JP2010033925A - Organic thin film patterning substrate and its manufacturing method, organic electric field light-emitting element and its manufacturing method, organic el display device, and organic el illumination - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an organic thin film patterning substrate which hardly leaves residues such as components of a resist material having an ink-repellent property at a range excluding a bank even though the bank with a self ink-repellent property, which is simple in process and is profitable at manufacturing costs, is used. <P>SOLUTION: In the manufacturing method for an organic thin film patterning substrate having banks on a substrate and zones partitioned by the banks and forming an organic thin film on the zones partitioned by the banks, a base-coated layer 12 is arranged on the substrate 11 directly or via the other layer by applying a hydrophilic compound containing composition, a resist layer 13 for a bank is arranged on the base-coated layer 12 by applying a light-sensitive composition including an ink-repellent component, and the bank 14 is formed by exposing and developing the resist layer 13 for a bank. The base-coated layer 12 of a non-image section is removed together with the resist layer 13 for the bank of the non-image section in this developing process. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic thin film patterning substrate used for forming pixels of an organic electroluminescent device, a color filter, a field emission, or other optical device used in a color display or the like, a manufacturing method thereof, and the organic thin film patterning substrate The present invention relates to an organic electroluminescent element using the organic electroluminescent element, a manufacturing method thereof, an organic EL display device using the organic electroluminescent element, and organic EL lighting.

  In recent years, the development of color displays has been remarkable, and the demand is also increasing. However, for further popularization, it is required to simplify the manufacturing process, use an inkjet system that has a simple manufacturing process, good yield, and low cost. Thus, a method for forming a pixel has been proposed. In the inkjet method, first, a bank for separately painting pixels is formed on a substrate to form a partitioned area, and ink for forming pixels of each of the three primary colors of RGB is discharged into the partitioned area and dried. Then, pixels are formed. Pixels formed with this ink are contained in a light emitting layer made of a luminescent substance in an organic electroluminescent element, a colored layer made of a pigment or a dye in a color filter, and a light emitting part or an electron source containing a phosphor in a field emission. By using a field emission device, application to each application is possible.

  However, in this ink jet system, as a specific problem, there are a problem of color mixing and white spots.

  Color mixing occurs when ink mixes between adjacent pixels of different colors. For example, in the case of a light emitting layer of an organic electroluminescent element, the film thickness of the light emitting layer to be formed is usually about several tens of nanometers. Considering the solid content concentration contained in the tank, the height of the bank, etc., it is necessary to eject a larger amount of ink than the volume of the opening of the bank. As a result, the ink overflows beyond the bank and is adjacent. Since it flows into the pixel region, there occurs a situation in which light emission of a desired color and luminance cannot be obtained.

  In order to avoid this, various techniques for making the bank ink repellent have been proposed. By adopting these technologies, even when an amount of ink exceeding the height of the bank is applied, the surface of the bank is repelled so that the ink is repelled, and other colors that are adjacent to the bank. Ink does not reach this area, and color mixing can be prevented.

On the other hand, white spots occur when the applied ink cannot be sufficiently and uniformly diffused in the area surrounded by the bank, and a phenomenon in which coloring does not occur or a region with uneven luminance is seen. As a result, the bias of the voltage generated thereby adversely affects the device life.
In order to avoid this, it is necessary to maintain sufficient and uniform ink wettability in the area partitioned by the bank.

  Conventionally, as a technique for making the ink repellent of the bank, a technique based on fluorine plasma treatment is generally used. However, in this method, when the bank is made ink repellent, ink wettability other than the bank must be ensured. Even areas that must be processed are affected by the ink repellency, which leads to white spots.

  In order to solve this problem, in Patent Document 1 and Patent Document 2, an operation of performing a plurality of processes is performed after a bank is formed. However, the process is very complicated and not practical.

In Patent Document 3 and Patent Document 4, a self-ink-repellent bank is formed using a resist material having ink-repellency. Since these techniques can form an ink-repellent bank only by a bank manufacturing process by photolithography, it is preferable in terms of process, but a component of a resist material having ink repellency remains in a region other than the bank, This has the problem that it is difficult to be sufficiently removed in the development process. In particular, when the bank forming surface is not an inorganic material such as glass but an organic material, the affinity between the bank forming component and the lower layer that is the bank forming surface is strong, so it is easy to integrate and the resist material component having ink repellency is the lower layer. There is a problem that when the thin film is adsorbed on the bank forming surface and white spots occur, or when an organic thin film is formed in an area partitioned by the bank, the film cannot be formed uniformly. Further, if development processing is performed under severe conditions in order to remove these components, there is a problem that the lower layer is damaged.
Japanese Patent Laid-Open No. 2002-55218 JP 2002-55222 A JP-A-10-115703 JP 2005-60515 A

The present invention is an organic thin film patterning method in which a residue such as a component of a resist material having ink repellency is unlikely to remain in a region other than a bank even if a self-ink repellant bank that is simple in process and advantageous in production cost is used. It is an object of the present invention to provide a method for manufacturing a manufacturing substrate.
The present invention also provides an organic thin film patterning substrate capable of uniformly forming an organic thin film only in a region partitioned by a bank and hardly causing color mixing or white spot, and an organic electroluminescent device using the same. The task is to do.

  As a result of intensive studies to solve the above problems, the present inventors applied a hydrophilic compound-containing composition to form an undercoat layer, and then used a photosensitive composition containing an ink repellent component. When the bank resist layer is formed, the undercoat layer is removed together with the non-image part of the bank resist layer at the time of development in the photolithography process, and this hydrophilic compound-containing composition has very good development omission. In the case where is an organic layer, no residue remains and the ink repellent component does not need to contact the lower layer, so that the problem of white spots can be avoided and the present invention has been completed.

  That is, the gist of the present invention is to manufacture an organic thin film patterning substrate having a bank and a region partitioned by the bank on the substrate, and used for forming an organic thin film in the region partitioned by the bank. In the method, an undercoat layer forming step of providing an undercoat layer by applying a hydrophilic compound-containing composition containing a hydrophilic compound directly or via another layer on the substrate, and on the undercoat layer A resist layer forming step of applying a photosensitive composition containing an ink repellent component to provide a bank resist layer, and a bank forming step of forming a bank by exposing and developing the bank resist layer; The undercoat layer of the non-image area is removed together with the bank resist layer of the non-image area in the development process of the bank forming step. A method of manufacturing a substrate, resides in.

  Another gist of the present invention is that an organic thin film patterning substrate produced by the method for producing an organic thin film patterning substrate is used, and a light emitting layer is formed as an organic thin film in a region partitioned by a bank of the organic thin film patterning substrate. A method for producing an organic electroluminescent element, characterized in that

  Still another subject matter of the present invention is an organic thin film patterning substrate having a bank and a region partitioned by the bank on the substrate, and used for forming an organic thin film in the region partitioned by the bank. The bank is formed on an undercoat layer containing a hydrophilic compound, and the bank resides in an organic thin film patterning substrate characterized by containing an ink repellent component.

  Still another subject matter of the present invention is an organic electroluminescent device having a bank and a region partitioned by the bank on a substrate, and having an organic thin film in the region partitioned by the bank, The organic electroluminescent device is characterized in that it is formed on an undercoat layer containing a hydrophilic compound, and the bank contains an ink repellent component.

  Still another subject matter of the present invention resides in an organic EL display device and an organic EL illumination characterized by using such an organic electroluminescent element.

According to the organic thin film patterning substrate of the present invention, using a self-ink-repellent bank that is simple in process and advantageous in terms of production cost, uniform, mixed colors and white spots are formed in the area partitioned by the bank. It is possible to form an organic thin film with few problems. The organic thin film patterning substrate of the present invention is particularly useful when an organic thin film is formed by an ink discharge type coating method such as an ink jet method in which mixed colors and white spots are likely to occur.
The organic thin film patterning substrate according to the present invention can provide a high-quality organic electroluminescence device, a color filter, a field emission display (field electron emission device), etc. without color mixing or white spots. In addition, it is possible to provide a high-quality organic EL display device and organic EL illumination using the organic electroluminescent element.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. It is not specified in the contents.

In the present invention, “(meth) acrylic acid” means that both “acrylic acid” and “methacrylic acid” are included, and “(meth) acrylate”, “(meth) acryloyl” and the like are the same. Is the meaning. The term “(poly)” in front of the monomer name means that both the “monomer” and the “polymer” are included, and “acid (anhydride)”, “(anhydrous)” are included. ... "Acid" means to include both "acid" and its "acid anhydride".
“(Co) polymerization” means to include both “polymerization” and “copolymerization”.
In the present invention, the “total solid content” means all components excluding the solvent among the constituent components of the composition.

  Moreover, in this invention, the molecular weight of various resin is a weight average molecular weight (Mw) of standard polystyrene conversion measured by GPC (gel permeation chromatography).

[Method of manufacturing organic thin film patterning substrate]
The organic thin film patterning substrate manufacturing method of the present invention has a bank and a region partitioned by the bank on the substrate, and is used to form the organic thin film in the region partitioned by the bank. In the method of manufacturing the patterning substrate,
An undercoat layer forming step of providing an undercoat layer by applying a hydrophilic compound-containing composition containing a hydrophilic compound directly or via another layer on the substrate;
A resist layer forming step of providing a bank resist layer by applying a photosensitive composition containing an ink repellent component on the undercoat layer;
A bank forming step of forming a bank by exposing and developing the resist layer for bank; and
In the development process of the bank forming process, the undercoat layer in the non-image area is removed together with the bank resist layer in the non-image area.

  Hereinafter, the manufacturing method of the organic thin film patterning substrate of the present invention will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing an embodiment of a process for producing an organic thin film patterning substrate of the present invention and an organic thin film forming step on the produced organic thin film patterning substrate.

{Undercoat layer forming step}
In the production method of the present invention, first, an undercoat layer 12 is provided by applying a hydrophilic compound-containing composition containing a hydrophilic compound directly or via another layer on the substrate 11 (FIG. 1A). ).

  Here, the other layers that can be formed on the substrate 1 are, for example, an electrode layer such as an anode and a cathode, a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport if used for an organic electroluminescence device. Examples include layers such as a layer and a light emitting layer. The other layer may be a single layer or a laminate of two or more layers. These electrode layers such as the anode and the cathode, the hole injection layer, the hole transport layer, the electron injection layer, the electron transport layer, the light emitting layer, and the substrate will be described in detail in the description section of the organic electroluminescence device described later.

In the organic thin film patterning substrate manufacturing method of the present invention, a bank resist layer is formed by applying a photosensitive composition containing an ink repellent component (hereinafter sometimes referred to as “ink repellent resist material”). After that, when the bank is formed by exposure and development, the ink-repellent resist material hardly remains in the area partitioned by the bank. It is suitable for the case where the undercoat layer 12 is provided through an organic layer having a strong affinity with such an ink repellent resist material and in which the ink repellent resist material tends to remain. That is, in the conventional method, since the ink-repellent resist material could not be removed unless the development process was performed under severe conditions, the other layer was damaged by this development process when the other layer was interposed on the substrate. There were many cases to receive. However, according to the manufacturing method of the present invention, since the ink repellent resist material hardly remains and it is not necessary to perform development processing under severe conditions, a bank can be formed without damaging other layers on the substrate. .
Other layers on the substrate are suitable because the effects of the present invention are particularly effective when the ink repellent resist material has strong affinity with the ink repellent resist material and the ink repellent resist material tends to remain. When the organic thin film patterning substrate of the present invention is an organic electroluminescent device substrate, the other layers are particularly suitable for organic layers such as a hole injection layer and a hole transport layer.

  In the present invention, the undercoat layer is usually formed by applying and drying the hydrophilic compound-containing composition on the entire surface of the substrate or other layer.

<Hydrophilic compound-containing composition>
The hydrophilic compound-containing composition used for forming the undercoat layer contains a hydrophilic compound and usually further contains a solvent.

In the present invention, the hydrophilic compound is a compound that dissolves or swells in water. Specifically, a compound having a functional group such as a carboxy group, a hydroxyl group, a sulfonic acid (salt) group, a phosphonic acid (salt) group, an amino group, an amide group, or a quaternary ammonium base in the molecule is preferable. . In particular, the hydrophilic compound is preferably an organic compound.
The hydrophilic compound is not particularly limited as long as it satisfies the above-mentioned conditions and can form a film, but in order to ensure the resistance to the photosensitive composition for forming the film and the subsequent bank resist layer. The hydrophilic compound is preferably a hydrophilic resin. Here, the hydrophilic resin is a resin having the above functional group, and usually refers to a resin obtained by polymerizing or condensing a unit (monomer or polymer) containing the above functional group. Moreover, the polymer material whose weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) normally is about 1000-2,000,000 is said.

  Examples of hydrophilic resins that can be used as hydrophilic compounds include polyvinyl alcohol, polysaccharides, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, sucrose octaacetate, and alginic acid. Ammonium, sodium alginate, polyvinylamine, polyallylamine, polystyrenesulfonic acid, polyacrylic acid, water-soluble polyamide, maleic anhydride copolymer, gum arabic, water-soluble soybean polysaccharide, white dextrin, pullulan, curdlan, chitosan, alginic acid In addition to enzyme-decomposed etherified dextrin, (co) polymers (co) polymerized using hydrophilic monomers, and the like can be mentioned.

  Examples of hydrophilic monomers include (meth) acrylic acid or its alkali metal salts and amine salts, itaconic acid or its alkali metal salts and amine salts, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol ( (Meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt, vinylsulfonic acid or its alkali metal salt and amine salt, vinylpyrrolidone, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxypolyoxyethylene glycol mono (me ), Such as acrylate, a carboxyl group, a sulfo group, a phosphoric acid group, an amino group or a salt thereof, hydroxyl group and a monomer having a hydrophilic group selected from an amide group and an ether group.

  Moreover, what was illustrated as said hydrophilic monomer as hydrophilic compounds other than hydrophilic resin is mentioned, It is also preferable that these are contained with a monomer in a hydrophilic compound containing composition.

  Examples of the hydrophilic compound include vinylpyrrolidone (co) polymers, (meth) acrylic acid (co) polymers, polyvinyl alcohol and derivatives thereof, and celluloses such as hydroxyethylcellulose, carboxymethylcellulose, and methylcellulose. A hydrophilic resin such as is preferable.

  The hydrophilic compound-containing composition used in the present invention may contain one kind of these hydrophilic compounds or may contain two or more kinds.

  The hydrophilic compound is preferably contained in the total solid content of the hydrophilic compound-containing composition in an amount of preferably 10% by weight or more, more preferably 20% by weight or more and 100% by weight or less. When the content of the hydrophilic compound in the hydrophilic compound-containing composition is less than the above lower limit, it becomes difficult to completely remove the formed undercoat layer by development, leading to white spots. In addition, it becomes difficult to form a uniform organic thin film in the region delimited by the bank by the ink ejection type coating method.

  The hydrophilic compound-containing composition according to the present invention may contain other components as necessary in addition to the hydrophilic compound. Other components include, for example, photopolymerization initiators, thermal polymerization initiators, ethylenically unsaturated compounds and other reactive compounds, surfactants, fillers, substrate adhesion enhancers, development accelerators such as acids and alcohols, colors Examples thereof include materials, thermal polymerization inhibitors, plasticizers, storage stabilizers, and surface protective agents. In particular, by adding a photopolymerization initiator or an ethylenically unsaturated compound to the hydrophilic compound-containing composition, the composition is made photosensitive, and can be polymerized at the time of exposure together with the bank resist layer. It is useful in the sense of ensuring the adhesiveness of.

  Examples of the photopolymerization initiator and ethylenically unsaturated compound used in this case include those exemplified as the photopolymerization initiator and ethylenically unsaturated compound contained in the photosensitive composition described below. . When the hydrophilic compound-containing composition contains a photopolymerization initiator, the content is usually 0.01% by weight or more, usually 10% by weight or less, preferably 5% by weight in the total solid content of the composition. % Or less. When the hydrophilic compound-containing composition contains an ethylenically unsaturated compound, the content thereof is usually 1% by weight or more, preferably 3% by weight or more, and usually 80% by weight or less, preferably in the total solid content of the composition. Is 50% by weight or less. If the content of the photopolymerization initiator and the ethylenically unsaturated compound is too small, the photosensitivity due to the inclusion thereof cannot be obtained, and if too large, the content of the hydrophilic compound is relatively reduced, The above problem occurs.

