JPWO2019230328A1 - Display device and manufacturing method of display device - Google Patents

Abstract

An object of the present invention is a high-quality display device having improved light extraction efficiency and improved light resistance and moisture heat resistance in a color filter type display device having a color filter layer composed of a colorant and quantum dots, and a failure. The purpose of the present invention is to provide a method for manufacturing a display device having few defects and improved production efficiency. The display device of the present invention is a display device including a color filter unit, wherein the color filter unit is composed of at least a base material, a color filter layer and a flattening layer, and the color filter layer or the flattening layer. A display device, wherein at least one layer of the above contains an organic metal oxide having a structure represented by the following general formula (1). General formula (1) R- [M (OR1) y (O-) xy] n-R

Description

The present invention relates to a display device and a method for manufacturing the display device. More specifically, the present invention enhances the light extraction efficiency of a color filter type display device having a color filter layer composed of a colorant and quantum dots, and also has light resistance and moisture resistance. The present invention relates to a high-quality display device having improved thermal properties and a method for manufacturing a display device having few failure defects and improved production efficiency.

In the industrial world, many electronic members such as transistors and diodes are deteriorated by water and oxygen, so they are subjected to a process called sealing process or passivation process. In particular, display devices that allow organic compounds to carry electron conduction, such as organic thin films, organic thin-film solar cells, and organic electroluminescence devices (hereinafter referred to as "organic EL devices"), are extremely sensitive to water molecules and are extremely sensitive. Advanced sealing technology is required.

Organic EL displays, which are one of the display devices, are in the limelight because they have less viewing angle dependence, higher contrast ratio, and thinner film than liquid crystal display devices, and various studies have been carried out. There is. In addition, large-sized TVs have been introduced to the market, which has spurred the market expansion to flat-panel displays.

Further, in the case of organic EL displays, the development of organic EL displays using a flexible base material made of a resin film or the like and having flexibility is in the limelight from the viewpoint of expanding the degree of freedom in the field of application. By applying a flexible base material to organic EL displays, etc., in addition to the demand for weight reduction and size increase, it is possible to realize roll-to-roll production suitability, increase the degree of freedom in shape, and display curved surfaces. It is widely used in place of the glass base material, which is heavy, fragile, and difficult to increase in area.

However, the flexible base material has a problem that the gas barrier property is inferior to that of the glass base material. For example, when a flexible base material is used as a base material for an organic EL element, it has high water vapor permeability and oxygen permeability, and therefore, when applied to an organic EL element that is sensitive to moisture and oxygen, it has sufficient gas barrier properties. However, it cannot be said that the constituent organic functional layer and the like are deteriorated by moisture and oxygen, causing pixel shrinkage and decrease in brightness, which is a factor of impairing durability.

As one of the methods for solving the above problems, a flexible organic EL display for forming an organic functional layer including an electrode and a light emitting layer by using a flexible base material provided with a gas barrier layer having a high gas barrier property has been studied. (See, for example, Patent Document 1).

On the other hand, in the development of display devices, from the viewpoints of reducing manufacturing costs, improving yields on large-screen TVs, simplifying manufacturing processes, etc., for example, a white light emitting organic EL element is used as a light emitting member on the light extraction side. A method of arranging a color filter composed of a colorant and emitting RGB light is being studied. Furthermore, as a configuration of the color filter, even in the RGB painting method, there is a limit to the high definition of the displayed color image due to the manufacturing accuracy using the vapor deposition mask and the influence of the shadow due to the vapor deposition. As an attempt, a quantum dot-containing organic light emitting element (hereinafter, also referred to as "QD-OLED") using a color filter that contains quantum dots and emits color-converted light is being studied as a color filter (for example, "QD-OLED"). See Patent Documents 2 and 3).

However, in the color filter method using the above-mentioned colorant and the color filter method using quantum dots, since it is necessary to provide a flattening layer when forming the color filter unit, the refractive index is small, and further, the color filter layer. There is a problem that the difference in refractive index becomes large, the loss of the extracted light is high, the luminous performance displayed through the color filter unit deteriorates, and the luminous brightness as a light emitting device is lowered. As a countermeasure, it is necessary to increase the luminous efficiency of the light emitting layer itself, and efforts have been made to secure desired light extraction characteristics, for example, emission brightness. Further, since the filler to be filled after forming the color filter is composed of a transparent resin layer made of an organic polymer, there is also a problem that the transmittance is lowered by at least 1% or more. In addition, the color filter easily takes in water, and the water is released from the color filter after sealing, which causes deterioration of the organic functional layer and the like of the organic EL elements arranged close to each other, resulting in sealing defects. There was a problem that the resulting yield decreased.

Japanese Unexamined Patent Publication No. 2011-156752 Japanese Unexamined Patent Publication No. 2016-80811 Japanese Unexamined Patent Publication No. 2017-26796

The present invention has been made in view of the above problems, and the problem to be solved is to improve the light extraction efficiency in a color filter type display device having a color filter layer composed of a colorant and quantum dots, and to have light resistance. It is also an object of the present invention to provide a high-quality display device having improved moisture resistance and heat resistance, and a method for manufacturing a display device having few failure defects and improved production efficiency.

As a result of diligent studies in view of the above problems, the present inventor is a display device including a color filter unit, wherein the color filter unit is composed of at least a base material, a color filter layer and a flattening layer. Organic metal oxidation having a structure represented by the following general formula (1) in which at least one of the color filter layer or the flattening layer is formed from a composition containing a metal alkoxide containing a fluorine atom or a metal carboxylate. By containing a substance, an organic thin film that functions as a moisture-permeable sealing film can be obtained, and as a result, a high-quality display device with improved light extraction efficiency as a color filter unit and improved light resistance and moisture heat resistance. We have found that it is possible to realize the above, and have arrived at the present invention.

That is, the present inventors have worked on the creation of a technique capable of realizing the following phenomena for the purpose of overcoming the above-mentioned various problems.

(I) Having a dryness (desiccant property) that reacts with water molecules.

(II) To release a substance that has the property of repelling water as a function of reaction with water.

(III) It is possible to apply and deposit under atmospheric pressure.

If a material and technology that combines these three elements can be constructed, the permeation of water molecules into the heart of the electronic device can be effectively prevented, and a water-repellent substance will be generated according to the amount of permeated water. If it becomes a method to prevent water vapor permeation, which is a new technical concept completely different from the conventional water vapor barrier property, and if it can be applied (coated) under atmospheric pressure, it will be possible to seal a large area at low cost, and it will come from now on. It is considered that there is a possibility that the hidden problem, that is, the inexpensive and effective sealing process, which was actually a bottleneck of the manufacturing cost, can be solved at once toward the IoT era.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. 1. A display device equipped with a color filter unit.
The color filter unit is composed of at least a base material, a color filter layer and a flattening layer.
A display device characterized in that at least one of the color filter layer and the flattening layer contains an organometallic oxide having a structure represented by the following general formula (1).
General formula (1) R- [M (OR ₁ ) _y (O-) _xy ] _n- R
(In the formula, R represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group, where R represents fluorine as a substituent. It may be a carbon chain containing an atom. M represents a metal atom. OR ₁ represents a fluorinated alkoxy group. X represents the valence of the metal atom, and y represents an arbitrary integer between 1 and x. Represents the degree of polycondensation.)

