched between the electrodes may be composed of an organic light emitting layer alone, an organic light emitting layer and a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a charge generation layer, etc. It is good also as a laminated structure with the light emission auxiliary layer for assisting light emission. The hole transport layer, hole injection layer, electron transport layer, electron injection layer, and charge generation layer are appropriately selected as necessary.

  In the present invention, at least one of the organic EL layers composed of a light emitting auxiliary layer such as an organic light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and a charge generation layer is used as an organic EL layer material. When printing is formed above the first electrode 602 by a relief printing method using a resin relief plate having a projection pattern made of resin on a base material using an ink dissolved or dispersed in a solvent. Can be applied to. Hereinafter, a case where an organic light emitting ink in which an organic light emitting material is dissolved or dispersed in a solvent is used will be described.

  The organic light emitting layer is a layer that emits light when an electric current is passed. Organic light-emitting materials formed by the organic light-emitting layer include 9,10-diarylanthracene derivatives, pyrene, coronene, perylene, rubrene, 1,1,4,4-tetraphenylbutadiene, tris (8-quinolato) aluminum complex, tris (4-methyl-8-quinolato) aluminum complex, bis (8-quinolato) zinc complex, tris (4-methyl-5-trifluoromethyl-8-quinolato) aluminum complex, tris (4-methyl-5-cyano-) 8-quinolate) aluminum complex, bis (2-methyl-5-trifluoromethyl-8-quinolinolate) [4- (4-cyanophenyl) phenolate] aluminum complex, bis (2-methyl-5-cyano-8-quinolinolate) [4- (4-cyanophenyl) phenolate] aluminum complex, Lis (8-quinolinolato) scandium complex, bis [8- (para-tosyl) aminoquinoline] zinc complex and cadmium complex, 1,2,3,4-tetraphenylcyclopentadiene, poly-2,5-diheptyloxy- A low molecular weight light emitting material such as para-phenylene vinylene can be used.

Also, coumarin phosphors, perylene phosphors, pyran phosphors, anthrone phosphors, polyphyrin phosphors, quinacridone phosphors, N, N′-dialkyl-substituted quinacridone phosphors, naphthalimide phosphors, A material obtained by dispersing a low molecular weight light emitting material such as an N, N′-diaryl-substituted pyrrolopyrrole fluorescent material or a phosphorescent light emitting material such as an Ir complex in a polymer can be used. As the polymer, polystyrene, polymethyl methacrylate, polyvinyl carbazole and the like can be used.
Further, poly (2-decyloxy-1,4-phenylene) (DO-PPP) and poly [2,5-bis- [2- (N, N, N-triethylammonium) ethoxy] -1,4-phenyl- PPP derivatives such as alto-1,4-phenyllene] dibromide, poly [2- (2′-ethylhexyloxy) -5-methoxy-1,4-phenylenevinylene] (MEHPPV), poly [5-methoxy- ( 2-propanoxysulfonide) -1,4-phenylenevinylene] (MPS-PPV), poly [2,5-bis- (hexyloxy) -1,4-phenylene- (1-cyanovinylene)] (CN— Polymer light-emitting materials such as PPV), poly (9,9-dioctylfluorene) (PDAF), and polyspirofluorene may be used. Furthermore, polymer precursors, such as a PPV precursor and a PPP precursor, are mentioned. Other existing light emitting materials can also be used.

  Examples of the hole transport material forming the hole transport layer include metal phthalocyanines such as copper phthalocyanine and tetra (t-butyl) copper phthalocyanine, and metal-free phthalocyanines, quinacridone compounds, 1,1-bis (4-di-p -Tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N′-di (1- Naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine and other aromatic amine-based low molecular hole injection transport materials, polyaniline, polythiophene, polyvinylcarbazole, poly (3,4 -Ethylenedioxythiophene) and polymer hole transport materials such as polystyrene sulfonic acid mixtures, thiophene oligomer materials, and other existing positive It can be selected from among transport material.