  Of course, the hydrophilic compound-containing composition does not need to be photosensitive, and the bank resist layer can be adequately selected even if it is not photosensitive by selecting the material and developer of the bank resist layer and controlling the thickness of the undercoat layer. It is possible to ensure adhesion to the layer, and it is also possible to devise measures such as avoiding bank tailing by utilizing the fact that it is not photosensitive.

  The solvent contained in the hydrophilic compound-containing composition is not particularly limited as long as the solid content of the hydrophilic compound-containing composition can be dissolved or dispersed and enables uniform coating. Is preferable to be dissolved rather than being dispersed in this solvent. From the viewpoint of securing this solubility, it is preferable to use water and / or alcohol solvents, and in particular, water and / or alcohol solvents are used. The main component of the solvent contained in the hydrophilic compound-containing composition is preferable.

  Water and / or alcohol solvents are also preferable in that the organic layer is not dissolved, particularly when the undercoat layer is provided on the organic layer. In particular, the organic layer is a hole of the organic electroluminescent device. This is useful when it is an injection layer or a hole transport layer. Furthermore, after forming the undercoat layer, when applying the photosensitive composition described later in the bank resist layer forming step, the undercoat layer is not caused to flow out by the organic solvent contained in the photosensitive composition. The solid content of the hydrophilic compound-containing composition is highly soluble in water and / or alcohol solvents, and is preferably hardly soluble or insoluble in an organic solvent which is a solvent for the photosensitive composition described later.

  Specific examples of the alcohol solvent used in the hydrophilic compound-containing composition include alkyl alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, and tert-butyl alcohol. , Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methyl- 3-ethoxybutanol, 3-methyl-3-n-propoxybutanol, 3-methyl-3-isopropoxybutanol, 3-methyl Such as ru-3-n-butoxysibutanol, 3-methyl-3-isobutoxysibutanol, 3-methyl-3-sec-butoxybutanol, 3-methyl-3-tert-butoxysibutanol, 3-methoxybutanol, etc. Examples include alkoxy alcohols.

  The alkyl group chain of the alcohol solvent is preferably not so long from the viewpoint of the solubility of the hydrophilic compound. As the alkyl alcohols, those having an alkyl group with about 2 to 4 carbon atoms are preferred, and glycol ethers are preferred. Are preferably those in which the alkylene group of the alkylene glycol moiety has about 3 to 5 carbon atoms, and the alkoxy alcohols preferably have an alkoxy group having about 2 to 4 carbon atoms.

  The solvent for the hydrophilic compound-containing composition may be a solvent other than water or an alcohol solvent, and the solvent other than water or an alcohol solvent that can be used for the hydrophilic compound-containing composition is dioxane. , Tetrahydrofuran, 1,2-diethoxyethane, 1,2-dimethoxyethane, 1,2-dibutoxyethane and other ethers, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone and other ketones, 3-methoxybutyl Examples thereof include esters such as acetate, butyl diglycol acetate, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. These may be used alone or mixed with water or an alcohol solvent.

The solvent contained in the hydrophilic compound-containing composition may be only one selected from water, the above-described alcoholic solvent, and other solvents, or may be a mixed solvent of two or more.
However, the solvent in the hydrophilic compound-containing composition is preferably composed of water and / or an alcohol solvent, and other solvents can be mixed and used. The solvent is preferably contained in an amount of 5% by weight or more, particularly 20% by weight or more and 100% by weight or less. In particular, the water and / or alcohol solvent is preferably contained as a main component of the solvent of the hydrophilic compound-containing composition. “Contained as a main component of the solvent” means that water, an alcohol-based solvent, or a mixed solvent of water and an alcohol-based solvent is contained in the largest amount in the solvent.

  The total solid concentration in the hydrophilic compound-containing composition is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less. is there. When the total solid content concentration of the hydrophilic compound-containing composition is below the lower limit, it is difficult to form a coating film, and when it exceeds the upper limit, it may be difficult to form a thin film.

  A coating method for forming the undercoat layer by coating and drying the hydrophilic compound-containing composition directly or on another layer on the substrate is not limited. For example, spin coating method, wire bar method It can be applied by a flow coating method, a die coating method, a roll coating method, a spray coating method, a dip coating method or the like. These coating methods can be freely selected depending on the film thickness.

As a drying method, a method of drying using a hot plate, an IR oven, or a convection oven is preferable. The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, usually 200 ° C. or lower, preferably 130 ° C. or lower. Further, the drying time is preferably 15 seconds or more, preferably 30 seconds or more, preferably 5 minutes or less, and preferably 3 minutes or less. If the drying temperature is too low or the drying time is short, it may not be sufficiently dried and may flow out when the photosensitive composition is applied. The drying temperature is too high or the drying time is too long. In addition, there is a problem of productivity reduction and thermal deterioration of the substrate and other layers, which is not preferable.
The drying may be a reduced pressure drying method in which the temperature is not increased and drying is performed in a reduced pressure chamber, or a combination of reduced pressure drying and heat drying may be used.

The thickness of the undercoat layer obtained after drying is not particularly limited, but is preferably 1/3 or less of the completed bank height including the undercoat layer (the height of _{HA in} FIG. 1D). Is particularly preferably / 4 or less, more preferably 1/200 or more, and particularly preferably 1/50 or more. When the film thickness of the undercoat layer is larger than this, there are the following problems. That is, since the undercoat layer has higher wettability with respect to the ink for forming the organic thin film than the portion of the bank resist layer, when forming the organic thin film, the organic thin film is exposed at the exposed portion of the undercoat layer on the bank wall surface. The coating thickness becomes high, and the film is dried in this state, and after drying, a non-uniform organic thin film is formed in which the central part of the area partitioned by the bank is thin and the periphery is thick. There is a risk. On the contrary, if the thickness of the undercoat layer is smaller than the lower limit, it is difficult to obtain the effect of the present invention due to the formation of the undercoat layer.

  The specific thickness of the undercoat layer is preferably 5 nm or more, more preferably 7 nm or more, particularly preferably 10 nm or more, preferably 4 μm or less, more preferably 1 μm or less, and particularly preferably 0.5 μm or less. If the film thickness of the undercoat layer is less than this lower limit, the effect of the undercoat layer is difficult to obtain, and if it exceeds the upper limit, the organic thin film is difficult to be uniformly formed in the region partitioned by the bank as described above. Further, when the undercoat layer is not photosensitive, it is difficult to hold the upper bank resist layer.

{Resist layer forming step}
After the undercoat layer 12 is formed as described above, a photosensitive composition containing an ink repellent component is applied to form a bank resist layer 13 (FIG. 1B). Usually, this photosensitive composition is applied to the entire surface of the undercoat layer 12 to form the bank resist layer 13 on the entire surface of the undercoat layer 12.

<Photosensitive composition>
The photosensitive composition used for forming the bank resist layer 13 contains an ink repellent component as an essential component, but usually further contains a solvent, and further contains an ethylenically unsaturated group and a carboxy group. , An ethylenically unsaturated compound, and a photopolymerization initiator are preferably contained.

(Ink repellent component)
In the present invention, ink repellency is a property that repels ink that forms an organic thin film formed in a region partitioned by banks, and an ink repellency component is a material having such ink repellency. means. Preferably, by containing an ink repellent component, the contact angle of the ink forming the organic thin film with respect to the bank is 20 ° or more, more preferably 30 ° or more, and particularly preferably 45 ° or more. The contact angle referred to here is measured under the same conditions as the contact angle measured in the examples described later.

  The ink repellency component is not particularly limited as long as it has an effect of imparting ink repellency to the bank, and examples thereof include fluorine-containing compounds and silicon-containing compounds.

The photosensitive composition usually contains a solvent, and an organic solvent is preferably used as the solvent. Therefore, as the ink repellent component, a fluorine-containing compound is preferable from a silicon-containing compound in terms of solubility in an organic solvent, but the photosensitive composition may contain both of them.
The molecular weight of the fluorine-containing compound is not particularly limited, and it may be a low molecular weight compound or a high molecular weight compound.

  As the fluorine-containing compound, a compound containing a perfluoroalkyl group (perfluoroalkyl group-containing compound) is preferable. For example, JP-A-7-35916, JP-A-11-281815, International Publication No. 2004-042474, In addition to the liquid repellent compounds disclosed in JP 2005-60515 A, JP 2005-315984 A, JP 2006-71086 A, etc., BYK-340 (manufactured by Big Chemie), Modiper F200, F600 , F3035 (above, made by NOF Corporation) Footgent M series, S series, F series, G series, D series, oligomer series (above, made by Neos Corporation), Unidyne (made by Daikin Industries) , Trifluoropropyltrichlorosilane (manufactured by Shin-Etsu Silicone) , Commercially available or such SURFLON S-386 (manufactured by AGC Seimi Chemical Co., Ltd.), a resin obtained by copolymerizing perfluoro group-containing acrylic monomer as a component and the like can also be mentioned. Furthermore, a compound containing a perfluoropolyether group capable of avoiding a perfluoroalkyl group having more than 6 carbon atoms, which is concerned about safety, is also effective.

  In addition, as the fluorine-containing compound, a fluorinated epoxy resin, a fluorinated polyimide resin, a fluorinated polyamide resin, a fluorinated polyurethane resin, a fluorinated siloxane resin, and a modified resin thereof can be used.

  In addition, when the photosensitive composition containing the ink repellent component used for this invention is developed after exposure, it is not preferable that an ink repellent component flows out by a development process. In this respect, it is effective to use an ink repellent resin as the ink repellent component, but as the ink repellent component, a compound having a crosslinkable group capable of undergoing a crosslinking reaction upon exposure (hereinafter referred to as “crosslinkable”). It may be referred to as “group-containing ink repellent agent”).

Examples of the fluorine-containing compound that is the crosslinkable group-containing ink repellent include, for example, MegaFac RS-101, RS-102, RS-105, RS-401, RS-402, RS-501, RS-502 (above, DIC Co., Ltd.), OPTOOL DAC (manufactured by Daikin Industries), perfluoro (meth) acrylate, perfluorodi (meth) acrylate, and the like, but are not limited thereto.
These ink repellent components can be used alone or in combination of two or more.

  Further, the content of the ink repellent component in the photosensitive composition varies depending on the fluorine content of the ink repellent component, and the fluorine content in the ink repellent component (the fluorine concentration of the compound of the ink repellent component) is 10. In the case of wt% or more, the ink repellent component is preferably 0.001 wt% or more, more preferably 0.05 wt% or more, and more preferably 10 wt% or less, based on the total solid content excluding the solvent of the photosensitive composition. Is preferable, and 6% by weight or less is more preferable. When the fluorine content of the ink repellent component is less than 10% by weight, the ink repellent component is preferably 0.1% by weight or more, more preferably 1% by weight or more, based on the total solid content of the photosensitive composition, 70 % By weight or less is preferable, and 50% by weight or less is more preferable. If the content of the ink repellency component is less than this, the ink repellency of the bank is insufficient and the ink flows out to the adjacent section, resulting in color mixing. If it is more than this, it is difficult to ensure developability. .

(Binder resin)
It is preferable that the photosensitive composition contains a binder resin. Binder resin may be used individually by 1 type, and may use 2 or more types together.

  The binder resin is not particularly limited as long as it is a resin that can be developed with a developer, but an alkali developer is preferable as the developer, and thus an alkali-soluble resin is preferable. As the alkali-soluble resin, for example, acrylic resins, carboxy group-containing urethane resins, modified epoxy resins, modified novolac resins, cardo resins, resins containing various ethylenically unsaturated groups and carboxy groups, and the like are preferably used. However, resins containing various ethylenically unsaturated groups and carboxy groups are particularly preferred.

  The content of the binder resin in the photosensitive composition is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, usually 70% by weight or less, based on the total solid content excluding the solvent. Preferably it is 60 weight% or less, More preferably, it is 50 weight% or less. If the content of the binder resin in the photosensitive composition is below this lower limit, it will be difficult to ensure the shape of the bank, and if it exceeds the upper limit, sensitivity and developability may be reduced.

  Hereinafter, among binder resins suitable for the photosensitive composition according to the present invention, [A] an acrylic acid resin, [B] a resin containing an ethylenically unsaturated group and a carboxy group, and [C] a modified novolak. The resin will be described in detail.

[A] Acrylic acid resin The acrylic resin preferably contains a component derived from a monomer having a carboxy group or a phenolic hydroxyl group in the side chain or main chain in order to ensure alkali solubility. Resins that can be developed in solution are preferred.
For example, a (meth) acrylic acid-based (co) polymer or a (meth) acrylic acid-based resin having a carboxy group (in particular, a (co) polymer containing a (meth) acrylic acid ester) is preferable. These acrylic resins are advantageous in that copolymers having different performances can be obtained by combining with various monomers, and the production method is easy to control.

  The acrylic resin according to the present invention is preferably, for example, a (co) polymer mainly composed of the following monomers.

That is, examples of the monomer include a compound obtained by adding an acid (anhydride) to hydroxyalkyl (meth) acrylate.
Examples of the hydroxyalkyl (meth) acrylate include (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- ( (Meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acrylic) Leuoxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) ) Ester, maleic acid (2- (meth) acryloyloxypropyl) ester Succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxybutyl) ester, phthalic acid ( Examples include 2- (meth) acryloyloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, and the acid (anhydride) includes (anhydrous) succinic acid and (anhydrous) phthalic acid. , (Anhydrous) maleic acid and the like.

  Any of these hydroxyalkyl (meth) acrylates and acids (anhydrides) may be used alone or in combination of two or more.

  Monomers that can be copolymerized with the above monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, cinnamic acid, maleic acid, fumaric acid, maleic anhydride, itacone. Unsaturated group-containing carboxylic acids such as acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (Meth) acrylate, glycidyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth ) Esters of (meth) acrylic acid such as acrylate, compounds obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to (meth) acrylic acid, acrylonitrile, Acrylonitriles such as methacrylonitrile, (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide, etc. Acrylamides, vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl pivalate and the like. These may be used alone or in combination of two or more.

  An ethylenically unsaturated group (ethylenic double bond) may be introduced into an acrylic resin having a carboxy group or a hydroxyl group in advance. Thereby, it can be set as resin containing an ethylenically unsaturated group and a carboxy group.

  In this case, it is usually preferably 2 mol% or more, more preferably 5 mol% or more, preferably 50 mol% or less, more preferably 40 mol, based on the carboxy group or hydroxyl group of the acrylic resin having a carboxy group or hydroxyl group. It is preferable to bind a compound having no more than% ethylenic double bond. Moreover, the content of the carboxy group in the acrylic resin is preferably in the range of 5 to 200 mg-KOH / g as the acid value. When the acid value is less than 5 mg-KOH / g, it becomes insoluble in an alkaline developer, and when it exceeds 200 mg-KOH / g, the development sensitivity may be lowered.

  The weight average molecular weight (Mw) of the acrylic resin is preferably in the range of 1,000 to 100,000. When the weight average molecular weight is less than 1,000, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, the developability tends to decrease.

[B] Resin containing ethylenically unsaturated group and carboxy group The resin containing ethylenically unsaturated group and carboxy group is a resin having at least one known ethylenically unsaturated group and carboxy group. It is preferable to use 1 type (s) or 2 or more types.

Examples of such resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Combined; acid-modified epoxy acrylate, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, and the like.
Among these, from the viewpoint of alkali developability and the like, a carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the [B-1] side chain and [B-2] acid-modified epoxy (meth) acrylate are preferable. is there.