2. The display device according to item 1, further comprising a light emitting layer.

3. 3. The value of the ratio of fluorine atoms to the total number of carbon atoms and fluorine atoms of the organometallic oxide contained in the color filter layer or the flattening layer satisfies the condition defined by the following formula (a). The display device according to paragraph 1 or 2.
Equation (a) 0.05 ≤ F / (C + F) ≤ 1.00

4. The metal atom (M) contained in the organometallic oxide is Ti, Zr, Sn, Ta, Fe, Zn, or Al, according to any one of the first to third terms. The display device described.

5. The display device according to any one of items 1 to 4, wherein the refractive index of the flattening layer is in the range of 1.6 to 1.9.

6. The display device according to any one of items 1 to 5, wherein the absolute value of the difference in refractive index between the flattening layer and the color filter layer is less than 0.1.

7. The display device according to any one of items 1 to 6, wherein the color filter unit contains quantum dots.

8. The display device according to any one of items 1 to 7, wherein the display device is an organic light emitting element, an inorganic light emitting element, or a color electronic paper.

9. The display device according to item 8, wherein the organic light emitting element is an organic electroluminescence element or a quantum dot-containing organic light emitting element.

10. The display device according to item 8, wherein the inorganic light emitting element is a quantum dot-containing inorganic light emitting element or a micro LED.

11. A method for manufacturing a display device, which manufactures a display device including the color filter unit according to any one of items 1 to 10.
A method for manufacturing a display device, which comprises forming a color filter layer constituting the color filter unit by using a mixed solution of a metal alkoxide or a metal carboxylate and a fluoroalcohol.

12. The method for manufacturing a display device according to item 11, wherein the color filter layer is formed by a wet coating method.

13. The method for manufacturing a display device according to item 12, wherein the wet coating method is an inkjet printing method.

According to the present invention, a high-quality display device having improved light extraction efficiency in a color filter type display device having a color filter layer composed of a colorant and quantum dots, and improved light resistance and moisture heat resistance. It is possible to provide a method for manufacturing a display device having few failure defects and improved production efficiency.

The technical features of the surface light emitting panel having the configuration specified in the present invention and the mechanism for expressing the effect are presumed as follows.

In the present invention, in a display device including a color filter unit, at least one of the color filter layer or the flattening layer constituting the color filter unit has an organometallic oxidation having a structure represented by the general formula (1). By containing the substance, the constituent layer containing the organometallic oxide functions as a chemical reaction type moisture getter, and releases a water-repellent or hydrophobic substance by the amount of the reaction with the moisture. It provides a constituent film having new moisture absorption characteristics and sealing characteristics with respect to moisture permeation.

That is, the organometallic oxide having the structure represented by the general formula (1) produces an equimolar fluoroalcohol equal to the quenched water molecule by hydrolysis, which has a water-repellent function or a hydrophobic function. Since it has, it prevents further intrusion of water. Therefore, the effect of preventing the intrusion of water is extremely higher than that of the conventional chemical reaction type hygroscopic agent, and the single composition membrane has a dryness (desiccant property) and a synergistic function in which a water repellent function is added by reaction with water. It is an innovative technology that exerts an effect (synergy effect), which is a feature not found in conventional hygroscopic agents and organic thin films.

Further, the color filter layer or the flattening layer containing an organic metal oxide having a structure represented by the general formula (1) according to the present invention uses a metal alkoxide solution as a raw material and is generally called a sol-gel method. A method of synthesizing an organic-inorganic hybrid compound by hydrolysis of a metal alkoxide and a subsequent polycondensation reaction to form the constituent layer is adopted.

The sol-gel method is widely known as a conventional method for forming an inorganic oxide into a film by a coating method. This method is generally a method in which an inorganic oxide is formed by hydrolysis of a metal alkoxide and a subsequent polycondensation reaction using a metal alkoxide solution as a raw material, and a part of the metal alkoxide is not an alkoxy group but an alkyl group. In the case of an aryl group or an aryl group, the group is retained even after the sol-gel reaction, so that an organic-inorganic hybrid compound film based on an inorganic oxide can be formed.

Basically, all metal elements that can be alkoxylated can be applied to this sol-gel method, but in most cases, gelation occurs when they are made into a solution in the air and cannot be applied, so they are practically used. It is limited to silicon (tetraalkoxysilane). The reason for this is that when the metal element is titanium or zirconium, the alkoxide compound itself is Lewis acid, which catalytically accelerates the dehydration polycondensation reaction after the hydrolysis reaction, resulting in immediate gelation. This is because it will be stored.

Also, in the case of alkali metals and alkaline earth metals, even if they are alkoxides, they are basic, so the initial hydrolysis reaction is very fast, while the dehydration polycondensation reaction is slow, so organic metal oxides are obtained. Is difficult. Since silicon alkoxide has intermediate properties, it is currently only suitable for organometallic oxide synthesis or organometallic oxide thin film formation by the sol-gel method.

On the other hand, when the metal alkoxide is dissolved in the excess alcohol (A), the metal alkoxide is replaced with the alcohol (A) due to the chemical equilibrium, and the metal alkoxide of the alcohol (A) is produced. At this time, the alcohol (A) When the alcohol is substituted with a fluorine atom, the resulting metal-fluorinated alkyloxy compound (hereinafter referred to as “metal-fluorinated alkoxide”) can relax the sol-gel reaction rate.

This reduces the electron density on the metal element due to the electron attraction effect of the fluorine atom and accelerates the alkoxide reaction of the water molecule, but the effect of removing water by the fluorine atom is larger than that, and the water molecule cannot approach the metal element. Therefore, the so-called frequency factor is greatly reduced, resulting in a slower hydrolysis rate, and for example, titanium and zirconium, and transition metals having an empty d orbit (for example, tetravalent vanadium and 4). Since the alkoxide compound (such as valent tungsten) is Lewis acid, it exhibits an acid catalytic effect and accelerates dehydration polycondensation and dealcohol polycondensation reactions, so that high-molecular-weight organic metal oxides are easily generated. It is due to.

Due to this effect, (I) having a dryness (desiccant property) that reacts with water molecules, (II) releasing a substance having a property of repelling water as a function of the reaction with water, and ( III) It became possible to satisfy all of the possibilities of coating and film formation under atmospheric pressure, and in particular, the requirement described in (III) was practically impossible to handle with ordinary metal alkoxide due to the progress of gelation. Even in the presence of fluorinated alcohol, this is possible, and by applying high energy such as ultraviolet rays, plasma irradiation, and microwave irradiation to the completed constituent layer, a high-density organic metal is continuously formed from the thin film surface. An oxide film is formed, and as a result, the thin film has the dryness (desiccant property) of (I), and unreacted metal fluorinated alkoxide remains inside, so that the incoming water molecule and it Reacts to produce a fluorinated alcohol that repels water, thus exerting the effect of (II), and as a result, it becomes possible to form a new thin film having both the effects of (I) and (II).

Further, the metal alkoxide substituted with the fluoroalkoxide can effectively suppress the reaction between different kinds of metal alkoxides and the salt formation because the frequency factor decreases due to the exclusion effect by the fluorine atom. Alternatively, a plurality of metal alkoxides can coexist in the solution as metal fluoride alkoxide, and the thin film obtained from the solution can be given a mixed inorganic oxide thin film.