  When an inorganic material is used as the hole transport material, the inorganic material includes chromium (Cr), tungsten (W), vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), titanium (Ti ), Zirconium (Zr), hafnium (Hf), scandium (Sc), yttrium (Y), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni) ), Copper (Cu), zinc (Zn), cadmium (Cd) and other oxides, nitrides, and oxynitrides can be formed using a vacuum evaporation method. By providing a hole transport layer made of an inorganic material, a more stable organic EL device having excellent thermal stability and resistance can be obtained.

  Examples of the electron transport material for forming the electron transport layer include 2- (4-biphenyl) -5- (4-tetrabutylphenyl) -1,3,4-oxadiazole, 2,5-bis (1- Naphthyl) -1,3,4-oxadiazole, oxadiazole derivatives, bis (10-hydroxybenzo [h] quinolinolato) beryllium complexes, triazole compounds, and the like can be used.

Solvents that dissolve or disperse the organic light emitting material include toluene, xylene, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, 2-methyl- (t-butyl) Benzene, 1,2,3,4-tetramethylbenzene, pentylbenzene, 1,3,5-triethylbenzene, cyclohexylbenzene, 1,3,5-tri-isopropylbenzene and the like can be used alone or in combination. . Moreover, surfactant, antioxidant, a viscosity modifier, a ultraviolet absorber, etc. may be added to organic luminescent ink as needed.

  Examples of the solvent for dissolving or dispersing the hole transport material and the electron transport material include, for example, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, water and the like Alternatively, a mixed solvent thereof can be used. In particular, water or alcohols are suitable when forming a hole transport material into an ink.

  The organic light emitting layer and the light emission auxiliary layer are formed by a wet film forming method. Note that in the case where these layers have a laminated structure, it is not necessary to form all of the layers by a wet film formation method. As the wet film forming method, spin coating method, die coating method, dip coating method, discharge coating method, pre-coating method, roll coating method, bar coating method and the like, relief printing method, inkjet printing method, offset printing method, Examples of the printing method include a gravure printing method. In particular, when patterning organic light emitting layers of three colors of RGB, it can be selectively formed on the pixel portion by a printing method, and an organic EL element capable of color display can be manufactured. The film thickness of the organic light emitting medium layer is 1000 nm or less, preferably 50 nm to 150 nm, even when formed by a single layer or stacked layers.

  Again, the present invention is not only for forming an organic light emitting layer by a relief printing method using an organic light emitting ink, but also for a hole transport layer or an electron transport layer by a relief printing method using a hole transport ink or an electron transport ink. It can also be used when forming a light emission auxiliary layer.

  Next, a second electrode is formed. When the second electrode is a cathode, a material having high electron injection efficiency is used as the material. Specifically, a single metal such as Mg, Al, or Yb is used, or a compound such as Li, oxidized Li, or LiF is sandwiched by about 1 nm at the interface in contact with the light emitting medium, and Al or Cu having high stability and conductivity is laminated. And use. Or, in order to achieve both electron injection efficiency and stability, one or more metals such as Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, etc., which have low work function, and stable Ag, Al An alloy system with a metal element such as Cu is used. Specifically, alloys such as MgAg, AlLi, and CuLi can be used. Further, in the case of a top emission type organic EL device, the cathode needs to have transparency, and for example, transparency can be achieved by a combination of these metals and a transparent conductive layer such as ITO.

  As a method for forming the second electrode, a dry film formation method such as a resistance heating vapor deposition method, an electron beam vapor deposition method, a reactive vapor deposition method, an ion plating method, or a sputtering method can be used. Moreover, when it is necessary to make a 2nd electrode into a pattern, it can pattern by a mask etc. The thickness of the second electrode is preferably 10 nm to 1000 nm. In the present invention, the first electrode can be a cathode and the second electrode can be an anode.