[B-1] Carboxy group-containing vinyl resin having an ethylenically unsaturated group in the side chain As a carboxy group-containing vinyl resin having an ethylenically unsaturated group in the side chain, [B-1-1] containing a carboxy group Reaction product of vinyl resin and epoxy group-containing unsaturated compound, “B-1-2” Co-weight of compound having two or more unsaturated groups and unsaturated carboxylic acid and / or unsaturated carboxylic acid ester Examples thereof include [B-1-3] E-R-N-T resin.

[B-1-1] Reaction product of carboxy group-containing vinyl resin and epoxy group-containing unsaturated compound Specifically, the carboxy group-containing vinyl resin is one or more of unsaturated carboxylic acids. And a copolymer of one or more of vinyl compounds.

  Here, examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and the like.

  Examples of the vinyl compound include styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl. (Meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, hydroxy Methyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, -(Meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate, Etc.

  Among the carboxy group-containing vinyl resins, a (meth) acrylate- (meth) acrylic acid copolymer and a styrene- (meth) acrylate- (meth) acrylic acid copolymer are preferable. In the (meth) acrylate- (meth) acrylic acid copolymer, a copolymer composed of 5 to 80 mol% (meth) acrylate and 20 to 95 mol% (meth) acrylic acid is more preferable. A copolymer comprising 10 to 90 mol% of (meth) acrylate and 10 to 90 mol% of (meth) acrylic acid is particularly preferable.

  Moreover, in a styrene- (meth) acrylate- (meth) acrylic acid copolymer, styrene 3-60 mol%, (meth) acrylate 10-70 mol%, (meth) acrylic acid 10-60 mol%, The copolymer which consists of 5-50 mol% of styrene, 20-60 mol% of (meth) acrylates, and 15-55 mol% of (meth) acrylic acid is especially preferable.

  In addition, the acid value of these carboxy group-containing vinyl resins is adjusted according to the amount of the epoxy group-containing unsaturated compound to be reacted with them and the acid value required in the obtained reaction product, Usually, it is 50-500 mg-KOH / g. The weight average molecular weight (Mw) of the carboxy group-containing vinyl resin is preferably 1,000 to 300,000.

  On the other hand, the epoxy group-containing unsaturated compound includes an aliphatic epoxy group-containing unsaturated compound and an alicyclic epoxy group-containing unsaturated compound. The aliphatic epoxy group-containing unsaturated compound includes, for example, allyl glycidyl. Ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumarate monoalkyl monoglycidyl ester, maleic acid monoester Examples thereof include alkyl monoglycidyl esters.

  Examples of the alicyclic epoxy group-containing unsaturated compound include 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, and 7,8-epoxy [tricyclo [5. 2.1.0] dec-2-yl] oxymethyl (meth) acrylate and the like.

  One or more of the carboxy group-containing vinyl resins as described above and one or more of the epoxy group-containing unsaturated compounds are 5 to 90 mol% of the carboxy groups of the carboxy group-containing vinyl resin. The reaction is preferably carried out at a quantitative ratio of the epoxy group-containing unsaturated compound of about 30 to 70 mol%. In addition, reaction can be implemented by a well-known method.

  The acid value of the reaction product of the carboxy group-containing vinyl resin and the epoxy group-containing unsaturated compound is preferably 30 to 250 mg-KOH / g. The weight average molecular weight (Mw) is preferably 1,000 to 300,000.

“B-1-2” a copolymer of a compound having two or more unsaturated groups and an unsaturated carboxylic acid and / or unsaturated carboxylic acid ester As a compound having two or more unsaturated groups, for example, Allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl (meth) acrylamide, vinyl (meth) ) Acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide and the like.

  On the other hand, as unsaturated carboxylic acid or unsaturated carboxylic acid ester, 1 type (s) or 2 or more types, such as (meth) acrylic acid or (meth) acrylic acid ester, are mentioned, for example.

  The proportion of the compound having two or more kinds of unsaturated groups in the entire copolymer is about 10 to 90 mol%, preferably about 30 to 80 mol%.

  The acid value of the copolymer of a compound having two or more unsaturated groups and an unsaturated carboxylic acid and / or unsaturated carboxylic acid ester is preferably 30 to 250 mg-KOH / g. The weight average molecular weight (Mw) is preferably 1,000 to 300,000.

[B-1-3] E-R-N-T resin E-R-N-T resin is (E) component: 5 to 90 mol% of epoxy group-containing (meth) acrylate, and (R) component : (E) 10 to 95 mol% of another radical polymerizable compound that can be copolymerized with the component is copolymerized, and 10 to 100 mol% of the epoxy group contained in the obtained copolymer, (N) Component: A resin obtained by adding an unsaturated monobasic acid and adding (T) component: polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group produced when this (N) component is added. is there.

  Here, as the epoxy group-containing (meth) acrylate ((E) component) in the E-R-N-T resin, for example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Of these, glycidyl (meth) acrylate is preferred. These (E) components may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

As described above, the copolymerization ratio of the component (E) in the copolymer of the component (E) and the component (R) is usually 5 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more. It is. Moreover, it is 90 mol% or less normally, Preferably it is 80 mol% or less, More preferably, it is 70 mol% or less. Here, the component (R) is another radical polymerizable compound that can be copolymerized with the component (E).
When the copolymerization ratio of the component (E) in the copolymer of the component (E) and the component (R) is excessively large, the heat resistance and strength tend to decrease due to the relatively small amount of the component (R). is there. When the copolymerization ratio of the component (E) is excessively small, the addition amount of the polymerizable component and the alkali-soluble component tends to be insufficient.

  On the other hand, the copolymerization ratio of the (R) component in the copolymer of the (E) component and the (R) component is 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, as described above. It is. Moreover, it is 95 mol% normally, Preferably it is 80 mol% or less, More preferably, it is 70 mol% or less. When the copolymerization ratio of the (R) component in the copolymer of the (E) component and the (R) component is excessively large, the addition amount of the polymerizable component and the alkali-soluble component is relatively small due to the relatively small amount of the (E) component. Tends to be insufficient. Moreover, when the copolymerization ratio of the component (R) is excessively small, heat resistance and strength tend to decrease.

  Here, as the component (R), for example, one or more of mono (meth) acrylates having a partial structure represented by the following formula (13) are preferably used.

(In Formula (13), R ^{1d to} R ^6d each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, or propyl, and R ^7d and R ^8d are each independently a hydrogen atom or a methyl group, an ethyl group, an alkyl group having 1 to 3 carbon atoms propyl group. ^{Further, R 7d} and ^{R 8d} are optionally linked to form a ring ^{.R 7d} and ^{R 8d} The ring formed by linking is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.)

  In the above formula (13), mono (meth) acrylate having a structure represented by the following formula (14), formula (15), or formula (16) is preferable. By introducing these partial structures, it is possible to increase the heat resistance and strength of mono (meth) acrylate. In addition, 1 type may be used for these mono (meth) acrylates and it may use 2 or more types together by arbitrary combinations and a ratio.

  As the mono (meth) acrylate having a partial structure represented by the formula (13), various known ones can be used, and those represented by the following formula (17) are particularly preferable.

(In the formula ^{(17), R 9d} represents a hydrogen atom or a methyl group, R ^10d represents the formula (13) above.)

The content of the mono (meth) acrylate having the partial structure represented by the formula (13) in the copolymer of the component (E) and the component (R) is usually 5 mol% or more, preferably 10 mol. % Or more, more preferably 15 mol% or more. Moreover, it is 90 mol% or less normally, Preferably it is 70 mol% or less, More preferably, it is 50 mol% or less.
When the content of the mono (meth) acrylate represented by the formula (13) in the copolymer of the component (E) and the component (R) is excessively small, the heat resistance tends to be insufficient. Moreover, when there is too much content of the mono (meth) acrylate shown by Formula (13), there exists a tendency for dispersion stability to fall.

Examples of the component (R) include radical polymerizable compounds other than mono (meth) acrylate having a partial structure represented by the above-described formula (13) as shown in the following specific examples.
styrene;
Α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene;
Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene;
Methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid- sec-butyl, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) acrylic Isobornyl acid, adamantyl (meth) acrylate, (meth) acrylic acid Allyl sulfonate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, (meth ) Salicyl acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, (meta ) Cresyl acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro (meth) acrylate -Iso-propyl, triphenylmethyl (meth) acrylate, (meth (Meth) acrylic acid esters such as cumyl acrylate, (meth) acrylic acid 3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl ;
(Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic amides such as N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide;
Vinyl compounds such as (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate;
Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate;
Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide;
N- (meth) acryloylphthalimide:

Among these, in order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the (R) component.
In this case, the copolymerization ratio of at least one selected from styrene, benzyl (meth) acrylate and monomaleimide is usually 1 mol% or more, preferably 3 mol% or more, and usually 70 mol% or less, preferably It is 50 mol% or less.

  As the (N) component (unsaturated monobasic acid) to be added to the epoxy group contained in the copolymer of the (E) component and the (R) component, known ones can be used. Examples of such unsaturated monobasic acids include unsaturated carboxylic acids having an ethylenically unsaturated double bond.

  Specific examples of the unsaturated carboxylic acid having such an ethylenically unsaturated double bond include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, Examples thereof include vinyl acetate, vinylidene chloride, maleimide, and (co) polymers thereof, among which acrylic acid and / or methacrylic acid are preferable. These (N) components may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The amount of the (N) component added to the epoxy group contained in the copolymer obtained by the copolymerization reaction of the (E) component and the (R) component is usually 10 mol of the epoxy group contained in the copolymer. %, Preferably 30 mol% or more, more preferably 50 mol% or more. When the addition ratio of the component (N) is excessively small, there is a tendency that an adverse effect due to the remaining epoxy group occurs, for example, stability with time decreases.
As a method of adding the (N) component to the copolymer of the (E) component and the (R) component, a known method can be employed.

The (T) component (polybasic acid anhydride) added to the hydroxyl group produced when the (N) component is added to the copolymer of the (E) component and the (R) component is not particularly limited and is publicly known. Can be used.
In addition, (T) component may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. By adding such components, alkali-solubility can be achieved.

The amount of the (T) component added is usually 10 mol% or more, preferably 20 mol, of the hydroxyl group produced when the (N) component is added to the copolymer of the (E) component and the (R) component. % Or more, more preferably 30 mol% or more. Moreover, it is 100 mol% or less normally, Preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.
If the amount of component (T) added is excessively large, the remaining film rate during development tends to decrease. If the amount of component (T) added is too small, the solubility tends to be insufficient.

  In addition, as a method of adding the (T) component to the hydroxyl group generated when the (N) component is added to the copolymer of the (E) component and the (R) component, a known method is arbitrarily adopted. can do.

The E-R-N-T resin further increases the photosensitivity by adding a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group to a part of the carboxy group generated after the addition of the (T) component. Can be improved.
Moreover, developability can also be improved by adding the glycidyl ether compound which does not have a polymerizable unsaturated group to a part of produced | generated carboxy group after (T) component addition.
Furthermore, you may add both of these after (T) component addition.

Examples of the E-R-N-T resin described above include resins described in JP-A-8-297366 and JP-A-2001-89533.
The weight average molecular weight (Mw) of the E-R-N-T resin is not particularly limited, but is usually 3,000 or more, preferably 5,000 or more, and usually 100,000 or less, preferably 50,000. 000 or less. If the weight average molecular weight (Mw) of the E-R-N-T resin is too small, the heat resistance and the film strength tend to be inferior. When the weight average molecular weight (Mw) of the E-R-N-T resin is excessively large, the solubility in the developer tends to be lowered. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the E-R-N-T resin is preferably 2.0 to 5.0.

[B-2] Acid-modified epoxy (meth) acrylate resin As the acid-modified epoxy (meth) acrylate resin, an α, β-unsaturated group-containing carboxylic acid adduct of an epoxy resin is added to a polyvalent carboxylic acid and / or An unsaturated group- and carboxy-group-containing epoxy resin to which the anhydride is added is mentioned. That is, (B-2-ii) the carboxy group of (B-2-ii) α, β-unsaturated monocarboxylic acid is added to the epoxy group of the epoxy resin by ring-opening addition, whereby an ester bond ( An ethylenically unsaturated bond is added via -COO-), and a carboxy group of (B-2-iii) polyvalent carboxylic acid and / or anhydride thereof is added to the resulting hydroxyl group. Things. Hereinafter, the constituent components of the unsaturated group- and carboxy group-containing epoxy resin which is an acid-modified epoxy (meth) acrylate resin will be described.

(B-2-i) Epoxy resin As an epoxy resin, it can select from well-known epoxy resins suitably and can be used. Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Examples thereof include epoxy resins, dihydroxyoxyfluorene type epoxy, dihydroxyalkyleneoxylfluorene type epoxy, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, and the like. Among these, from the viewpoint of high cured film strength, phenol novolac epoxy resin or cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, copolymer of glycidyl methacrylate and alkyl (meth) acrylate, 9 , 9-bis (4′-hydroxyphenyl) fluorene diglycidyl ether, and the like. Furthermore, a copolymer of glycidyl methacrylate and an alkyl (meth) acrylate is preferable from the viewpoint of a high taper angle and melting characteristics.

(B-2-ii) α, β-unsaturated monocarboxylic acid Examples of α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. And pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta ( Examples include meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, reaction product of (meth) acrylic acid and ε-caprolactone, and the like. Among these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

(B-2-iii) Polyvalent carboxylic acid and / or anhydride thereof Examples of the polyvalent carboxylic acid and / or anhydride thereof include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3- Methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethyl Examples include hexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and anhydrides thereof. Among these, from the viewpoint of image reproducibility and developability, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and tetrahydrophthalic anhydride is more preferable.

  The acid-modified epoxy (meth) acrylate resin in the present invention preferably has an acid value of 20 to 200 mg-KOH / g, and more preferably 30 to 180 mg-KOH / g. The weight average molecular weight (Mw) of the acid-modified epoxy (meth) acrylate resin is usually 1,000 or more, preferably 1,500 or more, usually 30,000 or less, preferably 20,000 or less, Preferably it is 10,000 or less.

  The acid-modified epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the (B-2-i) epoxy resin is dissolved in an organic solvent, and the (B-2-ii) α, β-unsaturated monocarboxylic acid is added in the presence of a catalyst and a thermal polymerization inhibitor. In addition, an addition reaction may be used, and (B-2-iii) a method of continuing the reaction by adding a polyvalent carboxylic acid and / or an anhydride thereof may be used.

  Here, examples of the organic solvent used for the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.

  Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, and tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride. One kind or two or more kinds of quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibins such as triphenylstibine are included.

  Furthermore, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

(B-2-ii) The amount of α, β-unsaturated monocarboxylic acid is usually 0.7 to 1.3 chemistry with respect to one chemical equivalent of the epoxy group of (B-2-i) epoxy resin. The amount can be equivalent, preferably 0.9 to 1.1 chemical equivalent.
Moreover, as temperature at the time of addition reaction, it is 60-150 degreeC normally, Preferably it can be set as the temperature of 80-120 degreeC.
Furthermore, the blending amount of (B-2-iii) polyvalent carboxylic acid and / or anhydride thereof is usually 0.1 to 1.2 chemical equivalents per one chemical equivalent of the hydroxyl group generated in the addition reaction. The amount is preferably 0.2 to 1.1 chemical equivalents.

  Specific examples of structural repeating units are shown below for the acid-modified epoxy (meth) acrylate resin.

[C] Modified Novolak Resin The modified novolak resin is obtained by reacting (Ci) one or more of the novolak resins with (C-ii) one or more of the unsaturated group-containing epoxy compounds. It can be obtained by adding one or more of (C-iii) polybasic acid and / or its anhydride to the hydroxyl group of the product. (However, a resol resin may be used instead of the novolac resin.)

(Ci) novolak resin Examples of the novolak resin include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4′-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4 -At least one phenol such as benzenetriol, benzoic acid, 4-hydroxyphenylacetic acid, salicylic acid, phloroglucinol, etc. under an acid catalyst, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, pro Propionaldehyde, benzaldehyde, salicylaldehyde, aldehydes such as furfural, or ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and at least one and polycondensation resin obtained by the.

  The condensation reaction of the phenols and aldehydes is performed in the absence of a solvent or in a solvent. A resole resin polycondensed in the same manner can be used except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin.