For example, even in the case of titanium tetraisopropoxide and barium dibutoxide, which normally form a Lewis acid / Lewis base pair and gel, even if each is diluted with a large excess of tetrafluoropropanol (TFPO) and then mixed, the gel is formed. It is possible to form a thin film by the sol-gel method by applying it as it is, and by applying high energy such as ultraviolet rays to the thin film, it is possible to form a mixed organic metal oxide film.

Further, the present invention can also produce an organic metal oxide by a sol-gel method (hereinafter, also referred to as "sol-gel reaction").

As described above, by using the metal alkoxide solution in which the sol-gel reaction rate is relaxed, it becomes possible to improve the stability of the solution and facilitate the handling at the time of film formation. On the other hand, high energy is required to form a high-density organometallic oxide film from the finished film, but because it is absorbed by oxygen molecules and nitrogen molecules, the sol-gel reaction stays on the film surface. There was a problem that it may not progress to the inside.

On the other hand, in the present invention, it is a feature of the present invention that the conflicting problems before and after film formation are solved by performing a sol-gel reaction of a metal alkoxide.

That is, the organometallic oxide according to the present invention is not limited to a composition for obtaining a moisture absorbing function for producing a water-repellent or hydrophobic compound, and stably forms a plurality of metal alkoxides which have been difficult to coexist in the past. The presence and the resulting mixed organometallic oxide thin film itself also falls into the category. This is a technology that seems to be feasible in the past, but could not be realized in practice, and it is expected that the realization of this technology will bring out unprecedented functions in various application areas, and the present invention is an industry. The positive impact on the world is great.

Therefore, the present invention has a different concept from the conventional thin film formation by the sol-gel method using a metal alkoxide, the function of the thin film to be formed is also different, and a mixed organometallic oxide thin film which has not been possible until now. It should be distinguished from similar prior art because it can also be realized.

Schematic cross-sectional view showing an example of an organic EL display device provided with a color filter unit. Schematic cross-sectional view showing another example of an organic EL display device provided with a color filter unit. Schematic diagram showing the configuration of the inkjet printing method, which is an example of the wet coating method. Schematic cross-sectional view showing an example of a typical configuration of an organic EL element constituting a display device.

The display device of the present invention is a display device including a color filter unit, wherein the color filter unit is composed of at least a base material, a color filter layer and a flattening layer, and the color filter layer or the flattening layer. At least one layer of the above is characterized by containing an organic metal oxide having a structure represented by the general formula (1). This feature is a technical feature common to the inventions according to the following embodiments.

In the display device of the present invention having the above structure, by using a fluoroalcohol solvent and applying a desired metal species, molecules entering from the outside can be replaced, and water is taken in and replaced by a hydrolysis reaction. And, it becomes possible to put it in a chemically bonded state having a hydroxy group, and as a result, a color filter unit having an excellent moisture absorbing function can be obtained, and a flattening layer can absorb moisture that invades from the outside or diffuses from the color filter layer. Since water is absorbed or the color filter layer itself absorbs water, it is possible to realize a highly reliable display device having water resistance by suppressing the diffusion of water into the constituent layers of the display device, particularly the organic functional layer group.

As an embodiment of the present invention, the durability of the light emitting layer is dramatically improved by applying it to a display device having a light emitting layer having a low resistance to moisture from the viewpoint of being able to further exhibit the effect intended by the present invention. It is possible to realize a highly reliable display device.

Further, the value [F / (C + F)] of the ratio of fluorine atoms to the total number of carbon atoms and fluorine atoms of the organic metal oxide contained in the color filter layer or the flattening layer is set to 0.05 to 1.00. By setting it within the range, it is possible to control the content of fluorinated alcohol as a solvent and form a color filter layer that exhibits a desired moisture absorption effect.

Further, by setting the metal atom (M) contained in the organic metal oxide to Ti, Zr, Sn, Ta, Fe, Zn, or Al, a high refractive index can be obtained in the applicable constituent layer, and light can be obtained. A metal alkoxide can be obtained that can increase the extraction efficiency.

Further, by setting the refractive index of the flattening layer in the range of 1.6 to 1.9, the light extraction efficiency of the light emitted from the light emitting layer can be increased in the flattening layer, and as a result, the flattening layer can be improved. It is possible to improve the brightness of the display device, and accordingly, it is possible to extend the life of the light emitting element constituting the display device.

Further, the absolute value of the difference in refractive index between the flattening layer and the color filter layer can be set to less than 0.1 by appropriately selecting an organic metal oxide composed of a metal type according to a desired refractive index. As a result, it is possible to reduce the light loss due to the light refraction caused by the difference in the refractive index between the flattening layer and the color filter layer, improve the brightness of the display device, and extend the life of the light emitting element constituting the display device. can.

Further, by applying the color filter type display device of the present invention to an organic light emitting element, an inorganic light emitting element, or color electronic paper, high quality display with improved light extraction efficiency and improved light resistance and moisture heat resistance. Since the device can be realized, the life of the element can be extended, and the sealing defect due to the large-sized television can be suppressed, the quality can be improved and the yield can be improved.

Further, the method for manufacturing a display device of the present invention is a method for manufacturing a display device for manufacturing a display device including the color filter unit of the present invention, wherein the color filter layer constituting the color filter unit is made of metal alkoxide or metal alkoxide. It is characterized in that it is formed by using a mixed solution of a metal alkoxide and a fluoroalcohol.

Further, in the manufacturing method of the display device of the present invention, forming the color filter layer by a wet coating method has a high refractive index and a moisture absorbing capacity, and does not damage the organic functional layer group. It can be provided, it does not require large equipment, it is possible to apply it to a local part with high accuracy, and it is possible to control the layer thickness to be formed, and it is possible to accurately form an optical path length suitable for light extraction. This is preferable in that the light extraction efficiency can be maximized.

It is preferable that the wet coating method is an inkjet printing method in that the above effects can be more exhibited.

In the present invention, the configuration from the first base material, the TFT unit, the first electrode to the second sealing layer is referred to as a light emitting display unit or an organic EL element unit.

Further, the configuration from the first electrode to the second sealing layer is referred to as an organic EL element (OLED).

Further, a configuration composed of a base material, a color filter layer and a flattening layer is referred to as a color filter unit.

Hereinafter, the configuration of the display device including the color filter unit of the present invention and its components will be described in detail with reference to the drawings. In the present application, "~" representing a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

<< Basic configuration of display device >>
The display device of the present invention includes a color filter unit, and the color filter unit is characterized in that it is composed of at least a base material, a color filter layer, and a flattening layer.

A typical configuration of the display device of the present invention is, for example, a TFT unit having a thin film transistor (hereinafter abbreviated as "TFT") or the like on a base material, and a light emitting layer on the top thereof. A light emitting element including the light emitting element, for example, an organic EL element (OLED) is arranged to form a light emitting display unit D. On the other hand, a color filter unit according to the present invention is formed on the back surface side of the base material, and a polarizing plate is arranged on the outermost surface side thereof. When the light emitting element device is an organic EL element, a circularly polarizing plate (λ / 4 polarizing plate) is applied as the polarizing plate. In the display device of the present invention including the color filter unit, it is preferable to apply a white light emitting type element to the light emitting layer constituting the light emitting element.

Further, in the display device provided with the color filter unit of the present invention, the "top emission type" that takes out the emitted light from the surface side where the light emitting element device is arranged with respect to the base material, or the color filter unit that sandwiches the base material. It may be any of the "bottom emission type" that extracts the emitted light from the back surface side on which the above is arranged.