  As an organic EL element, it is possible to emit light by sandwiching an organic light emitting layer between electrodes and letting an electric current flow. However, some of the organic light emitting material, the light emission auxiliary layer forming material, and the electrode forming material contain moisture in the atmosphere. Since it is easily deteriorated by oxygen, a sealing body is usually provided for shielding from the outside.

For example, the sealing body is formed by using a glass cap or a metal cap having a recess with respect to the substrate (support 604) on which the first electrode 602, the organic light emitting layer, the light emission auxiliary layer, and the second electrode are formed. Sealing is performed by adhering a cap and a substrate (support 604) with an adhesive around the periphery of the electrode 602, the organic light emitting medium layer, and the second electrode so that there is a recess.

  The sealing body is provided with a resin layer on a sealing material on a substrate (support 604) on which, for example, the first electrode 602, the organic light emitting layer, the light emission auxiliary layer, and the second electrode are formed. It is also possible to attach the sealing material and the substrate with layers.

  At this time, the sealing material needs to be a base material having low moisture and oxygen permeability. Examples of the material include ceramics such as alumina, silicon nitride, and boron nitride, glass such as alkali-free glass and alkali glass, metal foil such as quartz, aluminum, and stainless steel, and moisture-resistant film. Examples of moisture-resistant films include films formed by CVD of SiOx on both sides of plastic substrates, films with low permeability and water-absorbing films, or polymer films coated with a water-absorbing agent. The water vapor transmission rate is preferably 10 −6 g / m 2 / day or less.

  Examples of the resin layer include a photo-curing adhesive resin made of an epoxy resin, an acrylic resin, a silicone resin, a thermosetting adhesive resin, a two-component curable adhesive resin, and an ethylene ethyl acrylate (EEA) polymer. Examples thereof include acrylic resins, vinyl resins such as ethylene vinyl acetate (EVA), thermoplastic resins such as polyamide and synthetic rubber, and thermoplastic adhesive resins such as acid-modified products of polyethylene and polypropylene. Examples of methods for forming a resin layer on a sealing material include solvent solution method, extrusion lamination method, melting / hot melt method, calendar method, nozzle coating method, screen printing method, vacuum laminating method, hot roll laminating method, etc. Can be mentioned. A material having a hygroscopic property or an oxygen absorbing property may be contained as necessary. Although the thickness of the resin layer formed on a sealing material is arbitrarily determined by the magnitude | size and shape of the organic EL element to seal, about 400 micrometers-500 micrometers are desirable.

  The substrate (support 604) on which the first electrode 602, the organic light emitting layer, the light emission auxiliary layer, and the second electrode are formed and the sealing body are bonded to each other in the sealing chamber. When the sealing body has a two-layer structure of a sealing material and a resin layer, and a thermoplastic resin is used for the resin layer, it is preferable to perform only pressure bonding with a heated roll. When a thermosetting adhesive resin is used, it is preferable to perform heat curing at a curing temperature after pressure bonding with a heated roll. In the case where a photocurable adhesive resin is used, curing can be performed by further irradiating light after pressure bonding with a roll. Note that although the resin layer is formed over the sealing material here, the resin layer may be formed over the substrate (support 604) and attached to the sealing material.

  Before or instead of sealing with a sealing body, for example, as a passivation film, it is also possible to form a sealing body with an inorganic thin film, such as a silicon nitride film having a thickness of 150 nm using a CVD method. It is also possible to combine these.

Examples will be described below.
(Preparation of printed substrate)
As a substrate to be printed, a thin film transistor that functions as a switching element provided on a support, a planarization layer formed thereabove, and a pixel electrode that is electrically connected to the thin film transistor through a contact hole on the planarization layer An active matrix substrate provided with

  A partition wall was formed in such a shape as to cover the edge of the pixel electrode provided on the substrate and partition the pixel. The partition walls were formed by forming a positive resist ZWD6216-6 manufactured by Nippon Zeon Co., Ltd. on the entire surface of the substrate with a spin coater to a thickness of 2 μm, and then forming the partition walls by photolithography.