  The weight average molecular weight (Mw) of the novolak resin is usually 1,000 to 20,000, preferably 1,000 to 10,000, and more preferably 1,000 to 8,000. When the weight average molecular weight is less than 1,000, image strength is not ensured, and when it exceeds 20,000, developability is deteriorated.

(C-ii) Unsaturated group-containing epoxy compound As the unsaturated group-containing epoxy compound, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, glycidyloxy (poly) alkylene glycol (meth) Examples include acrylate, methyl glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) vinyl, and the like.
Of these, glycidyl methacrylate and (3,4-epoxycyclohexyl) methyl (meth) acrylate are particularly preferable.

  A known method can be used for the reaction of the novolak resin and the unsaturated group-containing epoxy compound. For example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. As a catalyst, an unsaturated group-containing epoxy compound can be added to the novolak resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours.

  The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (the total of the novolak resin and the unsaturated group-containing epoxy compound). In order to prevent polymerization during the reaction, a polymerization inhibitor (for example, one or more of methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, dibutylhydroxytoluene, phenothiazine, etc.) is added. The amount used is preferably 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.

  The ratio of adding the unsaturated group-containing epoxy compound to the phenolic hydroxyl group of the novolak resin is 1 to 100 mol%. This ratio can be adjusted by the amount of the unsaturated group-containing epoxy compound added to the phenolic hydroxyl group.

(C-iii) Polybasic acid and / or its anhydride A polybasic acid and / or its anhydride can be further added to the hydroxyl group of the reaction product of the novolak resin and the unsaturated group-containing epoxy compound. As the polybasic acid and / or anhydride thereof used here, known ones can be used, such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Dibasic carboxylic acids such as chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid or anhydrides thereof; trimellitic acid, pyromellitic acid And polybasic carboxylic acids such as benzophenone tetracarboxylic acid and biphenyl tetracarboxylic acid, or anhydrides thereof. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone or in combination of two or more.

  The addition rate of the polybasic acid and / or its anhydride is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 30 to 30 mol% of the hydroxyl group of the reaction product of the novolak resin and the unsaturated group-containing epoxy compound. 100 mol%. If this addition rate is too small, developability may be insufficient.

(Ethylenically unsaturated compounds)
It is preferable that the photosensitive composition contains an ethylenically unsaturated compound.
As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer solution for exposed and non-exposed areas associated therewith. From the viewpoint that the difference in solubility can be expanded, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group (meta ) Acrylate compounds are more preferred.

  The content of the ethylenically unsaturated compound in the photosensitive composition is usually 5% by weight or more, preferably 10% by weight or more, usually 80% by weight or less, preferably 70% by weight or less, based on the total solid content excluding the solvent. It is. If the content of the ethylenically unsaturated compound in the photosensitive composition is below this lower limit, sufficient sensitivity may not be obtained during exposure, and if it exceeds the upper limit, a preferred bank shape may not be ensured. .

  The ethylenically unsaturated compound suitably contained in the photosensitive composition according to the present invention will be described below.

  Examples of compounds having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.

  The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

Specific examples of esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
Reaction products of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.

Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, etc.

  In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts These reactants can be mentioned. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate, tri (meth) acrylate, etc. of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.

  As the (meth) acryloyloxy group-containing phosphates, those represented by the following general formula (5), (6), or (7) are preferable.

〔式（５），（６）および（７）中、Ｒ^１０は水素原子またはメチル基を示し、ｐおよびｒは１〜２５の整数、ｑは１、２、または３である。〕

[In the formulas (5), (6) and (7), R ¹⁰ represents a hydrogen atom or a methyl group, p and r are integers of 1 to 25, and q is 1, 2 or 3. ]

  Here, p and r are preferably 1 to 10, particularly 1 to 4, and specific examples of (meth) acryloyloxy group-containing phosphates include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth ) Acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and the like. These may be used alone or as a mixture.

Examples of urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate. ) Acrylate compound, aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tris Aromatic polyisocyanates such as isocyanate phenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, a reaction product of a polyisocyanate compounds and the like.
Examples of such urethane (meth) acrylates include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

  Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol As a compound having two or more hydroxyl groups in one molecule, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, etc. manufactured by Asahi Kasei Corporation Biuret type, A compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted. A compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, For example, “Duranate ME20-100” manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. 1 or more hydroxyl groups and 1 molecule Two or more, can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.

  Examples of epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds such as tellurium, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds And aromatic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, heterocyclic polyepoxy compounds such as triglycidyl tris (2-hydroxyethyl) isocyanurate, and reactants with polyepoxy compounds such as It is done.

  Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds in which the crosslinking rate is improved by sulfurating the ether bond of the containing ethylenically unsaturated compound with phosphorus pentasulfide to change it to a thioether bond, and for example, Japanese Patent No. 3164407 and JP-A-9- The polyfunctional (meth) acrylate compound and silica sol having a particle diameter of 5 to 30 nm (for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.)), methyl ethyl ketone-dispersed organosilica sol (Nissan Chemical) “MEK” ST "), methyl isobutyl ketone-dispersed organosilica sol (" MIBK-ST "manufactured by Nissan Chemical Co., Ltd.)], etc.] using an isocyanate group or mercapto group-containing silane coupling agent. Examples thereof include compounds in which the strength and heat resistance as a cured product are improved by reacting and binding a compound with a silica sol via a silane coupling agent.

  The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

  In the present invention, as the ethylenically unsaturated compound, esters or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc., five or more functional groups. Are particularly preferred.

(Photopolymerization initiator)
It is preferable that the photosensitive composition contains a photopolymerization initiator.
A photoinitiator will not be specifically limited if it is a compound which superposes | polymerizes an ethylenically unsaturated group with a photoactive ray, A well-known photoinitiator can be used.

  The content of the photopolymerization initiator in the photosensitive composition is usually 0.01% by weight or more, preferably 0.1% by weight or more, and more preferably based on the total solid content of the photosensitive composition excluding the solvent. Is 0.5% by weight or more, usually 30% by weight or less, preferably 20% by weight or less. When the content of the photopolymerization initiator in the photosensitive composition is excessively large, the adhesion to the substrate may be lowered. On the other hand, if it is too small, curability may be lowered.

  The blending ratio of the photopolymerization initiator to the ethylenically unsaturated compound in the photosensitive composition is usually 1/1 as the value of (ethylenically unsaturated compound) / (photopolymerization initiator) (weight ratio). ~ 100/1, preferably 2/1 to 50/1. If the blending ratio of the ethylenically unsaturated compound and the photopolymerization initiator deviates from this range, adhesion and curability may be lowered.

  Below, the specific example of the photoinitiator which can be used for the photosensitive composition concerning this invention is given.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Halomethylated triazine derivatives such as ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Halomethylated oxadiazole derivatives such as diazole;
2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( Hexaarylbiimidazole derivatives such as 2′-fluorophenyl) -4,5-diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl- [ Acetophenone derivatives such as 4- (methylthio) phenyl] -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-di-fluoro-3- (pyru-1-yl ) -Titanocene derivatives such as phen-1-yl;
Acetophenone oxime-o-acetate, 1,2-octanedione-1- [4- (phenylthio) -2- (o-) described in JP 2000-80068 A, JP 2006-036750 A, etc. Benzoyloxime)], 1- [9-ethyl-6- (2-benzoyl) -9H-carbazol-3-yl] ethanone-1- (o-acetyloxime) and the like:

  Other photopolymerization initiators that can be used in the present invention include Fine Chemicals, March 1, 1991, Vol. 20, no. 4, P16 to P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503, etc. The thing described in is mentioned.

  One of these photopolymerization initiators may be included alone in the photosensitive composition, or two or more thereof may be included.

  The photopolymerization initiator may be used in combination with the following hydrogen donating compounds for the purpose of improving sensitivity.

Examples of the hydrogen donating compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline. , Β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and other mercapto group-containing compounds;
Polyfunctional thiol compounds such as hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate;
N, N-dialkylaminobenzoic acid ester, N-phenylglycine, N-phenylglycine derivatives such as ammonium salt and sodium salt;
Derivatives such as phenylalanine, ammonium salts and sodium salts of phenylalanine;
Derivatives such as esters of phenylalanine;
Etc.
These may be used alone or in combination of two or more.

  Among these, from the viewpoint of the sensitivity of the photosensitive composition, mercapto group-containing heterocyclic compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole are preferable.

  From the viewpoint of the rectangularity of the pattern, one or more hydrogen donating compounds selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and the photopolymerization initiator as described above It is preferable to use one or more hexaarylbiimidazole derivatives in combination as a photopolymerization initiator system.

  Furthermore, you may mix | blend a thermal-polymerization initiator with the photoinitiator system in this invention. Specific examples of such a thermal polymerization initiator include azo compounds, organic peroxides and hydrogen peroxide. These may be used alone or in combination of two or more.

  In the case where a hydrogen donating compound or a thermal polymerization initiator is used in combination with the photopolymerization initiator, it is preferable that the total of these be the photopolymerization initiator content ratio in the photosensitive composition described above. The combined ratio of the photopolymerization initiator, the hydrogen donating compound and the thermal polymerization initiator is 5 to 300% by weight of the hydrogen donating compound with respect to the photopolymerization initiator and the thermal polymerization is started with respect to the photopolymerization initiator. It is preferable to make the agent 5 to 300% by weight.

(Amino compound)
The photosensitive composition according to the present invention may contain an amino compound in order to accelerate curing.
In this case, the content of the amino compound in the photosensitive composition is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content of the photosensitive composition. Moreover, it is 0.5 weight% or more normally, Preferably it is 1 weight% or more. If the content of the amino compound in the photosensitive composition is excessively large, the storage stability of the photosensitive composition may be deteriorated. Moreover, when there is little content, the hardening acceleration effect cannot be expected.

Examples of the amino compound include an amino compound having at least two methylol groups as functional groups and alkoxymethyl groups obtained by subjecting the methylol group to alcohol condensation modification having 1 to 8 carbon atoms.
More specifically, for example,
Melamine resin obtained by polycondensation of melamine and formaldehyde;
Benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde;
Glycoluril resin obtained by polycondensation of glycoluril and formaldehyde;
Urea resin obtained by polycondensation of urea and formaldehyde;
A resin obtained by copolycondensation of two or more of melamine, benzoguanamine, glycoluril, urea or the like with formaldehyde;
Modified resin obtained by alcohol condensation modification of the methylol group of the above resin;
Etc. These may be used alone or in combination of two or more.

  Among the amino compounds, melamine resins and modified resins thereof are preferable, modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins having 80% or more are particularly preferable.

Specific examples of the amino compound include melamine resin and modified resin thereof, for example, “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, manufactured by Mitsui Cytec Co., Ltd. 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nikarak” (registered trademark) MW-390, MW of Sanwa Chemical Co., Ltd. -100LM, MX-750LM, MW-30M, MX-45, MX-302 and the like.
Moreover, as said benzoguanamine resin and its modified resin, "Cymel" (trademark) 1123, 1125, 1128 etc. are mentioned, for example.
Examples of the glycoluril resin and modified resins thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172, “Nicarak” (registered trademark) MX-270, and the like.
Examples of the urea resin and its modified resin include “UFR” (registered trademark) 65, 300, “Nicarak” (registered trademark) MX-290 manufactured by Mitsui Cytec Co., Ltd., and the like.

(Other ingredients)
In the photosensitive composition, a colorant, a coatability improver, a development improver, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, a silane coupling agent, an epoxy compound, and other resins are appropriately blended. Can do.

<Colorant>
As the colorant, known colorants such as pigments and dyes can be used. Further, for example, when a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the photosensitive composition without agglomeration. In particular, by coloring the bank black, there is an effect that a clear pixel can be obtained. In addition to black dye, carbon black, titanium black, and the like as the black colorant, mixing with an organic pigment and coloring it black is also effective as an effect of imparting low conductivity.
The content of the colorant is usually 60% by weight or less, preferably 40% by weight or less, based on the total solid content of the photosensitive composition.

<Surface modifier, development improver>
As the surface modifier or development improver, for example, a known cationic, anionic, nonionic, fluorine-based or silicon-based surfactant can be used. Further, as the development improver, known ones such as organic carboxylic acids or anhydrides thereof can be used. Moreover, the content is 20 weight% or less normally with respect to the total solid of a photosensitive composition, Preferably it is 10 weight% or less.

<Polymerization inhibitor, antioxidant>
In the photosensitive composition, from the viewpoint of stability improvement, polymerization inhibitors such as hydroquinone and methoxyphenol, and hindered phenolic oxidation such as 2,6-di-tert-butyl-4-cresol (BHT) are used. It is preferable to contain an inhibitor. The content is usually in the range of 5 ppm to 1000 ppm, preferably 10 ppm to 600 ppm, based on the total solid content of the photosensitive composition. When the content is too small, the stability tends to deteriorate. On the other hand, if it is excessively large, curing may be insufficient, for example, when curing with light and / or heat. In particular, when used in a normal photolithography method, it is necessary to set the optimum amount in view of both storage stability and sensitivity of the photosensitive composition.

<Silane coupling agent>
It is also preferable to add a silane coupling agent to the photosensitive composition in order to improve adhesion to the substrate. Various types of silane coupling agents such as epoxy, methacrylic, amino and imidazole can be used, and epoxy and imidazole silane coupling agents are particularly preferred. The content thereof is usually 20% by weight or less, preferably 15% by weight or less, based on the total solid content of the photosensitive composition.

<Epoxy compound>
It is also preferable to add an epoxy compound to the photosensitive composition in order to improve curability and adhesion to the substrate.
As the epoxy compound, constituting a repeating unit of a so-called epoxy resin, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin, a polyglycidyl ester compound obtained by reacting a polycarboxylic acid compound and epichlorohydrin, and Examples include compounds ranging from low molecular weight substances to high molecular weight substances such as polyglycidylamine compounds obtained by reacting a polyamine compound and epichlorohydrin.

  Examples of the polyglycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and diglycidyl ether of bis (3,5-dimethyl-4-hydroxyphenyl). Type epoxy, diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide-added bisphenol A, diglycidyl ether of fluorene type bisphenol Type epoxy, phenol novolac type epoxy, cresol novolac type epoxy and the like. These polyglycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride, a divalent acid compound or the like to introduce a carboxy group.

  Examples of the polyglycidyl ester compound include diglycidyl ester type epoxy of hexahydrophthalic acid, diglycidyl ester type epoxy of phthalic acid, and the like. Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like.

  As content of an epoxy compound, it is 40 weight% or less normally with respect to the total solid of a photosensitive composition, Preferably it is 30 weight% or less. When there is too much content of an epoxy compound, the storage stability of a photosensitive composition may deteriorate.

(solvent)
The photosensitive composition used in the present invention usually contains a solvent and is used in a state where each of the aforementioned components is dissolved or dispersed in the solvent (hereinafter, the photosensitive composition containing the solvent is referred to as “photosensitive composition solution”). ").

  Although there is no restriction | limiting in particular as the solvent, For example, water and the organic solvent described below are mentioned.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri Ethylene glycol monomethyl ether Triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, glycol alkyl ether acetates such as 3-methoxy-1-butyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;

Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;

Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

  The solvent is capable of dissolving or dispersing each component in the photosensitive composition, and is selected according to the method of using the photosensitive composition, but a solvent having a boiling point in the range of 60 to 280 ° C is selected. It is preferable to do this. More preferably, it has a boiling point of 70 ° C. or higher and 260 ° C. or lower. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, isopropanol, etc. Is preferred. These solvents can be used alone or in combination of two or more.

These solvents are such that the ratio of the total solid content in the photosensitive composition solution is usually 10% by weight or more, preferably 15% by weight or more, usually 90% by weight or less, preferably 50% by weight or less. It is preferably used.
If the total solid concentration in the photosensitive composition is below this lower limit, a uniform coating film may not be obtained, and if it exceeds the upper limit, the required film thickness may not be controlled.