In the color filter unit according to the present invention, the color filter layer is mainly classified into type A composed of a colorant and type B to which quantum dots are applied.

The configuration of a typical display device of the present invention will be described with reference to the drawings, but the configuration shown below is an example thereof, and the present invention is not limited to these illustrated configurations. In the description of each figure, the numbers described at the end of the components represent the symbols in each figure.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL type display device including a type A color filter unit composed of a colorant as a color filter layer and a light emitting device.

In the display device 1 shown in FIG. 1, the extraction electrode 6 and the TFT 4 are arranged on the first base material 2 located at the center, preferably the first base material 2 provided with the gas barrier layer (not shown). An organic EL unit D composed of a TFT unit 3 and an organic EL element (OLED) is arranged.

The TFT 4 is not an essential requirement and is not necessary, for example, in passive matrix type display applications. When a TFT is used, it may be an amorphous Si type or an oxide type, LTPS (low temperature polysilicon), HTPS (high temperature polysilicon) or OTFT (organic thin layer transistor). When a flexible substrate is used, a gas barrier layer is preferably formed on a flexible substrate having high temperature resistance such as varnish or polyimide, and a TFT is formed on the gas barrier layer. For the method of forming the TFT on these flexible substrates, for example, the method described in JP-A-2016-162535 can be referred to.

Next, an OLED is arranged on the upper part of the TFT unit 3.

In the OLED, the first electrode 5 is arranged at a position corresponding to the coloring filter of each color constituting the color filter. An organic functional layer group 7 including a light emitting layer and a second electrode 8 are arranged on the first electrode 5, and a first sealing layer 9 and a second sealing layer 10 are provided on the first electrode 5 as a sealing structure. It is formed. In FIG. 1, as a configuration of the second sealing layer, a configuration in which an alpet 12 composed of a protective film 14 and an aluminum foil 13 is arranged via a first adhesive layer 11 is illustrated. In FIG. 1, the organic functional layer group 7 and the second electrode 8 are shown as a common configuration, but if necessary, they may have an independent configuration corresponding to each coloring filter as in the case of the first electrode 5.

In the OLED, the region where the first electrode 5, the organic functional layer group 7 including the light emitting layer, and the second electrode 8 are all located is the light emitting area LA.

On the other hand, the color filter unit 16A according to the present invention is arranged via the second adhesive layer 15 on the surface of the first base material 2 opposite to the surface on which the OLED is arranged. The color filter unit 16A includes a red color filter CF _R1 containing a red colorant, a green color filter CF _G1 containing a green colorant, and a blue color filter CF _{B1 containing a blue colorant on the second base material 17.} The color filter layers 18 arranged at positions separated from each other are arranged. The width of each color filter CF is designed to be wider than the light emitting area LA of the OLED.

Next, a flattening layer 19 is arranged on the upper part of the color filter layer 18 and is bonded to the back surface side of the first base material 2 via the second adhesive layer 15. The present invention is characterized in that at least one layer of the color filter layer 18 or the flattening layer 19 contains an organometallic oxide having a structure represented by the general formula (1) according to the present invention.

Finally, the polarizing plate 20 is arranged on the outside of the color filter unit 16A.

In the display device 1, the organic EL device was designed with white light-emitting type, by passing the respective color filters white light, red light emitting light L _R, the green luminescent light L _G, the blue emitting light L _B bottom emission It is taken out by the method.

By adopting the configuration shown in FIG. 1, at least one layer of the color filter layer 18 or the flattening layer 19 contains an organic metal oxide having a structure represented by the general formula (1) according to the present invention. , Moisture generated from the color filter unit, moisture absorption that traps moisture and oxygen that infiltrate from the back side, and water repellency that reacts with moisture to develop organic functional layers, etc. The effect can be prevented.

FIG. 2 is a schematic cross-sectional view showing an example of a type B color filter unit composed of quantum dots as a color filter layer, and the light emitting device is an organic EL type display device.

The display device 1 shown in FIG. 2 has the same configuration as the display device shown in FIG. 1 except for the color filter layer 18.

In the color filter unit 16B shown in FIG. 2, the red color filter _{CF R2} constituting a green color filter _{CF G2,} a blue color filter _{CF B2} is, quantum dots QD _R of each red emission, green light emission quantum dots QD _G, blue light emission it is configured to respectively containing quantum dots QD _B.

Next, details of each component of the display device of the present invention will be sequentially described.

《Color filter unit》
The color filter unit according to the present invention is composed of at least a base material, a color filter layer and a flattening layer.

[Organometallic oxide having a structure represented by the general formula (1)]
The present invention is characterized in that at least one of the color filter layer or the flattening layer contains an organometallic oxide having a structure represented by the following general formula (1).

General formula (1) R- [M (OR ₁ ) _y (O-) _xy ] _n- R
In the above general formula (1), R represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group. However, R may be a carbon chain containing a fluorine atom as a substituent. M represents a metal atom. OR ₁ represents a fluorinated alkoxy group. x represents the valence of the metal atom and y represents any integer between 1 and x. n represents the degree of polycondensation.

Hereinafter, the details of the organometallic oxide having the structure represented by the general formula (1) will be described.

The organic metal oxide according to the present invention is a polycondensate of an organic metal oxide or an organic metal oxide obtained by alcohol-decomposing a metal alkoxide in the presence of an excess alcohol and substituting the metal with an alcohol. At that time, by using a long-chain alcohol in which a fluorine atom is substituted at the β-position of the hydroxy group, an organometallic oxide containing a fluorinated alkoxide is obtained, and the moisture absorbing function according to the present invention is exhibited.

On the other hand, the organometallic oxide can promote the sol-gel reaction and form a polycondensate by sintering or irradiating with ultraviolet rays. At that time, when a long-chain alcohol in which a fluorine atom is substituted at the β-position of the hydroxy group is used, hydrolysis is performed by reducing the frequency factor of water existing around the metal in the metal alkoxide due to the water-repellent effect of the fluorine atom. It is characterized in that the rate is reduced, and by utilizing this phenomenon, a three-dimensional polymerization reaction can be suppressed and a uniform and dense organic thin film containing a desired organic metal oxide can be formed.

The organometallic oxide having a hygroscopic function according to the present invention is shown in the following reaction scheme I. In the structural formula of the polycondensate of the organometallic oxide after sintering, "M" in the "OM" portion further has a substituent, but is omitted.

The organic metal oxides, polycondensed organic thin film formed by the sintering or UV irradiation, by the following reaction scheme II, was hydrolyzed by moisture (H 2 _O) from the outside of the system, water-repellent or hydrophobic It releases hydrolyzed alcohol (R'-OH), which is a sex substance. This fluorinated alcohol further prevents the permeation of water into the electronic device.

That is, in the organic metal oxide having a hygroscopic function according to the present invention, since the fluorinated alcohol produced by hydrolysis is water-repellent or hydrophobic, in addition to the original drying property (desiccant property), it repels water by reaction with water. It has a feature not found in conventional hygroscopic agents, that is, a water function is added and a synergistic effect (synergy effect) is exerted on the sealing property.

In the following structural formula, "M" in the "OM" part further has a substituent, but is omitted.

The organometallic compound according to the present invention preferably contains an organometallic oxide having a structure represented by the general formula (1) as a main component. The "main component" in the present invention is preferably the organometallic oxide in which 70% by mass or more of the total mass of the hygroscopic agent releases a hydrophobic substance, and more preferably 80% by mass or more. , Particularly preferably 90% by mass or more.