  A poly- (3,4) -ethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) 1.5 wt% aqueous solution with a film thickness of 100 nm was formed as a hole transport layer on the pixel electrode by spin coating. Further, the PEDOT / PSS thin film thus formed was dried at 100 ° C. for 1 hour under reduced pressure to produce a substrate to be printed.

(Preparation of organic light emitting layer forming ink)
The following organic light-emitting inks comprising three colors of red, green, and blue (RGB) were prepared. Red light emitting ink (R): 1% by weight toluene solution of polyfluorene derivative (red light emitting material manufactured by Sumitomo Chemical Co., Ltd.) Green light emitting ink (G): 1% by weight toluene solution of polyfluorene derivative (green light emitting manufactured by Sumitomo Chemical Co., Ltd.) Material) Blue light emitting ink (B): 1% by weight toluene solution of polyfluorene derivative (blue light emitting material manufactured by Sumitomo Chemical Co., Ltd.).

(Preparation of resin plate with diffuse light reflection layer)
[Manufacture of support]
Add 0.3 µm of titanium oxide to polyester urethane adhesive and mix it on a chrome-plated steel sheet with a thickness of 250 µm and a width of 330 mm, and apply evenly to a width of 250 mm using a bar coater. It put in the dryer and dried for 3 minutes, and the laminated body which has a light irregular reflection layer with a film thickness of about 10 micrometers was obtained. When observed under a fluorescent lamp, the appearance was white. At this time, when the 90 ° tensile strength was measured based on JIS K6854-1, the 90 ° tensile strength was 15 N / cm.

Next, a polyester urethane-based adhesive was applied as a light transmission layer in a width of 300 mm so that the light irregular reflection layer was not exposed, and the same treatment was performed. At this time, the 90 ° tensile strength of the base material and the light transmission layer was 31 N / cm. Subsequently, polyamide is the main component, trimethylolpropane triglycidyl ether acrylate is used as the monomer having crosslinkability, benzyldimethyl ketal is used as the polymerization initiator, the solution is made using an organic solvent, and 30 μm is obtained using a roll coater. It was applied and dried for 3 minutes in a hot air dryer at 80 ° C., and irradiated with 3000 mJ / cm ² using a high-pressure mercury lamp to form a layer (solvent resistant layer) to which a surface conditioner was applied. In addition, when providing a surface conditioning agent, 1.5% of fluorine-type or silicon-type resin was provided in the resin layer which has the said polyamide as a main component.

  Polyamide as a hydrophilic polymer, trimethylolpropane triglycidyl ether acrylate as a monomer having crosslinkability, trimethylolpropane, a photosensitive resin using benzyldimethyl ketal as a polymerization initiator, and melt-coated to 40 μm, A photosensitive resin material that is the basis of the relief printing was formed.

In contrast to this photosensitive resin material, a chromium of a synthetic quartz base material in which a 25 μm stripe-shaped opening and a 125 μm light-shielding portion are formed corresponding to the pixel region of the organic electroluminescence display element. The resin relief printing plate was exposed using the mask as the original plate of the resin relief printing pattern and the mask set in a proximity exposure apparatus. The proximity gap was 100 μm, and the exposure dose at 405 nm was 400 mJ / cm ² . After the exposure, a developing pattern was obtained by spraying water as a developer using a line conveying spray developing machine. After the development, hot air drying was performed, and after the post-exposure, a resin relief plate was obtained. In addition, in order to produce an organic EL display, plate making was performed separately for each color of red, blue, and green.

(Check edge detection accuracy)
The convex line width of the produced resin relief printing plate having the diffused light reflection layer was measured with AMIC 1400KY manufactured by Sokkia Co., Ltd. As a result of measurement using the edge detection method, the average line width is 24.8 μm.
The result was ± 0.1 μm, which was well below ± 5% of the target accuracy. In addition, about the convex part line width, the cross check was performed with the scanning electron microscope S-4500 by Hitachi, Ltd., and the reliability of the measurement data was confirmed.