<Application of photosensitive composition>
As a coating method for forming the bank resist layer 13 by coating the photosensitive composition as described above on the undercoat layer 12 as shown in FIG. 1B, for example, a spinner method, a wire A bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be employed.
Above all, the die coating method is used from a comprehensive point of view, such as drastically reducing the amount of coating solution used, having no influence from mist adhering to the spin coating method, and suppressing foreign matter generation. preferable.

The coating amount of the photosensitive composition is, as a dry film thickness, the height of the bank including the undercoat layer 12, that is, the thickness _HA in FIG. 1D is usually 0.5 μm or more, preferably 1 μm or more, The amount is such that the film thickness is more preferably 1 μm or more, usually 10 μm or less, preferably 9 μm or less, more preferably 7 μm or less. At this time, it is important that the dry film thickness or the height of the finally formed bank is uniform over the entire area of the substrate. If this variation is large, uneven defects will occur in the substrate patterned with the organic thin film.

<Dry>
It is preferable to use a hot plate, an IR oven, or a convection oven for drying after applying the photosensitive composition on the undercoat layer.

The drying conditions can be appropriately selected according to the kind of the solvent component of the photosensitive composition, the performance of the dryer to be used, and the like, usually 40 ° C. or higher, preferably 50 ° C. or higher, usually 130 ° C. or lower, preferably 110 Dry at a temperature below ℃. Further, the drying time is preferably 15 seconds or more, preferably 30 seconds or more, preferably 5 minutes or less, and preferably 3 minutes or less. If the drying temperature is too low or the drying time is short, sufficient drying cannot be performed and the sensitivity becomes unstable. If the drying temperature is too high or the drying time is too long, the productivity decreases, the substrate, etc. There is a problem of thermal deterioration of the layer, which is not preferable.
The drying may be a reduced pressure drying method in which the temperature is not raised and drying is performed in a reduced pressure chamber, or may be used in combination with heat drying.

{Bank formation process}
As described above, the bank forming resist layer 13 is formed on the undercoat layer 12 by coating and drying the photosensitive composition containing the ink repellent component on the entire surface, and then using the exposure mask 20 to form the bank pattern. Then, the bank 14 is formed by removing the non-image portion together with the undercoat layer 12 by development processing (FIGS. 1C and 1D).

<Exposure>
In the exposure, a negative exposure mask (mask pattern) 20 is superimposed on the bank resist layer 13 formed by applying and drying the photosensitive composition, and photoactivity such as ultraviolet light or visible light is passed through this exposure mask. This is done by irradiating a line light source. When exposure is performed using the exposure mask 20 as described above, the exposure mask is placed close to the bank resist layer, or the exposure mask is disposed at a position away from the bank resist layer, and the exposure mask 20 is interposed therebetween. A method of projecting exposure light may be used.
Further, a scanning exposure method using laser light without using an exposure mask may be used.

  At this time, in order to prevent the deterioration of the sensitivity of the bank resist layer due to oxygen, the exposure is performed in a deoxygenated atmosphere or after the formation of an oxygen blocking layer such as a polyvinyl alcohol layer on the bank resist layer. May be.

  The light source used for said exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

  The optical filter may be of a type that can control the light transmittance at the exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.

Energy of exposure generally, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 300 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 150 mJ / cm ² or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

<Development>
An image pattern can be formed by developing after performing the exposure described above. The developer used for development is not limited, but an aqueous solution of an alkaline compound or an organic solvent is preferably used.
The developer may further contain a surfactant, buffer, complexing agent, dye or pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), co The organic alkaline compound such emissions and the like. These alkaline compounds may be a mixture of two or more.

In addition, when using the organic thin film patterning substrate of the present invention for an organic electroluminescent device, it is preferable to use an aqueous solution of an organic alkaline compound as a developing solution from the viewpoint of little adverse effect on device performance.
In this case, if the concentration of the organic alkaline compound in the aqueous organic alkali solution is excessively high, the bank may be damaged, and if it is excessively low, sufficient developability may not be ensured.

Examples of the organic solvent include ethyl alcohol, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. An organic solvent may be used individually by 1 type, may use 2 or more types together, and may be used as aqueous solution.
For example, it may be used as an aqueous solution containing 0.05 to 5% by weight of organic alkali such as TMAH and 0.1 to 20% by weight of alcohol such as ethyl alcohol.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; alkylbenzenesulfonic acid Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts; amphoteric surfactants such as alkylbetaines and amino acids.

  There is no particular limitation on the development processing method, but it is usually 10 ° C. or higher, preferably 15 ° C. or higher, usually 50 ° C. or lower, preferably 45 ° C. or lower, at immersion development, spray development, brush development, ultrasonic development. Etc. are performed.

  During development, the undercoat layer in the non-image area is removed together with the bank resist layer. Accordingly, the bank resist layer and the undercoat layer do not remain in the non-image portion, and the substrate or other layer under the undercoat layer is exposed in the non-image portion. Here, the non-image portion is a portion that is removed by exposure and development, and is a portion other than remaining as a bank.

Since the undercoat layer exists at the interface between the bank resist layer and the substrate, and the undercoat layer and the bank resist layer form a completely integrated bank, for example, as proposed in Japanese Patent Application Laid-Open No. 2005-326799. It is completely different from a two-stage bank. Further, the side face as proposed in Japanese Patent Application Laid-Open No. 2005-174906 is different from the two-layered bank in which the side face is lyophilic and only the top surface is liquid repellent. Contains an ink-repellent component, and the undercoat layer exists only in the very lower layer at the interface with the substrate or other layers.
Although the bank consisting of the undercoat layer and the bank resist layer is integrated in shape, the undercoat layer maintains a film when the photosensitive composition is applied. The appearance of layering is observed.

<Additional exposure and thermosetting>
After development, if necessary, additional exposure may be performed by a method similar to the above exposure method, or thermosetting treatment may be performed.
The conditions for the additional exposure are the same as the above exposure conditions.
The temperature of the thermosetting treatment condition is usually 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher, usually 280 ° C. or lower, preferably 250 ° C. or lower, more preferably 240 ° C. or lower. 5 minutes or more, preferably 20 minutes or more, usually 60 minutes or less. In particular, for the expression of liquid repellency, it is preferable to carry out the thermosetting treatment at 200 to 240 ° C. for about 20 to 60 minutes.

{Features of manufacturing method}
The organic thin film patterning substrate obtained by the production method of the present invention has a bank and a region partitioned by the bank on the substrate, and is used for forming an organic thin film in the region partitioned by the bank. As described above, the bank is formed on an undercoat layer containing a hydrophilic compound, and the bank itself contains an ink repellent component.

  The organic thin film patterning substrate is surrounded by the bank because the ink repellency component contained in the bank does not remain on the ink application surface, i.e., the area surrounded by the bank. This is suitable when an organic thin film is formed on the region by an ink ejection type coating method, and is particularly suitable for those having a bank on an organic layer as another layer on the substrate. Especially, it is suitable when forming a bank on the positive hole injection layer or positive hole transport layer of an organic electroluminescent element as an organic layer.

  That is, when the bank is formed on the organic layer, the affinity between the bank resist layer and the organic layer is high, and it is difficult to remove the bank resist layer in the non-image area during development. Moreover, if damage or ionic deposits are given to the organic layer by development, the device performance is remarkably deteriorated. Therefore, it is particularly important to completely develop and remove the bank resist layer in the non-image area without affecting the organic layer. In this case, if the manufacturing method of the present invention is used, the photosensitive composition is applied through an undercoat layer excellent in development removability to form a bank resist layer, so that development removal is also performed under mild conditions. In addition, both the manufacturing process and the obtained device performance are remarkably improved as compared with the conventional method.

[Formation of organic thin film]
The organic thin film patterning substrate of the present invention is used to form an organic thin film in a region defined by banks on the substrate, and the organic electroluminescent device of the present invention forms an organic thin film in this way. Manufactured.
Hereinafter, a method for forming this organic thin film will be described.
In order to form the organic thin film 16 in the region 15 partitioned by the bank 14 on the substrate 11 of the organic thin film patterning substrate (FIG. 1E), the components of the organic thin film 16 are usually dissolved or dispersed in a solvent. The supplied ink is supplied into the bank partition region 15 and dried.

The method of supplying the ink into the bank partition region 15 is not particularly limited, but an ink discharge type coating method such as an ink jet method (droplet discharge method) or a nozzle print method (liquid flow discharge method) is preferable (Japanese Patent Laid-Open No. 59). JP-A-75205, JP-A-61-245106, JP-A-63-235901).
In other words, the ink ejection type coating method can selectively apply ink only to a specific region, has less material loss, and can form an organic thin film satisfactorily by an efficient manufacturing process. Have. In addition, since it is possible to perform both ink application and patterning at the same time, it is a very advantageous manufacturing method in terms of manufacturing cost.

  As an ink solvent used in an ink discharge type coating method, it is generally known that a relatively high amount of a high boiling point solvent component is added to prevent nozzle drying, and patterning is applied. In the simultaneous discharge-type coating method, unlike the spin coating method and die coating method, the solvent component in the composition affects the film thickness, shape, and uniformity of the final coating film as well as other effects. ("Surface Science Seminar", pages 65-77, 2001), it is preferable to select an optimum solvent in consideration of these factors.

  In particular, in the case of the ink jet method, when a droplet is deposited on the surface to be coated with a droplet size of 20 pl, a solvent having a droplet diameter of 100 to 400 μm after the lapse of 1 minute after the droplet deposition is preferable. More preferably, the droplet diameter is 150 to 300 μm. As a result, it is possible to prevent the occurrence of film thickness unevenness and pinholes and to ensure the linearity of the end portion. However, the influence of the solvent used in the ink is the largest in this respect as well. The droplet diameter obtained by the ink jet method has a strong correlation with the wet spreading property (contact angle). Usually, the droplet diameter can be increased by lowering the viscosity and the surface tension. Further, when the content of the solvent having high affinity to the coated surface is increased, the droplet diameter can be increased.

After the ink is supplied into the bank partition region, an organic thin film is formed by a drying process. For this drying condition, a known method can be freely selected, for example, a hot plate, an IR oven, a convection oven, etc. It is done. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. The environment can be selected from the atmosphere, N ₂ gas, reduced pressure, etc. according to the characteristics of the organic thin film to be formed.

[Organic electroluminescence device]
The organic electroluminescent device of the present invention is an organic electroluminescent device having a bank and a region partitioned by the bank on a substrate, and having an organic thin film in the region partitioned by the bank, The bank is formed on an undercoat layer containing a hydrophilic compound, and the bank contains an ink repellent component. That is, the organic electroluminescent element of the present invention is manufactured by forming an organic thin film in the bank partition region using the organic thin film patterning substrate of the present invention.

  In the organic electroluminescent element of the present invention, the organic thin film formed in the bank partition region is preferably a light emitting layer in that it can be color-coded with high accuracy. The bank is preferably formed on an organic layer, and the organic layer is preferably a hole injection layer and / or a hole transport layer.

  Below, the layer structure of the organic electroluminescent element of this invention, its general formation method, etc. are demonstrated with reference to FIG.

  FIG. 2 is a schematic cross-sectional view showing a structural example of the organic electroluminescence device of the present invention. In FIG. 2, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 Represents a light-emitting layer, 6 represents a hole blocking layer, 7 represents an electron transport layer, 8 represents an electron injection layer, and 9 represents a cathode.

  In the present invention, the wet film forming method refers to, for example, spin coating method, dip coating method, die coating method, bar coating method, blade coating method, roll coating method, spray coating method, capillary coating method, ink jet method, screen printing. This method is a wet film formation method such as a method, a gravure printing method, or a flexographic printing method. Among these film forming methods, a spin coating method, a spray coating method, and an ink jet method are preferable. This is because the liquid property specific to the coating composition used for the organic electroluminescent element is matched.

{substrate}
The substrate 1 serves as a support for the organic electroluminescent element, and a quartz or glass plate, a metal plate or a metal foil, a plastic film, a sheet, or the like is used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, polysulfone or the like is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too small, the organic electroluminescent element may be deteriorated by the outside air that has passed through the substrate, which is not preferable. For this reason, a method of providing a gas barrier property by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate is also a preferable method.

{anode}
The anode 2 serves to inject holes into the layer on the light emitting layer side.

  This anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or It is composed of a conductive polymer such as poly (3-methylthiophene), polypyrrole, or polyaniline.

  In general, the anode 2 is often formed by a sputtering method, a vacuum deposition method, or the like. In addition, when forming the anode 2 using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powder, an appropriate binder resin solution It is also possible to form the anode 2 by dispersing it and applying it onto the substrate 1. Furthermore, in the case of a conductive polymer, a thin film can be directly formed on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 (Appl. Phys. Lett. 60, 2711, 1992).

  The anode 2 usually has a single-layer structure, but it can also have a laminated structure made of a plurality of materials if desired.

  The thickness of the anode 2 varies depending on the required transparency. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably about 500 nm or less. When it may be opaque, the thickness of the anode 2 is arbitrary, and the anode 2 may be the same as the substrate 1. Furthermore, it is also possible to laminate different conductive materials on the anode 2 described above.

  For the purpose of removing impurities adhering to the anode 2 and adjusting the ionization potential to improve the hole injection property, the surface of the anode 2 is treated with ultraviolet (UV) / ozone, or with oxygen plasma or argon plasma. It is preferable to do.

{Hole injection layer}
The hole injection layer 3 is a layer that transports holes from the anode 2 to the light emitting layer 5, and is usually formed on the anode 2.

  The method for forming the hole injection layer 3 according to the present invention may be a vacuum deposition method or a wet film formation method, and is not particularly limited, but the hole injection layer 3 is formed by a wet film formation method from the viewpoint of reducing dark spots. It is preferable.

  The thickness of the hole injection layer 3 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.

<Formation of hole injection layer by wet film formation method>
When the hole injection layer 3 is formed by a wet film formation method, a material for forming the hole injection layer 3 is usually mixed with an appropriate solvent (a solvent for hole injection layer) to form a film-forming composition ( The composition for forming a hole injection layer) is prepared, and this composition for forming the hole injection layer is applied onto a layer (usually an anode) corresponding to the lower layer of the hole injection layer 3 by an appropriate technique. The hole injection layer 3 is formed by depositing and drying.

(Hole transporting compound)
The composition for forming a hole injection layer usually contains a hole transporting compound and a solvent as constituent materials of the hole injection layer.

  The hole transporting compound may be a high molecular compound or a low molecular compound as long as it is a compound having a hole transporting property that is usually used in a hole injection layer of an organic electroluminescence device. Is preferably a polymer compound.

  The hole transporting compound is preferably a compound having an ionization potential of 4.5 eV to 6.0 eV from the viewpoint of a charge injection barrier from the anode 2 to the hole injection layer 3. Examples of hole transporting compounds include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, compounds in which tertiary amines are linked by a fluorene group, hydrazones Compounds, silazane compounds, silanamin compounds, phosphamine compounds, quinacridone compounds, and the like.

  The hole transporting compound used as the material for the hole injection layer 3 may contain any one of these compounds alone, or may contain two or more. When two or more hole transporting compounds are contained, the combination thereof is arbitrary, but one or more of aromatic tertiary amine polymer compounds and one of other hole transporting compounds or Two or more types are preferably used in combination.

  Among the above examples, an aromatic amine compound is preferable from the viewpoint of amorphousness and visible light transmittance, and an aromatic tertiary amine compound is particularly preferable. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.

  The type of the aromatic tertiary amine compound is not particularly limited, but from the viewpoint of uniform light emission due to the surface smoothing effect, a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymerizable compound in which repeating units are linked) is further included. preferable. Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (I).

(In Formula (I), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar ^{3 to} Ar ⁵ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Represents a linking group selected from the group of linking groups, and among Ar ^{1 to} Ar ⁵ , two groups bonded to the same N atom may be bonded to each other to form a ring.