The organic metal oxide according to the present invention is not particularly limited as long as it can be produced by using the sol-gel method. For example, the metal and lithium introduced in "Science of sol-gel method" P13 and P20. , Sodium, copper, calcium, strontium, barium, zinc, boron, aluminum, gallium, yttrium, silicon, germanium, lead, phosphorus, antimony, vanadium, tantalum, tungsten, lantern, neodium, titanium, zirconium. As an example, a metal oxide containing the above-mentioned metal can be mentioned. Preferably, the metal atom represented by M is titanium (Ti), zirconium (Zr), tin (Sn), tantalum (Ta), iron (Fe), zinc (Zn), silicon (Si) and aluminum ( It is preferable to select from Al) from the viewpoint of obtaining the effect of the present invention.

In the above general formula (1), OR ₁ represents a fluorinated alkoxy group.

R ₁ represents an alkyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group substituted with at least one fluorine atom. Specific examples of each substituent will be described later.

R represents hydrogen, an alkyl group having one or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group. Alternatively, at least a part of hydrogen of each group may be substituted with halogen. It may also be a polymer.

The alkyl group is substituted or unsubstituted, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group, henicosyl group, docosyl and the like, but carbon is preferable. Those with a number of 8 or more are preferable. Further, these oligomers and polymers may be used.

The alkenyl group is substituted or unsubstituted, and specific examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and the like, and preferably one having 8 or more carbon atoms. Further, these oligomers or polymers may be used.

The aryl group is substituted or unsubstituted, and specific examples thereof include a phenyl group, a tolyl group, a 4-cyanophenyl group, a biphenyl group, an o, m, p-terphenyl group, a naphthyl group, an anthranyl group, and a phenanthrenyl group. There are a fluorenyl group, a 9-phenylanthranyl group, a 9,10-diphenylanthranyl group, a pyrenyl group and the like, and those having 8 or more carbon atoms are preferable. Further, these oligomers or polymers may be used.

Specific examples of the substituted or unsubstituted alkoxy group include a methoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, a trifluoromethoxy group, and the like, preferably those having 8 or more carbon atoms. Further, these oligomers and polymers may be used.

Specific examples of the substituted or unsubstituted cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbonan group, an adamantane group, a 4-methylcyclohexyl group, a 4-cyanocyclohexyl group and the like, preferably those having 8 or more carbon atoms. good. Further, these oligomers or polymers may be used.

Specific examples of the substituted or unsubstituted heterocyclic group include a pyrazole group, a pyrrolin group, a pyrazole group, a pyrazoline group, an imidazole group, a triazole group, a pyridine group, a pyridazine group, a pyrimidine group, a pyrazine group, a triazine group, and an indol group. Benzimidazole group, purine group, quinoline group, isoquinoline group, quinoline group, quinoxalin group, benzoquinoline group, fluorenone group, dicyanofluorenone group, carbazole group, oxazole group, oxadiazole group, thiazole group, thiazazole group, benzoxazole group , Benzoxiazole group, benzotriazole group, bisbenzoxazole group, bisbenzothiazole group, benzbenzimidazole group and the like. Further, these oligomers or polymers may be used.

Specific examples of the substituted or unsubstituted acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group and oxalyl. Group, malonyl group, succinyl group, glutalyl group, adipoil group, pimeroyl group, suberoyl group, azella oil group, sebacyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyle group, isocrotonoyl group, oleoil group, elelide group, maleoil group. , Fumaroyl group, citraconoyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoil group, hydroatropoil group, atropoil group, cinnamoyl group, floyl group, tenoyl group, nicotinoyyl Group, isonicotinoyl group, glycoloyl group, lactoyl group, glyceroyl group, tartronoyl group, maloyl group, tartaroyl group, tropoil group, benziloyl group, salicyloyl group, anisoyl group, vanilloyl group, veratroyl group, piperoniloyl group, protocatechuyl group, galloyl group. Group, Glyoxyloyl Group, Pyrvoyl Group, Acetacetyl Group, Mesooxalyl Group, Mesooxalo Group, Oxalacetyl Group, Oxalacet Group, Lebrinoyl Group These acyl groups may be substituted with fluorine, chlorine, bromine, iodine or the like. .. Preferably, the acyl group has 8 or more carbon atoms. Further, these oligomers or polymers may be used.

The metal alkoxide, metal carboxylate and fluorinated alcohol (R'-OH) become organometallic oxides according to the present invention by the following reaction scheme III. Here, as (R'-OH), the following structures of F-1 to F-16 are exemplified.

Examples of the metal alkoxide or metal carboxylate according to the present invention include the following _{compounds represented by M (OR) n} or M (OCOR) _n, and the organometallic oxide according to the present invention is the above-mentioned (R'-OH: F). When combined with -1 to F-16), it becomes a compound having the structure of the following exemplified compound numbers 1 to 135 (see the following exemplified compounds I, II and III). The organometallic oxide according to the present invention is not limited to this.

The method for producing an organometallic oxide according to the present invention is characterized in that it is produced using a mixed solution of a metal alkoxide and a fluoroalcohol.

As an example of the reaction, the reaction scheme IV of Exemplified Compound No. 1 and the structure of the organometallic oxide when applied to an organic thin film are shown below.

In the following structural formula, "Ti" in the "O-Ti" portion further has a substituent, but is omitted.

In the method for producing an organic metal oxide according to the present invention, after adding a fluoroalcohol to a metal alkoxide or a metal carboxylate and stirring and mixing as a mixture, water and a catalyst are added as necessary and reacted at a predetermined temperature. The method can be mentioned.

When the sol-gel reaction is carried out, a catalyst for the hydrolysis / polymerization reaction as shown below may be added for the purpose of promoting the hydrolysis / polycondensation reaction. What is used as a catalyst for the hydrolysis / polymerization reaction of the sol-gel reaction is "Technology for producing functional thin films by the latest sol-gel method" (written by Satoshi Hirashima, General Technology Center Co., Ltd., P29) and "Sol-gel". It is a catalyst used in a general sol-gel reaction described in "Science of Law" (written by Saio Sakuhana, Agne Shofusha, P154). For example, examples of acid catalysts include inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, and toluenesulfonic acid.

The amount of the catalyst used is preferably 2 molar equivalents or less, more preferably 1 molar equivalent or less, with respect to 1 mol of the metal alkoxide or metal carboxylate as a raw material for the organic metal oxide.

When the sol-gel reaction is carried out, the preferable amount of water added is 40 molar equivalents or less, more preferably 10 molar equivalents or less, with respect to 1 mol of the metal alkoxide or metal carboxylate as a raw material of the organic metal oxide. It is more preferably 5 molar equivalents or less.

In the present invention, the preferable reaction concentration, temperature, and time of the sol-gel reaction cannot be unequivocally determined because the types and molecular weights of the metal alkoxide or metal carboxylate used and the respective conditions are related to each other. That is, when the molecular weight of the alkoxide or metal carboxylate is high, or when the reaction concentration is high, if the reaction temperature is set high or the reaction time is set too long, the reaction product accompanies the hydrolysis and polycondensation reactions. There is a possibility that the molecular weight of the alkoxide will increase, resulting in high viscosity and gelation. Therefore, the usual preferable reaction concentration is generally in the range of 1 to 50% in terms of the mass% concentration of the solid content in the solution, and more preferably in the range of 5 to 30%. The reaction temperature is usually in the range of 0 to 150 ° C., preferably 1 to 100 ° C., more preferably 20 to 60 ° C., and the reaction time is about 1 to 50 hours, although it depends on the reaction time. Is preferable.