(Verification of plate defects)
Defects generated on the plate and adhered foreign substances were evaluated with a pattern defect apparatus. Although it was impossible to measure the portion without the light irregular reflection layer due to the metallic luster, the product of the present invention was able to confirm the defect (FIG. 7A). However, there were places that could not be detected by this alone. In the center of the created plate, a pattern derived from uneven resin drying is confirmed, and when edge detection and plate defect inspection are performed, edge detection and plate defect inspection cannot be performed at this location, and high-precision plate management is possible. There wasn't.

(Manufacture of organic EL elements)
The letterpress which was not confirmed by the defect inspection was fixed to the cylinder of the sheet-fed printing press. Using this and the above-described organic light emitting ink, printing was performed for each color on the substrate to be printed. The organic light emitting layer was printed so that the red organic light emitting layer, the green organic light emitting layer, and the blue organic light emitting layer were arranged in a stripe shape. After printing for each color, drying was performed in an oven at 130 ° C. for 1 hour. The average film thickness of each color of the formed pattern was 102 nm. After drying, a 10 nm film of calcium was formed on the organic light emitting layer formed by printing, and then silver was vacuum deposited on the film by 300 nm, and finally sealed using a glass cap to produce the organic EL device of the present invention. . When the light emission state of the organic EL element was confirmed, it was confirmed that there was no unusual abnormality such as uneven light emission.

<Comparative Example 1>
(Production of plate with light diffuse reflection layer exposed)
A relief plate was prepared in the same manner as in Example 1 except that a light diffused reflection layer was applied to a 330 mm width on a chromium plated steel plate having a thickness of 250 μm and a width of 330 mm, and an organic EL device was manufactured. Although there was no problem with edge detection and plate defects, when the light emission state of the organic EL element was confirmed, a light emission failure portion or the like was found, and when the portion was subjected to EDX analysis, titanium oxide was detected (see Table 1). ).

<Comparative example 2>
(Manufacture of resin plate without light diffuse reflection layer)
A relief printing plate was prepared by the same method as in Example 1 except that the light irregular reflection layer was not formed, and edge detection and plate defect inspection could not be carried out. When the light emission state of the organic EL element was confirmed, light emission unevenness and defective portions were found. When the plate pattern of the portion corresponding to the light emission unevenness was confirmed with a microscope, the pattern had foreign matter and twist.

<Comparative Example 3>
(Manufacture of a plate having an adhesion between the light diffuse reflection layer and the substrate of 10 N / cm or less)
Titanium oxide contained in the light diffuse reflection layer was added more than twice as compared with Example 1, and a letterpress was prepared in the same manner as described above to produce an organic EL element. At this time, the 90 ° tensile strength of the base material and the light irregular reflection layer was 7.0 N / cm. When the light emission state of the organic EL element was confirmed, no defective light emission was found. However, when edge detection and plate defect inspection were performed, there were locations where titanium oxide was agglomerated. Was not possible, and high-precision version control was not possible.

<Comparative example 4>
(Creation of a plate that adds a surface conditioner to a layer with oil, water or solvent resistance)
In the case of a plate that does not give a surface conditioner to a layer having oil resistance, water resistance, or solvent resistance, a pattern of drying unevenness caused by non-uniformity of drying property is confirmed (FIG. 7 (a)), and an edge is formed at that location. Detection and plate defect inspection could not be performed. Although two types of surface conditioners, fluorine and silicon, were tried, silicon was better (FIG. 7 (b)). It is considered that the fluorine system has a non-uniform film shape without eliminating the drying unevenness (FIG. 7C). When the addition ratio of the surface conditioner is less than 0.1% of the amount of resin to be applied, drying unevenness occurs. When it is more than 3%, aggregates are confirmed in the resin. Plate defect inspection was not possible, and high-precision plate management was not possible.

  From the above, edge detection and plate defect inspection became possible by adding a silicon-based surface conditioner.