（上記各式中、Ａｒ^６〜Ａｒ^１６は、それぞれ独立して、置換基を有していてもよい芳香族炭化水素基または置換基を有していてもよい芳香族複素環基を表す。Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または任意の置換基を表す。））

(In said each formula, Ar < ⁶ > -Ar < ¹⁶ > represents each independently the aromatic hydrocarbon group which may have a substituent, or the aromatic heterocyclic group which may have a substituent. R ¹ and R ² each independently represents a hydrogen atom or an arbitrary substituent.))

As the aromatic hydrocarbon group and the aromatic heterocyclic group of Ar ^{1 to} Ar ¹⁶ , a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene from the viewpoint of the solubility, heat resistance, hole injection / transport property of the polymer compound A group derived from a ring or a pyridine ring is preferred, and a group derived from a benzene ring or a naphthalene ring is more preferred.

The aromatic hydrocarbon group and aromatic heterocyclic group of Ar ^{1 to} Ar ¹⁶ may further have a substituent. The molecular weight of the substituent is usually 400 or less, preferably about 250 or less. As the substituent, an alkyl group, an alkenyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like are preferable.

When R ¹ and R ² are optional substituents, examples of the substituent include an alkyl group, an alkenyl group, an alkoxy group, a silyl group, a siloxy group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. .

  Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the general formula (I) include those described in WO2005 / 089024.

  The concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.01% by weight or more, preferably in terms of film thickness uniformity. Is 0.1% by weight or more, more preferably 0.5% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. If this concentration is too high, film thickness unevenness may occur, and if it is too low, defects may occur in the formed hole injection layer.

(Electron-accepting compound)
The composition for forming a hole injection layer preferably contains an electron accepting compound as a constituent material of the hole injection layer.

  The electron-accepting compound is preferably a compound having an oxidizing power and the ability to accept one electron from the above-described hole transporting compound, specifically, a compound having an electron affinity of 4 eV or more is preferable, and 5 eV or more. The compound which is the compound of these is further more preferable.

  Examples of such electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. Examples thereof include one or more compounds selected from the group. More specifically, an onium salt substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrafluoroborate (WO2005 / 089024); iron chloride (Only one of them may be used, or two or more may be used in any combination and ratio.) (Japanese Patent Laid-Open No. 11-251067), high-valent inorganic compounds such as ammonium peroxodisulfate A cyano compound such as tetracyanoethylene; an aromatic boron compound such as tris (pendafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365); a fullerene derivative; iodine and the like.

  These electron accepting compounds can improve the conductivity of the hole injection layer by oxidizing the hole transporting compound.

  The content of the electron-accepting compound in the hole-injecting layer or the composition for forming a hole-injecting layer with respect to the hole-transporting compound is usually 0.1 mol% or more, preferably 1 mol% or more. However, it is usually 100 mol% or less, preferably 40 mol% or less.

(Other components)
As a material for the hole injection layer, other components may be further contained in addition to the above-described hole transporting compound and electron accepting compound as long as the effects of the present invention are not significantly impaired. Examples of other components include various light emitting materials, electron transporting compounds, binder resins, and coating property improving agents. In addition, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

(solvent)
At least one of the solvents of the composition for forming a hole injection layer used in the wet film formation method is preferably a compound that can dissolve the constituent material of the hole injection layer. The boiling point of this solvent is usually 110 ° C. or higher, preferably 140 ° C. or higher, particularly 200 ° C. or higher, usually 400 ° C. or lower, and preferably 300 ° C. or lower. If the boiling point of the solvent is too low, the drying speed is too high and the film quality may be deteriorated. Further, if the boiling point of the solvent is too high, it is necessary to increase the temperature of the drying step, which may adversely affect other layers and the substrate.

  Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.

  Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , Phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, aromatic ethers such as 2,4-dimethylanisole, and the like.

  Examples of the ester solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.

Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-isopropylpropylphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, and methylnaphthalene. Can be mentioned.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

In addition, dimethyl sulfoxide and the like can also be used.
These solvent may use only 1 type and may use 2 or more types by arbitrary combinations and a ratio.

(Film formation method)
After preparing the composition for forming the hole injection layer, the composition is applied on the layer corresponding to the lower layer of the hole injection layer 3 (usually the anode 2) by wet film formation, and dried. The hole injection layer 3 can be formed.

  The temperature in the film forming step is preferably 10 ° C. or higher, and preferably 50 ° C. or lower, in order to prevent film loss due to the formation of crystals in the composition.

  Although the relative humidity in a film-forming process is not limited unless the effect of this invention is impaired remarkably, it is 0.01 ppm or more normally and 80% or less normally.

  After the film formation, the film of the composition for forming a hole injection layer is usually dried by heating or the like. Examples of the heating means used in the heating step include a clean oven, a hot plate, infrared rays, a halogen heater, microwave irradiation and the like. Among them, a clean oven and a hot plate are preferable in order to uniformly apply heat to the entire film.

  The heating temperature in the heating step is preferably heated at a temperature equal to or higher than the boiling point of the solvent used in the composition for forming a hole injection layer as long as the effects of the present invention are not significantly impaired. In the case of a mixed solvent containing two or more types of solvents used in the hole injection layer, at least one type is preferably heated at a temperature equal to or higher than the boiling point of the solvent. In consideration of an increase in the boiling point of the solvent, the heating step is preferably performed at 120 ° C. or higher, preferably 410 ° C. or lower.

  In the heating step, the heating time is not limited as long as the heating temperature is not lower than the boiling point of the solvent of the composition for forming a hole injection layer and sufficient insolubilization of the coating film does not occur. Is less than a minute. If the heating time is too long, the components of the other layers tend to diffuse, and if it is too short, the hole injection layer tends to be inhomogeneous. Heating may be performed in two steps.

<Formation of hole injection layer by vacuum deposition>
When the hole injection layer 3 is formed by a vacuum deposition method, one or more of the constituent materials of the hole injection layer 3 (the aforementioned hole transporting compound, electron accepting compound, etc.) are contained in a vacuum container. (If two or more materials are used, put them in each crucible), evacuate the vacuum vessel to about 10 ⁻⁴ Pa with an appropriate vacuum pump, and then heat the crucible (2 When using more than one kind of material, heat each crucible) and evaporate by controlling the amount of evaporation (when using more than two kinds of materials, evaporate by controlling the amount of evaporation independently) A hole injection layer 3 is formed on the anode 2 of the substrate placed face to face. In addition, when using 2 or more types of materials, the hole injection layer 3 can also be formed by putting those mixtures into a crucible, heating and evaporating.

The degree of vacuum at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 × 10 ⁻⁶ Torr (0.13 × 10 ⁻⁴ Pa) or more, usually 9.0 × 10 ⁻⁶ Torr. (12.0 × 10 ⁻⁴ Pa) or less. The deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 Å / second or more and usually 5.0 Å / second or less. The film forming temperature at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10 ° C. or higher, preferably 50 ° C. or lower.

{Hole transport layer}
The formation method of the hole transport layer 4 may be a vacuum deposition method or a wet film formation method, and is not particularly limited. However, from the viewpoint of reducing dark spots, the hole transport layer 4 is preferably formed by a wet film formation method.

  The hole transport layer 4 can be formed on the hole injection layer 3 when there is a hole injection layer and on the anode 2 when there is no hole injection layer 3. However, the organic electroluminescent element of the present invention may have a configuration in which the hole transport layer is omitted.

  The material for forming the hole transport layer 4 is preferably a material having high hole transportability and capable of efficiently transporting injected holes. Therefore, it is preferable that the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is high, and impurities that become traps are not easily generated during manufacturing or use. In many cases, it is preferable not to quench the light emitted from the light emitting layer 5 or to form an exciplex with the light emitting layer 5 to reduce the efficiency because it is in contact with the light emitting layer 5.

Such a material for the hole transport layer 4 may be any material conventionally used as a constituent material for the hole transport layer. For example, the hole transport property used for the hole injection layer 3 described above. What was illustrated as a compound is mentioned. In addition, two or more condensed aromatic rings including two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl are substituted with nitrogen atoms. Aromatic amine compounds having a starburst structure (J. Lumin., 72) such as aromatic diamines (Japanese Patent Laid-Open No. 5-234811), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine -74, 985, 1997), an aromatic amine compound consisting of a tetramer of triphenylamine (Chem. Commun., 2175, 1996), 2,2 ', 7,7'-tetrakis- ( Spiro compounds such as diphenylamino) -9,9′-spirobifluorene (Synth. Metals, 91, 209, 1997), 4,4′-N, N′-dicarbazole Examples thereof include carbazole derivatives such as biphenyl, etc. Polyarylene ether sulfone (Polym. Adv. Tech., 7) containing, for example, polyvinyl carbazole, polyvinyl triphenylamine (Japanese Patent Laid-Open No. 7-53953), and tetraphenylbenzidine. Volume, p. 33, 1996).

  When the hole transport layer 4 is formed by wet film formation, a composition for forming a hole transport layer is prepared in the same manner as the formation of the hole injection layer 3 and then heated and dried after wet film formation.

  The composition for forming a hole transport layer contains a solvent in addition to the above hole transport compound. The solvent used is the same as that used for the composition for forming a hole injection layer. The film forming conditions, heat drying conditions, and the like are the same as in the case of forming the hole injection layer 3.

  When the hole transport layer is formed by vacuum deposition, the film forming conditions are the same as those for forming the hole injection layer 3.

  The hole transport layer 4 may contain various light emitting materials, electron transport compounds, binder resins, coating property improving agents, and the like in addition to the hole transport compound.

  The hole transport layer 4 may be a layer formed by crosslinking a crosslinkable compound. Here, the crosslinkable compound is a compound having a crosslinking group, and forms a polymer by crosslinking. The crosslinkable compound may be any of a monomer, an oligomer, and a polymer. The crosslinkable compound may have only 1 type, and may have 2 or more types by arbitrary combinations and ratios.

  Examples of the crosslinking group of the crosslinking compound include: a group derived from a cyclic ether such as oxetane or epoxy; a group derived from an unsaturated double bond such as a vinyl group, a trifluorovinyl group, a styryl group, an acrylic group, methacryloyl, or cinnamoyl. A group derived from benzocyclobutane and the like.

  The number of crosslinkable groups possessed by the crosslinkable compound, that is, the monomer, oligomer or polymer having a crosslinkable group is not particularly limited, but is generally less than 2.0, preferably 0.8 or less, more preferably 0 per unit charge transport unit. A number that is .5 or less is preferred. This is to adjust the relative dielectric constant of the hole transport layer forming material to a suitable range. Moreover, when the number of crosslinking groups is too large, reactive active species are generated, which may adversely affect other materials. Here, when the material forming the crosslinkable polymer is a monomer body, the unit charge transport unit is a monomer body itself, and indicates a skeleton (main skeleton) excluding a crosslinking group. Even when other types of monomers are mixed, the main skeleton of each monomer is shown. When the material forming the crosslinkable polymer is an oligomer or polymer, in the case of repeating a structure in which conjugation is broken organically, the repeated structure is defined as a unit charge transport unit. In the case of a structure in which conjugation is widely connected, a minimum repeating structure exhibiting charge transporting property or a monomer structure is shown. For example, polycyclic aromatics such as naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, perylene, fluorene, triphenylene, carbazole, triarylamine, tetraarylbenzidine, 1,4-bis (diarylamino) benzene, etc. It is done.

  Furthermore, as the crosslinkable compound, it is preferable to use a hole transporting compound having a crosslinkable group. Examples of hole transporting compounds in this case include nitrogen-containing aromatic compound derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives, phthalocyanine derivatives, porphyrin derivatives; Examples include phenylamine derivatives; silole derivatives; oligothiophene derivatives, condensed polycyclic aromatic derivatives, metal complexes, and the like. Among them, nitrogen-containing aromatic derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives; triphenylamine derivatives, silole derivatives, condensed polycyclic aromatic derivatives, metal complexes, etc. Particularly preferred are triphenylamine derivatives.

  The molecular weight of the crosslinkable compound is usually 5000 or less, preferably 2500 or less, preferably 300 or more, more preferably 500 or more.

  In order to form a hole transport layer 4 by crosslinking a crosslinkable compound, a composition for forming a hole transport layer in which a crosslinkable compound is dissolved or dispersed in a solvent is usually prepared and deposited by a wet film formation method. Then, the crosslinkable compound is crosslinked.

  This composition for hole transport layer formation may contain the additive which accelerates | stimulates a crosslinking reaction other than a crosslinkable compound. Examples of additives that accelerate the crosslinking reaction include polymerization initiators and polymerization accelerators such as alkylphenone compounds, acylphosphine oxide compounds, metallocene compounds, oxime ester compounds, azo compounds, onium salts; condensed polycyclic hydrocarbons, And photosensitizers such as porphyrin compounds and diaryl ketone compounds. One of these may be used alone, or two or more may be used in any combination and ratio.

  Further, the composition for forming a hole transport layer may further contain a coating property improver such as a leveling agent and an antifoaming agent, an electron accepting compound, a binder resin, and the like.

  In this composition for forming a hole transport layer, the crosslinkable compound is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, usually 50% by weight or less, preferably It is contained in an amount of 20% by weight or less, more preferably 10% by weight or less.

  After forming a composition for forming a hole transport layer containing a crosslinkable compound at such a concentration on the lower layer (usually the hole injection layer 3), the composition is crosslinked by heating and / or irradiation with electromagnetic energy such as light. Are polymerized by crosslinking.

  Conditions such as temperature and humidity during film formation are the same as those during the wet film formation of the hole injection layer 3.

  The heating method after film formation is not particularly limited, and examples thereof include heat drying and reduced pressure drying. The heating temperature condition in the case of heat drying is usually 120 ° C. or higher, preferably 400 ° C. or lower.

  The heating time is usually 1 minute or longer, preferably 24 hours or shorter. The heating means is not particularly limited, and means such as placing a laminated body having a deposited layer on a hot plate or heating in an oven is used. For example, conditions such as heating on a hot plate at 120 ° C. or more for 1 minute or more can be used.

  In the case of irradiation with electromagnetic energy such as light, a method of irradiating directly using an ultraviolet / visible / infrared light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a halogen lamp, an infrared lamp, etc. Examples include a mask aligner and a method of irradiation using a conveyor type light irradiation device. In electromagnetic energy irradiation other than light, for example, there is a method of irradiation using a device that irradiates a microwave generated by a magnetron, a so-called microwave oven. As the irradiation time, it is preferable to set conditions necessary for reducing the solubility of the film, but irradiation is usually performed for 0.1 seconds or longer, preferably 10 hours or shorter.

  Heating and irradiation of electromagnetic energy such as light may be performed individually or in combination. When combined, the order of implementation is not particularly limited.

  The film thickness of the hole transport layer 4 thus formed is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, preferably 100 nm or less.

{Light emitting layer}
When the hole injection layer 3 or the hole transport layer 4 is provided, the light emitting layer 5 is provided on the hole transport layer 4. The light emitting layer 5 is a layer that is excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 between electrodes to which an electric field is applied, and becomes a main light emitting source.

<Light emitting layer material>
The light emitting layer 5 contains at least a material having a light emitting property (light emitting material) as a constituent material, and preferably a compound having a hole transporting property (hole transporting compound) or an electron transport. A compound (electron transporting compound) having the following properties: A light emitting material may be used as a dopant material, and a hole transporting compound, an electron transporting compound, or the like may be used as a host material. There is no particular limitation on the light-emitting material, and a material that emits light at a desired light emission wavelength and has favorable light emission efficiency may be used. Furthermore, the light emitting layer 5 may contain other components as long as the effects of the present invention are not significantly impaired. In addition, when forming the light emitting layer 5 with a wet film-forming method, it is preferable to use a low molecular weight material in any case.

(Luminescent material)
A light-emitting material is a material having a fluorescence quantum yield of 30% or more in a dilute solution at room temperature in an inert gas atmosphere, and is manufactured using it in comparison with the fluorescence spectrum in the dilute solution. A part or all of the EL spectrum obtained when a current is applied to the organic electroluminescent element formed is defined as a material attributed to light emission of the material.