The polycondensate of the organometallic oxide forms an organic thin film, and absorbs water and releases a fluorinated alcohol which is a hydrophobic substance by the following reaction scheme V.

In the following structural formula, "Ti" in the "O-Ti" portion further has a substituent, but is omitted.

[Second base material]
As the second base material applicable to the color filter unit according to the present invention, one having sufficient strength, flatness, heat resistance, light transmission and the like is preferable, and for example, it is used as a base material of a normal color filter. Examples thereof include transparent resin films and thin glass substrates such as non-alkali glass and soda glass.

Examples of the transparent resin film base material include polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polymethyl methacrylate (abbreviation: PMMA), polycarbonate (abbreviation: PC), polysulfone, and polyether sulfone (abbreviation: PC). Abbreviation: PES), polycycloolefin (abbreviation: COP), acrylic crosslinkable resin, epoxy crosslinkable resin crosslinkable resin, unsaturated polyester crosslinkable resin, high temperature resistant varnish, imidized polyimide, etc. Examples of the film base material used.

[Color filter layer]
The color filter layer constituting the color filter unit according to the present invention is a combination of red / green / blue (RGB) and yellow / magenta / cyan (YMC) as a plurality of color filters, a mixed system thereof, and for brightness adjustment. Transparent pixels can be applied. A flattening layer is formed on the plurality of color filters for flattening and the like.

Further, when an organometallic oxide having a structure represented by the general formula (1) is applied to the color filter layer or the flattening layer according to the present invention, the organometallic oxide contained in the color filter layer is used. It is preferable that the value of the ratio of the number of fluorine atoms to the total number of carbon atoms and fluorine atoms satisfies the condition specified by the following formula (a).

Equation (a) 0.05 ≤ F / (C + F) ≤ 1.00
The measurement significance of the formula (a) is to quantify that the organic thin film produced by the sol-gel method requires a certain amount or more of fluorine atoms. F and C in the above formula (a) represent the concentrations of fluorine atoms and carbon atoms, respectively.

The preferred range of the formula (a) is 0.2 ≦ F / (C + F) ≦ 0.6.

The fluorine ratio is determined by applying the sol-gel solution used for forming an organic thin film onto a silicon wafer to prepare a thin film, and then applying the thin film to SEM / EDS (Energy Dispersive X-ray Spectoroscopy: Energy Dispersive X-ray Analyzer). The concentrations of the fluorine atom and the carbon atom can be obtained by elemental analysis according to the above. As an example of the SEM / EDS device, JSM-IT100 (manufactured by JEOL Ltd.) can be mentioned.

SEM / EDS analysis has the feature of being able to detect elements at high speed, with high sensitivity and with high accuracy.

Examples of the method for forming the color filter include type A formed by using a colorant and type B formed by using quantum dots.

(Type A: Colorant composition)
<Colorant>
Typical colorants applicable to the formation of color filters are listed below.

Examples of the red colorant for forming the red color filter ( _{CFR1) include C.I.} I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, Red pigments such as 255, 264, 269, 272, 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red colorant.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171 and 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and the like.

Examples of the orange pigment include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like.

Examples of the green colorant for forming the green color filter (CF _{G1) include C.I.} I. Green pigments such as Pigment Green 7, 36, 58 can be used. The same yellow pigment as the red coloring composition can be used in combination with the green coloring composition.

Examples of the blue colorant for forming the blue color filter (CF _{B1) include C.I.} I. Pigment Blue 15: 3, 15: 4 blue pigment, C.I. I. In addition to the purple pigment of Pigment Violet 23, other pigments may be used in combination as appropriate.

Further, in combination with the above organic pigment, it is also possible to use an inorganic pigment in combination as necessary in order to secure good coatability, sensitivity, developability and the like while balancing saturation and lightness. Examples of inorganic pigments include metal oxide powders such as yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, and cobalt green, metal sulfide powder, and metal powder. Can be mentioned. Further, for color matching, the dye can be contained within a range that does not reduce the liquid crystal resistance and the heat resistance.

(Type B: Quantum dot configuration)
The quantum dots applicable to the type B of the color filter according to the present invention are particulate materials having a predetermined particle size that are composed of semiconductor crystals and exhibit the quantum dot effect. The energy level E of a quantum dot is generally expressed by the following equation (I), where Planck's constant is "h", the effective mass of electrons is "m", and the radius of fine particles is "R".

Equation (I) E∝h ² / mR ²
As shown by the formula (I), the band gap of ^{the quantum dots increases in proportion to "R-2} ", and the quantum dot effect can be obtained. By controlling and defining the particle size of the quantum dots in this way, the bandgap value of the quantum dots can be controlled. That is, by controlling and defining the particle size of the quantum dot particles, it is possible to provide diversity that ordinary molecules do not have. Therefore, by exciting with light or applying a voltage to an organic EL element containing quantum dots, electrons and holes are confined and recombined in the quantum dots to convert electrical energy into light of a desired wavelength. It can be converted and emitted. In the color filter according to the present invention, a particulate material that exhibits such a quantum dot effect is used as the quantum dots.

The particle size of the quantum dots is set to an appropriate value according to the desired emission spectrum, but is preferably in the range of 1 to 20 nm, and more preferably in the range of 1 to 10 nm. Specifically, the particle size of the quantum dots is in the range of 3.0 to 20 nm when the emission color is red, and within the range of 1.5 to 10 nm when the emission color is green. And. The range of such a particle size may be such that the average particle size of the quantum dots is included in these ranges.

The average particle size of the quantum dots can be measured by using a known measuring method. For example, a method of observing particles of a quantum dot material with a transmission electron microscope (TEM) and obtaining the number average particle size from the particle size distribution, or a particle size measuring device by a dynamic light scattering method, for example, "ZETASIER Nano". Examples include a method of measuring using "Series Nano-ZS" (manufactured by Malvern) and a method of deriving a particle size distribution from a spectrum obtained by the X-ray small angle scattering method using a particle size distribution simulation calculation of quantum dots. Be done.

The amount of the quantum dots added is preferably in the range of 0.01 to 50 parts by mass, preferably in the range of 0.05 to 25 parts by mass with respect to 100 parts by mass of all the constituent substances of the color filter to be added. It is more preferable, and it is particularly preferable that the content is in the range of 0.1 to 20 parts by mass. When the amount of quantum dots added is 0.01 parts by mass or more, the quantum dot effect can be significantly obtained by adjusting the emission energy of the dopant material in the light emitting layer to an appropriate wavelength and adjusting the absorption energy of the quantum dot material. , It is easy to stabilize the brightness and chromaticity of the extracted light. Further, when the amount of the added quantum dots is 50 parts by mass or less, the distance between the particles of the dispersed quantum dots can be sufficiently secured, so that the quantum dot effect due to the added quantum dots can be surely exhibited. ..