100 ... printing relief 101 ... convex pattern 102 ... layer to which a surface conditioner is applied (layer having oil resistance, water resistance or solvent resistance)
DESCRIPTION OF SYMBOLS 103 ... Light transmission layer 104 ... Light diffuse reflection layer 105 ... Base material 106 ... Laminate body 107 ... Photosensitive resin layer 108 ... Plate-shaped photosensitive resin laminate 301 ... Light shielding Part 302 ... Translucent part 303 ... Photomask 304 ... Glass 305 ... Actinic ray 401 ... Ink replenishing device 402 ... Ink chamber 403 ... Doctor 405 ... Plate cylinder 406 ... Printed substrate 407 ... Stage 408 ... Anilox roll 501 ... Substrate 502 ... First electrode 503 ... Hole transport layer 504 ... Second electrode 505 ... Partition wall 506 ... Glass cap 507 ... Adhesive 508 ... Red organic light emitting layer 509 ... Green organic light emitting layer 510 ... Blue organic light emitting layer 601 ... Organic EL element substrate 602 ... First electrode 603 ... Septum 604 ... support 605 ... active layer 606 ... gate insulating film 607 ... gate electrode 609 ... drain electrode 610 ... planarization layer 611 ... contact hole 613 ... TFT

Claims (15)

  On the support base material, a light irregular reflection layer that irregularly reflects light in a wavelength region of at least 400 nm to 800 nm, a light transmission layer that covers the entire surface including the end portion of the light irregular reflection layer, oil resistance, water resistance Or the protective layer which has the characteristic of either of solvent resistance, and the resin-made convex part are laminated | stacked in this order, The said protective layer contains a surface conditioning agent, The relief printing plate for high-definition pattern formation characterized by the above-mentioned.   On the support substrate, a light irregular reflection layer that irregularly reflects light in a wavelength region of at least 400 nm to 800 nm, and a light transmission layer that covers the entire surface including the ends of two opposite sides of the light irregular reflection layer, A high-definition characterized in that a protective layer having any of the properties of oil resistance, water resistance or solvent resistance and a resin convex portion are laminated in this order, and the protective layer contains a surface conditioner. Letterpress for pattern formation.   The relief printing plate for high-definition pattern formation according to claim 1 or 2, wherein the content of the surface conditioning agent in the protective layer is in the range of 0.1 to 3% by weight.   The relief for high-definition pattern formation according to claim 3, wherein the surface conditioner contains a silicon-based resin.   The relief plate for high-definition pattern formation according to claim 1 or 2, wherein the light irregular reflection layer contains a pigment.   6. The relief printing plate for high-definition pattern formation according to claim 5, wherein a particle diameter of the pigment is in a range of 0.2 to 0.8 [mu] m.   7. The relief printing plate for high-definition pattern formation according to claim 5 or 6, wherein the pigment contains titanium oxide.   The relief printing plate for high-definition pattern formation according to any one of claims 1 to 7, wherein an adhesive force between the protective layer and the light transmission layer is 15 N / cm or more.   The relief printing plate for high-definition pattern formation according to any one of claims 1 to 8, wherein an adhesive force between the light irregular reflection layer and the substrate is 10 N / cm or more.   10. The relief printing plate for forming a high-definition pattern according to claim 1, wherein an adhesive force between the light transmission layer and the base material is 15 N / cm or more.   The relief printing plate for high-definition pattern formation according to any one of claims 1 to 10, wherein the substrate is made of metal.   The relief plate for high-definition pattern formation according to any one of claims 1 to 11, wherein the resin convex portion includes at least a photosensitive resin.   An electronic circuit pattern is produced by printing using the relief plate for forming a high-definition pattern according to any one of claims 1 to 12.   An organic EL device is produced by printing using the high-definition pattern forming relief plate according to any one of claims 1 to 12.   A plate-like photosensitive resin laminate comprising at least a support substrate, a light diffuse reflection layer, a light transmission layer, a protective layer containing a surface adjusting agent, and a photosensitive resin layer laminated in this order.