  The light emitting material is not limited as long as it is usually used as a light emitting material of an organic electroluminescent element. For example, a fluorescent material or a phosphorescent material may be used, but a phosphorescent material is preferable from the viewpoint of internal quantum efficiency. Alternatively, blue may be used in combination, such as using a fluorescent material, and green and red using a phosphorescent material.

  As the light emitting material, for the purpose of improving the solubility in a solvent, a material in which the symmetry or rigidity of the molecule is reduced or a lipophilic substituent such as an alkyl group is introduced is used. preferable.

  Hereinafter, examples of fluorescent light emitting materials (fluorescent dyes) among the light emitting materials will be given, but the fluorescent dyes are not limited to the following examples.

  Examples of fluorescent dyes that give blue light emission (blue fluorescent dyes) include naphthalene, chrysene, perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof. Of these, anthracene, chrysene, pyrene, and derivatives thereof are preferable.

Examples of fluorescent dyes that give green light emission (green fluorescent dyes) include quinacridone, coumarin, aluminum complexes such as Al (C ₉ H ₆ NO) _3, and derivatives thereof.

  Examples of fluorescent dyes that give yellow light (yellow fluorescent dyes) include rubrene, perimidone, and derivatives thereof.

  Examples of fluorescent dyes that give red light emission (red fluorescent dyes) include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyrene) -4H-pyran) -based compounds, benzopyran, rhodamine, Examples thereof include xanthene such as benzothioxanthene and azabenzothioxanthene, and derivatives thereof.

  As the phosphorescent material, for example, a long-period type periodic table (hereinafter referred to as a long-period type periodic table when referred to as “periodic table” unless otherwise specified) is selected from the seventh to eleventh groups. A Werner complex or an organometallic complex containing a metal as a central metal.

  Preferred examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. Among these, iridium or platinum is more preferable.

  As the ligand of the complex, a ligand in which a (hetero) aryl group such as a (hetero) arylpyridine ligand or a (hetero) arylpyrazole ligand and a pyridine, pyrazole, phenanthroline, or the like is connected is preferable. A pyridine ligand and a phenylpyrazole ligand are preferable. Here, (hetero) aryl represents an aryl group or a heteroaryl group.

  Specific examples of the phosphorescent material include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2- Phenylpyridine) osmium, tris (2-phenylpyridine) rhenium, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, and the like.

  The molecular weight of the compound used as the light emitting material is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10,000 or less, preferably 5000 or less, more preferably 4000 or less, still more preferably 3000 or less, and usually 100 or more, Preferably it is 200 or more, More preferably, it is 300 or more, More preferably, it is the range of 400 or more. If the molecular weight of the luminescent material is too small, the heat resistance will be significantly reduced, gas generation will be caused, the film quality will be reduced when the film is formed, or the morphology of the organic electroluminescent element will be changed due to migration, etc. Sometimes come. On the other hand, if the molecular weight of the luminescent material is too large, it tends to be difficult to purify the organic compound, or it may take time to dissolve in the solvent.

  In addition, only 1 type may be used for the luminescent material mentioned above, and 2 or more types may be used together by arbitrary combinations and a ratio.

  The ratio of the light emitting material in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.05% by weight or more and usually 35% by weight or less. If the amount of the light emitting material is too small, uneven light emission may occur. If the amount is too large, the light emission efficiency may be reduced. In addition, when using together 2 or more types of luminescent material, it is made for the total content of these to be contained in the said range.

(Hole transporting compound)
The light emitting layer 5 may contain a hole transporting compound as a constituent material thereof. Here, among the hole transporting compounds, examples of the low molecular weight hole transporting compound include various compounds exemplified as (low molecular weight hole transporting compound) in the hole injection layer 3 described above. For example, two or more condensed aromatic rings containing two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl are bonded to the nitrogen atom. Aromatic amine compounds having a starburst structure such as substituted aromatic diamines (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine, etc. (Journal of Luminescence, 1997, Vol.72-74, pp.985), an aromatic amine compound comprising a tetramer of triphenylamine (Chemical Communi). ations, 1996, pp. 2175), spiro compounds such as 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene (Synthetic Metals, 1997, Vol. 91, pp. 209) and the like.

  Any one of these hole transporting compounds may be used, or two or more thereof may be used in any combination and ratio.

  Further, when the light emitting layer 5 contains a hole transporting compound, the ratio of the hole transporting compound in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but usually 0.1% by weight or more, Usually 65% by weight or less. If the amount of the hole transporting compound is too small, it may be easily affected by a short circuit, and if it is too large, the film thickness may be uneven. In addition, when using together 2 or more types of hole transportable compounds, it is made for the total content of these to be contained in the said range.

(Electron transporting compound)
The light emitting layer 5 may contain an electron transporting compound as a constituent material thereof. Here, among the electron transporting compounds, examples of low molecular weight electron transporting compounds include 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND), 2,5, -Bis (6 '-(2', 2 "-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), bathophenanthroline (BPhen), 2,9-dimethyl-4,7 -Diphenyl-1,10-phenanthroline (BCP, bathocuproin), 2- (4-biphenylyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole (tBu-PBD), 4 , 4′-bis (9-carbazole) -biphenyl (CBP) and the like.

  Any one of these charge transporting compounds may be used, or two or more thereof may be used in any combination and ratio.

  When the light emitting layer 5 contains an electron transporting compound, the content ratio of the electron transporting compound in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1% by weight or more, usually 65% by weight. % Or less. If the amount of the electron transporting compound is too small, it may be easily affected by a short circuit, and if it is too large, the film thickness may be uneven. In addition, when using together 2 or more types of electron transport compounds, it is made for the total content of these to be contained in the said range.

<Formation of light emitting layer>
When the light emitting layer 5 is formed by a wet film forming method, the above material is dissolved in an appropriate solvent to prepare a light emitting layer forming composition, and the film is formed using the composition.

  As the light emitting layer solvent to be contained in the light emitting layer forming composition for forming the light emitting layer 5 by a wet film forming method, any solvent can be used as long as the light emitting layer can be formed. Suitable examples of the solvent for the light emitting layer are the same as those described for the composition for forming a hole injection layer.

  The content ratio of the light emitting layer solvent in the light emitting layer forming composition for forming the light emitting layer 5 is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 0.01% by weight or more, usually 99% by weight. % Or less, preferably 95% by weight or less. In addition, when mixing and using 2 or more types of solvents as a solvent for light emitting layers, it is made for the sum total of these solvents to satisfy | fill this range.

  The solid content concentration of the light emitting material, hole transporting compound, electron transporting compound, etc. in the light emitting layer forming composition is usually 0.01% by weight or more, preferably 0.1% by weight or more, usually 70%. % By weight or less, preferably 30% by weight or less. If this concentration is too large, film thickness unevenness may occur, and if it is too small, defects may occur in the film.

  In order to form the light-emitting layer 5 using such a light-emitting layer forming composition, after the light-emitting layer forming composition is formed into a wet film, the obtained coating film is dried and the solvent is removed. The method of the wet film forming method is not limited as long as the effect of the present invention is not significantly impaired, and any of the methods described above can be used. A specific method of the wet film formation is the same as the method described in the formation of the hole injection layer 3.

  The thickness of the light-emitting layer 5 thus formed is arbitrary as long as the effects of the present invention are not significantly impaired, but are usually 3 nm or more, preferably 5 nm or more, and usually 200 nm or less, preferably 100 nm or less. It is. If the thickness of the light emitting layer 5 is too thin, defects may occur in the film, and if it is too thick, the driving voltage may increase.

{Hole blocking layer}
A hole blocking layer 6 may be provided between the light emitting layer 5 and an electron injection layer 8 described later. The hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.

  The hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5. Have

The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high. Examples of the material of the hole blocking layer 6 satisfying such conditions include, for example, bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum. Mixed ligand complexes such as, metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives, etc. Of styryl compounds (JP-A-11-242996), triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole 7-41759), phenanthroline derivatives such as bathocuproine (JP-A-10-79297), and the like. It is. Further, a compound having at least one pyridine ring substituted at positions 2, 4, and 6 described in International Publication No. 2005-022962 is also preferable as a material for the hole blocking layer 6.

  In addition, the material of the hole-blocking layer 6 may use only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  There is no restriction | limiting in the formation method of the hole-blocking layer 6, A wet film-forming method, a vapor deposition method, and another method are employable.

  The thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.

{Electron transport layer}
An electron transport layer 7 may be provided between the light emitting layer 5 and an electron injection layer 8 described later.

  The electron transport layer 7 is provided for the purpose of further improving the light emission efficiency of the device, and efficiently transports electrons injected from the cathode 9 between the electrodes to which an electric field is applied in the direction of the light emitting layer 5. Formed from a compound capable of

  As an electron transport compound used for the electron transport layer 7, usually, the electron injection efficiency from the cathode 9 or the electron injection layer 8 is high, and the injected electrons are transported efficiently with high electron mobility. The compound which can be used is used. Examples of the compound satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives , Distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compounds ( JP-A-6-207169), phenanthroline derivative (JP-A-5-331459), 2-t-butyl-9,10-N, N'-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide , N-type zinc sulfide, n-type zinc Such as emissions of zinc, and the like.

  In addition, the material of the electron carrying layer 7 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  There is no restriction | limiting in the formation method of the electron carrying layer 7, A wet film-forming method, a vapor deposition method, and another method are employable.

  The thickness of the electron transport layer 7 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.

{Electron injection layer}
The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the light emitting layer 5. In order to perform electron injection efficiently, the material for forming the electron injection layer 8 is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the film thickness is preferably from 0.1 nm to 5 nm.

  Furthermore, an organic electron transport compound represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium, or rubidium ( (As described in JP-A-10-270171, JP-A-2002-1000047, JP-A-2002-1000048, etc.), it is possible to improve the electron injection / transport properties and achieve excellent film quality. preferable. In this case, the film thickness is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less.

In addition, the material of the electron injection layer 8 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
There is no restriction | limiting in the formation method of the electron injection layer 8, A wet film-forming method, a vapor deposition method, and another method are employable.

{cathode}
The cathode 9 plays a role of injecting electrons into a layer (such as the electron injection layer 8 or the light emitting layer 5) on the light emitting layer 5 side.

  As the material of the cathode 9, the material used for the anode 2 can be used. However, a metal having a low work function is preferable for efficient electron injection. For example, tin, magnesium, indium, A suitable metal such as calcium, aluminum, silver, or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.

  In addition, the material of the cathode 9 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The film thickness of the cathode 9 is usually the same as that of the anode 2.

  Further, for the purpose of protecting the cathode 9 made of a low work function metal, it is preferable to further stack a metal layer having a high work function and stable to the atmosphere because the stability of the device is increased. For this purpose, for example, metals such as aluminum, silver, copper, nickel, chromium, gold and platinum are used. In addition, these materials may be used only by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

{Other layers}
The organic electroluminescent element according to the present invention may have another configuration without departing from the gist thereof. For example, as long as the performance is not impaired, an arbitrary layer may be provided between the anode 2 and the cathode 9 in addition to the layers described above, and an arbitrary layer may be omitted. .

Examples of the layer that may be included in addition to the layers described above include an electron blocking layer.
The electron blocking layer is provided between the hole injection layer 3 or the hole transport layer 4 and the light emitting layer 5 and prevents electrons moving from the light emitting layer 5 from reaching the hole injection layer 3. Thus, the probability of recombination of holes and electrons in the light emitting layer 5 is increased, the excitons generated are confined in the light emitting layer 5, and the holes injected from the hole injection layer 3 are efficiently collected. There is a role to transport in the direction of. In particular, when a phosphorescent material or a blue light emitting material is used as the light emitting material, it is effective to provide an electron blocking layer.

  The characteristics required for the electron blocking layer include high hole transportability, a large energy gap (difference between HOMO and LUMO), and a high excited triplet level (T1). Furthermore, in the present invention, when the light emitting layer 5 is produced by a wet film formation method using the composition for organic electroluminescence elements of the present invention, the electron blocking layer is also required to be compatible with the wet film formation. Examples of the material used for such an electron blocking layer include a copolymer of dioctylfluorene and triphenylamine typified by F8-TFB (described in International Publication No. 2004/084260).

  In addition, the material of an electron blocking layer may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  There is no restriction | limiting in the formation method of an electronic blockage | prevention layer, A wet film-forming method, a vapor deposition method, and another method are employable.

Further, at the interface between the cathode 9 and the light emitting layer 5 or the electron transport layer 7, for example, lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), lithium oxide (Li ₂ O), cesium carbonate (II) (CsCO ₃ ). Inserting an ultrathin insulating film (0.1 to 5 nm) formed by the above method is also an effective method for improving the efficiency of the device (Applied Physics Letters, 1997, Vol. 70, pp. 152; (Kaihei 10-74586; IEEE Transactions on Electron Devices, 1997, Vol. 44, pp. 1245; SID 04 Digest, pp. 154, etc.).

  Moreover, in the layer structure demonstrated above, it is also possible to laminate | stack components other than a board | substrate in reverse order. For example, in the layer configuration of FIG. 2, the other components on the substrate 1 are the cathode 9, the electron injection layer 8, the electron transport layer 7, the hole blocking layer 6, the light emitting layer 5, the hole transport layer 4, the positive layer. The hole injection layer 3 and the anode 2 may be provided in this order.

  Furthermore, it is also possible to constitute the organic electroluminescent element according to the present invention by laminating components other than the substrate between two substrates, at least one of which is transparent.

Further, a structure in which a plurality of components (light emitting units) other than the substrate are stacked in a plurality of layers (a structure in which a plurality of light emitting units are stacked) may be employed. In that case, (when the anode is ITO, the cathode is Al, these two layers) interfacial layer between the respective stages (between emission units) Alternatively, for example, a charge consisting of five vanadium oxide (V 2 _{O 5),} etc. When a generation layer (Carrier Generation Layer: CGL) is provided, a barrier between steps is reduced, which is more preferable from the viewpoint of light emission efficiency and driving voltage.

  Furthermore, the organic electroluminescent device according to the present invention may be configured as a single organic electroluminescent device, or may be applied to a configuration in which a plurality of organic electroluminescent devices are arranged in an array. You may apply to the structure by which the cathode is arrange | positioned at XY matrix form.

  Each layer described above may contain components other than those described as materials unless the effects of the present invention are significantly impaired.

{Formation of each layer}
In order to produce the organic electroluminescent device of the present invention as described above shown in FIG. 2 using the organic thin film patterning substrate of the present invention, an anode 2 and a hole injection layer 3 as an organic layer are formed on the substrate 1. 1 and / or the hole transport layer 4 is used as the substrate 11 shown in FIG. 1A, and the undercoat layer 12 and the bank forming resist layer 13 are sequentially stacked on the substrate 11 by the method described above. Thereafter, exposure and development are performed to form a bank 14 as shown in FIG. Thereafter, the light emitting layer 5 is formed as the organic thin film 16 in the region 15 partitioned by the bank 14 as shown in FIG. 1 (E). If necessary, the hole blocking layer 6, the electron transport layer 7, the electron It is preferable to form the injection layer 8 and further form the cathode 9 to form the organic electroluminescent element 10.

[Organic EL display device]
The organic EL display device of the present invention uses the above-described organic electroluminescent element of the present invention. There is no restriction | limiting in particular about the model and structure of the organic electroluminescent display apparatus of this invention, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention.
For example, the organic EL display device of the present invention can be obtained by the method described in “Organic EL display” (Ohm, published on Aug. 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata). Can be formed.

[Organic EL lighting]
The organic EL illumination of the present invention uses the above-described organic electroluminescent element of the present invention. There is no restriction | limiting in particular about the model and structure of the organic EL illumination of this invention, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention.

Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.
Tables 1 and 2 show the compositions of the hydrophilic compound-containing composition and the photosensitive composition used in the following Examples and Comparative Examples, respectively.
However, details of each component in Tables 1 and 2 are as follows.