Examples of the constituent materials of the quantum dots include simple elements of Group 14 of the Periodic Table such as carbon, silicon, germanium and tin, simple elements of Group 15 of the Periodic Table such as phosphorus (black phosphorus), and periods of selenium and tellurium. Table Group 16 single element, multiple periodic tables such as silicon carbide (SiC) Table Group 14 compound, tin oxide (IV) (SnO ₂ ), tin sulfide (II, IV) (Sn (II) Sn (IV) S ₃ ), tin sulfide (IV) (SnS ₂ ), tin sulfide (II) (SnS), tin selenium (II) (SnSe), tin telluride (II) (SnTe), lead sulfide (II) ) (PbS), lead (II) selenium (PbSe), lead (II) (PbTe), a compound of Group 14 of the Periodic Table and Group 16 of the Periodic Table, boron nitride (BN), phosphorus Boron oxide (BP), boron arsenide (BAs), aluminum nitride (AlN), aluminum phosphate (AlP), aluminum arsenide (AlAs), antimonized aluminum (AlSb), gallium nitride (GaN), gallium phosphate (Al) Group 13 of the periodic table of GaP), gallium arsenide (GaAs), gallium antimonized (GaSb), indium nitride (InN), indium phosphate (InP), indium arsenide (InAs), indium antimonized (InSb), etc. Compounds of elements and Group 15 elements of the Periodic Table (or Group III-V compound semiconductors), aluminum sulfide (Al ₂ S ₃ ), aluminum selenium (Al ₂ Se ₃ ), gallium sulfide (Ga ₂ S ₃ ), selenium Gallium oxide (Ga ₂ Se ₃ ), gallium telluride (Ga ₂ Te ₃ ), indium oxide (In ₂ O ₃ ), indium sulfide (In ₂ S ₃ ), indium selenium (In ₂ Se ₃ ), indium telluride Compounds of Group 13 elements of the Periodic Table and Group 16 elements of the Periodic Table such as (In ₂ Te ₃ ), Tallium chloride (I) (TlCl), Tallium bromide (I) (TlBr), Tallium iodide (I) Compounds of Group 13 elements of the periodic table such as (TlI) and elements of Group 17 of the periodic table, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenium (ZnSe), zinc tellurate (ZnTe), cadmium oxide (CdO), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurized (CdTe), mercury sulfide (HgS), mercury selenium (HgSe), mercury mercury (HgTe), etc. Elements and Periodic Table No. Compounds with group 16 elements (or group II-VI compound semiconductors), arsenic sulfide (III) (As ₂ S ₃ ), arsenide selenium (III) (As ₂ Se ₃ ), arsenic arsenide (III) (As ₂₎ Te ₃ ), antimony sulfide (III) (Sb ₂ S ₃ ), antimonic selenium (III) (Sb ₂ Se ₃ ), antimony telluride (III) (Sb ₂ Te ₃ ), bismuth sulfide (III) (Bi ₂₎ Compounds of periodic table group 15 elements and periodic table group 16 elements such as S ₃ ), bismuth selenium (III) (Bi ₂ Se ₃ ), bismuth tellurized (III) (Bi ₂ Te _{3), copper oxide} Compounds of elements of Group 11 of the periodic table such as (I) (Cu ₂ O) and copper (I) selenium (Cu ₂ Se) and elements of Group 16 of the periodic table, copper (I) (CuCl) chloride, bromide. Compounds of periodic table Group 11 elements and periodic table group 17 elements such as copper (I) (CuBr), copper iodide (I) (CuI), silver chloride (AgCl), silver bromide (AgBr), oxidation Compounds of periodic table group 10 elements such as nickel (II) (NiO) and periodic table group 16 elements, periodic table group 9 such as cobalt oxide (II) (CoO) and cobalt sulfide (II) (CoS). the compounds of the elements and the periodic table group 16 element, triiron tetraoxide (Fe 3 O _4), the compounds of the periodic table group 8 element and periodic table group 16 element such as iron sulfide (II) (FeS), Periodic table of manganese (II) oxide (MnO), etc. Periodic table of compounds of Group 7 elements and Group 16 element of periodic table, molybdenum sulfide (IV) (MoS ₂ ), tungsten oxide (IV) (WO ₂ ), etc. Periodic table of Group 6 elements and periodic table Chalcogens such as compounds of Group 16 elements, vanadium oxide (II) (VO), vanadium oxide (IV) (VO ₂ ), tantalum oxide (V) (Ta ₂ O ₅ ), etc. Compounds of Group 5 elements and Group 16 elements of the periodic table, elements of Group 4 of the periodic table such as titanium oxide (TiO ₂ , Ti ₂ O ₅ , Ti ₂ O ₃ , Ti ₅ O _9, etc.) and Group 16 of the periodic table Compounds with elements, compounds of periodic table Group 2 elements such as magnesium sulfide (MgS) and chalcogen (MgSe) and periodic table Group 16 elements, cadmium oxide (II) chromium (III) (CdCr ₂ O ₄₎ ), Cadmium selenium (II) chromium (III) (CdCr ₂ Se ₄ ), copper (II) sulfide _{(III) (CuCr 2} S ₄ ), mercury (II) selenium (II) chromium (III) ) (HgCr ₂ Se ₄ ) and other chalcogen spinels, barium titanate _{(BaTIO 3} ) and the like.

Among these, the substances constituting the quantum dots _{include compounds of Group 14 elements of the Periodic Table and Group 16 elements of the Periodic Table such as SnS 2} , SnS, SnSe, SnTe, PbS, PbSe, and PbTe, GaN, GaP, and the like. Group III-V compound semiconductors such as GaAs, GaSb, InN, InP, InAs, InSb, Ga ₂ O ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , In ₂ O ₃ , In ₂ S ₃ , Compounds of Group 13 elements of the Periodic Table and Group 16 elements of the Periodic Table, such as In ₂ Se ₃ and In ₂ Te ₃ , ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, Group II-VI compound semiconductors such as HgTe, As ₂ O ₃ , As ₂ S ₃ , As ₂ Se ₃ , As ₂ Te ₃ , Sb ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Compounds of Group 15 elements of the Periodic Table and Group 16 of the Periodic Table such as Bi ₂ O ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , and Bi ₂ Te _{3, and Group 2 elements of the Periodic Table such as MgS and MgSe} Compounds with Group 16 elements of the Periodic Table are preferred, among which Si, Ge, GaN, GaP, InN, InP, Ga ₂ O ₃ , Ga ₂ S ₃ , In ₂ O ₃ , In ₂ S ₃ , ZnO, ZnS, CdO and CdS are more preferable. Since these substances do not contain highly toxic negative elements, they are excellent in environmental pollution resistance and safety to living organisms, and since a pure spectrum can be stably obtained in the visible light region, they are light emitting devices. It is advantageous for the formation of. Of these materials, CdSe, ZnSe, and CdS are preferable in terms of light emission stability. From the viewpoint of luminous efficiency, high refractive index, and economic efficiency of safety, ZnO and ZnS quantum dots are preferable.

These substances constituting the quantum dots may be used alone or in combination of two or more. That is, within the range of the emission spectrum and the particle size, one kind of quantum dot particles may be contained, and two or more kinds of quantum dot particles may be contained. In addition to these substances, quantum dots may be doped with trace amounts of various elements as impurities, if necessary. By doping a small amount of various elements, the emission characteristics of quantum dots can be greatly improved.