<Hydrophilic compound-1>
Polyvinylpyrrolidone K-85 (manufactured by Nippon Shokubai Co., Ltd.)
<Hydrophilic compound-2>
Vinylpyrrolidone / vinyl acetate = 7/3 copolymer (Tokyo Kasei Co., Ltd.)
<Hydrophilic compound-3>
Polyacrylic acid Jurimer AC-10L (Nippon Pure Chemicals Co., Ltd.)
<Binder resin-1>
Resin produced in Synthesis Example 1 below <Binder Resin-2>
Resin <ethylenically unsaturated compound-1> produced in Synthesis Example 2 below
Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

<Ethylenic unsaturated compound-2>
Deconal acrylate DA-314 (manufactured by Nagase ChemteX Corporation)

<Ethylenic unsaturated compound-3>

<Photopolymerization initiator-1>
Irgacure 907 (Ciba Special Chemicals)

<Photopolymerization initiator-2>
CGI242 (Ciba Special Chemicals)

<Crosslinking agent-1>

<Ink Repellent Component-1>
Megafuck RS-102 (manufactured by DIC)
<Ink Repellent Component-2>
Optool DAC (Daikin Industries)
<Surface modifier-1>
Polyether-modified polydimethylsiloxane BYK-330 (by Big Chemie)
<Solvent-1>
Propylene glycol monomethyl ether acetate <Solvent-2>
3-methoxy-1-butanol

[Synthesis Example 1: Production of binder resin-1]
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. To this, 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate and 82 parts by weight of monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and further stirred at 140 ° C. for 2 hours. Continued. Next, the inside of the reaction vessel was purged with air, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain binder resin-1 which is an alkali-soluble resin represented by the following formula. . The weight average molecular weight (Mw) of this resin was about 8000.

[Synthesis Example 2: Production of Binder Resin-2]
120 g of m-cresol novolak resin having a weight average molecular weight (Mw) of 4000 and 71 g of glycidyl methacrylate were dissolved in 191 g of propylene glycol monomethyl ether acetate, 0.19 g of paramethoxyphenol and 1.9 g of tetraethylammonium chloride were added, and 13 hours at 90 ° C. Reacted. After confirming that the glycidyl methacrylate was 1% or less by gas chromatographic analysis, 45.6 g of tetrahydrophthalic anhydride and 45.6 g of propylene glycol monomethyl ether acetate were added, and the mixture was further reacted at 95 ° C. for 5 hours. It was confirmed by IR that there was no acid anhydride, and binder resin-2 represented by the following formula was obtained. The weight average molecular weight (Mw) of this resin was 7500.

[Examples 1-7]
According to the following procedure, a hole injection layer and a hole transport layer are formed on a substrate, and then an undercoat layer and a bank resist layer are sequentially formed, and then exposed and developed to form a part of the bank formation resist layer. Then, the contact angle between a portion where the bank resist layer was present (solid portion) and a portion where the bank resist layer was removed by development processing (clear portion) was measured using cyclohexylbenzene.

<Washing glass substrate>
The polishing surface of the glass substrate for display (“AN100” manufactured by Asahi Glass Co., Ltd.) is ultrasonically cleaned with a cleaning agent (“Sunwash TL-100” manufactured by Lion Corporation), washed with ultrapure water, ultrasonic washed with ultrapure water, After washing in the order of rinsing with ultrapure water, it was drained, then dried in an oven at 180 ° C. for 10 minutes, and finally subjected to UV ozone treatment (1000 mj / cm ^{2 with a} low-pressure mercury lamp) for 1 minute.

<Formation of hole injection layer>
On the glass substrate, a hole transporting polymer material having a repeating structure represented by the following formula (P1) (weight average molecular weight (Mw) 20000), 4-isopropyl-4 represented by the following formula (A1) A composition for forming a hole injection layer containing '-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate as a solvent was prepared. In this composition for forming a hole injection layer, the ratio (P1) :( A1) = 100: 40 (weight ratio) and the solid content concentration (content of (P1) and (A1)) is 2. It was 0% by weight.

  This coating solution was formed on a substrate by spin coating so as to have a dry film thickness of 30 nm, and heated at 230 ° C. for 3 hours to form a hole injection layer.

<Formation of hole transport layer>
A hole transport layer forming composition containing a hole transporting polymer material represented by the following formula (weight average molecular weight (Mw) 52000) and toluene as a solvent was prepared. The solid content concentration of the composition for forming a hole transport layer was 2.0% by weight.

  The composition for forming a hole transport layer was formed on the hole injection layer by spin coating so as to have a dry film thickness of 20 nm, and the hole transport layer was formed by heat polymerization at 230 ° C. for 1 hour. .

<Formation of undercoat layer>
Hydrophilic compound-containing compositions 1 to 4 shown in Table 1 were prepared. The preparation was performed by blending each component and mixing well.
Of these hydrophilic compound-containing compositions 1 to 4, the hydrophilic compound-containing compositions shown in Table 3 were applied onto the hole transport layer by spin coating so that the dry film thickness was 0.1 μm. An undercoat layer was formed. Drying was carried out on a hot plate at 80 ° C. for 1 minute.

<Formation of solid / clear image with bank resist>
Photosensitive compositions 1 to 3 shown in Table 2 were prepared. The preparation was performed by blending each component and mixing well.
Among the photosensitive compositions 1 to 3, the photosensitive composition shown in Table 3 was applied onto the undercoat layer by spin coating so as to have a dry film thickness of 3 μm, thereby forming a bank resist layer.
Drying was performed by vacuum drying for 1 minute, and further at 80 ° C. for 1 minute on a hot plate.

Thereafter, half of the bank resist layer forming surface was shielded from light and exposed to light at 300 mJ / cm ² using 3 kW high-pressure mercury.
Next, a 2.38 wt% TMAH aqueous solution (tetramethylammonium hydroxide) was used as a developing solution, followed by shower development at a water pressure of 0.1 MPa at 23 ° C. for 2 minutes, followed by rinsing with a water spray for 30 seconds, and compressed air. And drained.
Next, this was post-baked in an oven at 230 ° C. for 30 minutes to obtain a substrate having a solid portion and a clear portion of the bank resist layer.
The image forming process of the solid portion and the clear portion of the bank resist layer was performed under yellow light from which ultraviolet light was cut.

<Measurement of contact angle>
The contact angle with respect to cyclohexylbenzene was measured for the solid part and the clear part of the substrate having the solid part and the clear part of the obtained bank resist layer. The results are shown in Table 3.
The contact angle measurement conditions are as follows.
Measuring device: CA-D type manufactured by Kyowa Interface Science Co., Ltd. Measuring temperature: 23 ° C
Measurement humidity: 50%
Droplet size: 6 μm
Measured 10 seconds after liquid landing

[Comparative Examples 1-4]
In Examples 1-7, it carried out similarly except not forming an undercoat layer, the contact angle with respect to the cyclohexylbenzene of a solid part and a clear part was similarly measured, and the result was shown in Table 3.

  From Table 3, Examples 1 to 7 in which the undercoat layer is formed are smaller than those in Comparative Examples 1 to 4 in which the undercoat layer is not formed. It can be seen that the organic thin film can be formed uniformly in the formation of the organic thin film in the process.

[Examples 8 and 9]
The organic electroluminescent element shown in FIG. 2 was produced by the following procedure. In addition, the light emitting layer was formed in the area | region divided by the bank formed through the undercoat layer on the positive hole transport layer.

<Formation of anode>
An indium tin oxide (ITO) transparent conductive film deposited to a thickness of 150 nm on a glass substrate (manufactured by Sanyo Vacuum Co., Ltd., sputtered film) using ordinary photolithography technology and hydrochloric acid etching The anode 2 was formed by patterning. The patterned ITO substrate is cleaned in the order of ultrasonic cleaning with an aqueous surfactant solution, water cleaning with ultrapure water, ultrasonic cleaning with ultrapure water, and water cleaning with ultrapure water, followed by drying with compressed air, and finally UV irradiation. Ozone cleaning was performed.

<Formation of hole injection layer, hole transport layer, undercoat layer>
On the obtained anode 2, a hole injection layer 3, a hole transport layer 4, and an undercoat layer were formed in the same manner as in Example 1.
In Example 8, the undercoat layer was formed using the hydrophilic compound-containing composition 1 in Table 1, and in Example 9, the undercoat layer was formed using the hydrophilic compound-containing composition 4 in Table 1. Preparation of the hydrophilic compound-containing compositions 1 and 4 was carried out by blending each component and mixing them well.

<Bank formation>
The bank resist layer was formed in the same manner as in Example 1 using the photosensitive composition 1 in Table 2. The photosensitive composition 1 was prepared by blending each component and mixing them well.
Thereafter, exposure was performed using 3 kW high-pressure mercury under an exposure condition of 100 mJ / cm ² using a mask in which 30 μm-wide line-shaped openings were arranged in a lattice pattern at a pitch of 100 μm. Next, an aqueous solution containing 2.38% by weight of TMAH and 10% by weight of ethanol was used as a developing solution, followed by shower development at a water pressure of 0.1 MPa for 2 minutes at 23 ° C., followed by rinsing with a washing spray for 30 seconds, Cut off.
Next, this was post-baked in an oven at 230 ° C. for 30 minutes to obtain a bank.
The above bank formation process was performed under yellow light from which ultraviolet light was cut.

<Formation of light emitting layer>
Next, the organic compounds (C3), (C4) and the iridium complex (D2) shown below are mixed in a ratio of (C3) :( C4) :( D2) = 10: 10: 1 (weight ratio). A composition for forming a light-emitting layer having a solid content concentration of 1% by weight was prepared using cyclohexylbenzene.

This composition was ejected with a droplet amount of 25 pl into the bank section by inkjet.
The ink jet was drawn in a 25 × 50 pixel area using 25 nozzles simultaneously. This was dried at 130 ° C. under reduced pressure (10 kPa) for 1 hour.
Thus, the light emitting layer 5 having a thickness of 25 nm was formed.

<Formation of hole blocking layer>
Next, the substrate on which the light-emitting layer 5 has been formed is transferred into a vacuum deposition apparatus, exhausted until the degree of vacuum in the apparatus becomes 5.1 × 10 ⁻⁴ Pa or less, and then used as a hole blocking material with the following structure. A compound represented by the formula (XX) was formed into a film by a vacuum deposition method. The deposition rate was controlled in the range of 0.7 to 1.0 kg / second, and the hole blocking layer 6 having a film thickness of 5 nm was formed by being laminated on the light emitting layer 5.

<Formation of electron transport layer>
Next, a film of tris (8-hydroxyquinolinate) aluminum was formed by an evaporation method as an electron transporting material. The deposition rate was controlled in the range of 0.6 to 1.5 liters / second, and the electron transport layer 7 having a thickness of 30 nm was formed by being laminated on the hole blocking layer 6.

<Formation of electron injection layer>
Then, it moved to the vacuum evaporation apparatus for cathode evaporation, and exhausted until the vacuum degree in an apparatus became 2.1x10 <^-4> Pa or less.
As the electron injection layer 8, lithium fluoride (LiF) was first laminated on the electron transport layer 7 with a film thickness of 0.5 nm by controlling the deposition rate at 0.07 to 0.1% / second.

<Formation of cathode>
Further, the cathode 9 was formed with a thickness of 80 nm by controlling aluminum at a deposition rate of 0.7 to 6.1 liters / second as the cathode 9.

<Sealing>
An organic substrate having a light emitting area of 2 mm × 2 mm size is obtained by bonding a substrate on which each layer obtained by the above method is formed and a separately prepared sealing glass with an ultraviolet curable resin and irradiating with ultraviolet rays. An electroluminescent element was obtained.

[Comparative Example 5]
In Example 8, except that the undercoat layer was not formed, each layer was formed and sealed in the same manner to obtain an organic electroluminescent element.

[Evaluation of ink wetting and spreading]
In the step of forming the organic electroluminescent element, the wetting and spreading property of the light emitting layer was observed with a microscope after discharging and drying the light emitting layer forming coating solution by ink jet. In 8 and 9, it was found that the composition (ink) for forming the light emitting layer uniformly spreads in the area partitioned by the bank, but in Comparative Example 5, it was played and approached the corner.

[Element evaluation]
About the organic electroluminescent elements produced in Examples 8 and 9, when a light emission state was confirmed by applying a voltage, as shown in Table 4, the light emitting layer overflowed from the bank and was not mixed with the adjacent pixels, It was confirmed that substantially uniform light emission was exhibited in the bank and over the entire light emitting surface.

  In Table 4, the evaluation of ink wetting and spreading properties shows a photomicrograph of the light emitting layer, and the device evaluation shows a photomicrograph when a voltage is applied to the organic electroluminescent device.

It is typical sectional drawing which shows embodiment of the manufacturing procedure of the organic thin film patterning board | substrate of this invention, and the formation process of the organic thin film to the manufactured organic thin film patterning board | substrate. It is typical sectional drawing which showed an example of the organic electroluminescent element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Hole blocking layer 7 Electron transport layer 8 Electron injection layer 9 Cathode 10 Organic electroluminescent element 11 Substrate 12 Subbing layer 13 Bank resist layer 14 Bank 15 Bank partition area 16 Organic thin film 20 Exposure mask

Claims (15)

In a method for manufacturing a substrate for organic thin film patterning, which has a bank and a region partitioned by the bank on the substrate, and is used for forming an organic thin film in the region partitioned by the bank.
An undercoat layer forming step of providing an undercoat layer by applying a hydrophilic compound-containing composition containing a hydrophilic compound directly or via another layer on the substrate;
A resist layer forming step of providing a bank resist layer by applying a photosensitive composition containing an ink repellent component on the undercoat layer;
A bank forming step of forming a bank by exposing and developing the resist layer for bank; and
A method for producing an organic thin film patterning substrate, wherein the undercoat layer in the non-image area is removed together with the bank resist layer in the non-image area in the development process of the bank forming step.   2. The method of manufacturing an organic thin film patterning substrate according to claim 1, wherein the organic thin film is formed in an area partitioned by the bank by an ink ejection type coating method.   The method of manufacturing a substrate for organic thin film patterning according to claim 1, wherein the undercoat layer is provided on the substrate via an organic layer.   The said hydrophilic compound containing composition contains the solvent which has water and / or an alcohol solvent as a main component, The manufacture of the substrate for organic thin film patterning of any one of Claim 1 thru | or 3 characterized by the above-mentioned. Method.   The photosensitive composition contains a perfluoro group-containing compound as an ink repellent component, and further contains a resin containing an ethylenically unsaturated group and a carboxy group, an ethylenically unsaturated compound, and a photopolymerization initiator. The method for producing an organic thin film patterning substrate according to any one of claims 1 to 4, wherein:   6. The method of manufacturing an organic thin film patterning substrate according to claim 1, wherein an aqueous solution of an organic alkali compound is used as a developing solution in the developing process of the bank forming step.   An organic thin film patterning substrate manufactured by the method for manufacturing an organic thin film patterning substrate according to any one of claims 1 to 6, wherein the organic thin film patterning substrate is organically formed in a region partitioned by a bank of the organic thin film patterning substrate. A method for producing an organic electroluminescent device, comprising forming a light emitting layer as a thin film.   An organic thin film patterning substrate having a bank and a region partitioned by the bank on a substrate and used for forming an organic thin film in the region partitioned by the bank, wherein the bank is hydrophilic An organic thin film patterning substrate, wherein the bank is formed on an undercoat layer containing a compound, and the bank contains an ink repellent component.   9. The organic thin film patterning substrate according to claim 8, wherein the undercoat layer is formed on the substrate via an organic layer.   An organic electroluminescent device having a bank and a region partitioned by the bank on a substrate, and having an organic thin film in the region partitioned by the bank, wherein the bank includes a hydrophilic compound An organic electroluminescent element formed on the bank, wherein the bank contains an ink repellent component.   The organic electroluminescence device according to claim 10, wherein the undercoat layer is formed on a substrate through an organic layer.   The organic electroluminescent device according to claim 11, wherein the organic layer is a hole injection layer and / or a hole transport layer.   The organic electroluminescent element according to claim 10, wherein the organic thin film is a light emitting layer.   An organic EL display device using the organic electroluminescent element according to claim 10.   An organic EL illumination comprising the organic electroluminescence device according to claim 10.

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