The quantum dots may be particles having a core / shell type structure. That is, the quantum dot can be composed of a core portion that exerts the quantum dot effect and a shell portion composed of an inert inorganic substance or an organic ligand. Further, the core portion and the shell portion may be composed of different substances, and a gradient structure (inclined structure) may be formed between the core portion and the shell portion. When such a core / shell type quantum dot is used, the aggregation of the quantum dots can be suppressed and the dispersibility can be improved. Then, it becomes easy to adjust the emission brightness and the chromaticity, and stable emission characteristics can be obtained. The thickness of the shell portion is preferably in the range of 0.1 to 10 nm, more preferably in the range of 0.1 to 5 nm.

The quantum dots may also be surface-modified particles. The surface-modified particles can be obtained by adhering a surface modifier to the surface of such a single particle of the quantum dot or the surface of the shell portion of the core / shell type quantum dot. When the surface-modified quantum dots are used, the compatibility of the surface-modified quantum dots can be improved, and the surface-modified quantum dots can be well dispersed in the coating liquid forming the color filter. Further, during the production of quantum dots, it is possible to facilitate the growth of quantum dots having a desired particle size.

Examples of the surface modifier include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, tripropylphosphine, tributylphosphine, trihexylphosphine, and trioctylphosphine. Trialkylphosphins, polyoxyethylene alkylphenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether, and tri (n-hexyl) amines and tri (n-octyl) amines. , Tertiary amines such as tri (n-decyl) amines, organic phosphorus compounds such as tripropylphosphine oxide, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, tridecylphosphine oxide, and polyethylene glycol dilaurate. , Polyethylene glycol diesters such as polyethylene glycol distearate, organic nitrogen compounds such as nitrogen-containing aromatic compounds such as pyridine, lutidine, colisine and quinoline, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, Amino alkanes such as hexadecylamine and octadecylamine, dialkyl sulfides such as dibutyl sulfide, dialkyl sulfoxides such as dimethyl sulfoxide and dibutyl sulfoxide, organic sulfur compounds such as sulfur-containing aromatic compounds such as thiophene, and palmitin. Higher fatty acids such as acids, stearic acids and oleic acids, alcohols, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like can be mentioned. Among these, as the surface modifier, a substance that coordinates and stabilizes the fine particles of quantum dots in the high temperature liquid phase is preferable from the viewpoint of production, and specifically, trialkylphosphines, organic phosphorus compounds, and aminos. Alcans, tertiary amines, organic nitrogen compounds, dialkyl sulfides, dialkyl sulfoxides, organic sulfur compounds, higher fatty acids, and alcohols are suitable.

Quantum dots can be produced by known methods. Specifically, for example, a molecular beam epitaxy method, a CVD method, a liquid phase synthesis method, or the like can be used. As a liquid phase synthesis method, for example, in a non-polar organic solvent such as alkanes such as n-heptane, n-octane and isooctane, or aromatic hydrocarbons such as benzene, toluene and xylene, a reverse micelle of the raw material aqueous solution is used. The reverse micelle method of forming and growing crystals in this reverse micelle phase, the hot soap method of injecting a thermally decomposable raw material into a high-temperature liquid phase organic medium to grow crystals, and the solution reaction of growing crystals by acid-base reaction at low temperature. The law etc. can be mentioned.

(Binder for forming color filters)
As a binder applicable for forming the color filter by holding each of the above colorants and quantum dots, at least one layer of the color filter layer or the flattening layer is the general formula (1) according to the present invention described above. ), The following various resin materials can be applied as long as the objective effect of the present invention is not impaired.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene, polybutadiene, polyimide resin and the like.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

Photosensitive resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups in linear polymers having reactive substituents such as hydroxy groups, carboxy groups, and amino groups. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting silicic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is a (meth) acrylic compound having a hydroxy group such as a hydroxyalkyl (meth) acrylate. A half-esterified product is also used.

In the formation of the color filter containing the colorant according to the present invention, a solvent can be contained. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, and methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

[Flat layer]
As the flattening layer according to the present invention, an organic resin such as an organic monomer, an oligomer, or a polymer can be preferably used in addition to the organometallic oxide having the structure represented by the general formula (1) according to the present invention. These organic resins preferably have a polymerizable group or a crosslinkable group, and are formed by coating from an organic resin composition coating solution containing these organic resins and, if necessary, a polymerization initiator, a crosslinker, or the like. It is preferable that the layer is cured by subjecting it to light irradiation treatment or heat treatment. Here, the "crosslinkable group" is a group capable of crosslinking a binder polymer by a chemical reaction occurring in a light irradiation treatment or a heat treatment. The chemical structure of the group having such a function is not particularly limited, and examples of the functional group capable of addition polymerization include cyclic ether groups such as an ethylenically unsaturated group and an epoxy group / oxetanyl group. Further, it may be a functional group that can become a radical by light irradiation, and examples of such a crosslinkable group include a thiol group, a halogen atom, an onium salt structure and the like. Of these, ethylenically unsaturated groups are preferable, and the functional groups described in paragraphs 0130 to 0139 of JP-A-2007-17948 are included.

Specific examples of the organic resin composition include a resin composition containing an acrylate compound having a radically reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, an epoxy acrylate, and a urethane acrylate. , A resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate is dissolved. It is also possible to use any mixture of the resin compositions as described above, even if it is a photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule. There are no particular restrictions.

Examples of the reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-. Pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, di Cyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-metricethyl acrylate , Methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1 , 3-Propanediol Acrylate, 1,4-Cyclohexanediol Diacrylate, 2,2-Dimethylol Propane Diacrylate, glycerol Diacrylate, Tripropylene Glycol Diacrylate, Gglycerol Triacrylate, Trimethylol Propanetriacrylate, Polyoxyethyltri Methylolpropan triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide-modified pentaerythritol triacrylate, ethylene oxide-modified pentaerythritol tetraacrylate, propionoxide-modified pentaerythritol triacrylate, propionoxide-modified pentaerythritol tetraacrylate, triethylene glycol Diacrylate, polyoxypropyltrimethylol propanetriacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2,4 -Trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and the above acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane , 1-Vinyl-2-pyrrolidone and the like. The above-mentioned reactive monomer can be used as one or a mixture of two or more kinds, or as a mixture with other compounds.

The photosensitive resin composition contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, and 4,4-dichlorobenzophenone. 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2 -Amil anthraquinone, β-chloroanthraquinone, antron, benzanthron, dibenzsberon, methylene antron, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylene)- 4-Methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione -2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanthrion-2- (o-benzoyl) oxime, Michler ketone, 2-methyl [4- (methylthio) phenyl] -2-monophorino-1 -Propane, 2-benzyl-2-dimethylamino-1- (4-monophorinophenyl) -butanone-1, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobuty Photoreducing dyes such as lonitrile, diphenyldisulfide, benzthiazoledisulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin, methylene blue, and ascorbic acid, triethanolamine, etc. Examples thereof include a combination of reducing agents, and these photopolymerization initiators can be used in one kind or a combination of two or more kinds.

[Method of forming color filter unit]
A method for forming the color filter unit 16 composed of the second base material 17, the color filter layer 18, and the flattening layer 19 described above according to the present invention will be described.

As shown in FIGS. 1 and 2, the color filter unit 16 arranges the second base material 17 at a position facing the first base material 2 used in the TFT forming step and the organic EL device forming step described later. On the second base material 17, a plurality of color filters that emit light in a specific wavelength range of red, green, and blue as the color filter layer 18 according to the present invention are applied, and a coloring material (colorant or quantum) for displaying those colors is applied. Using a photosensitive resin material containing (dots), it is arranged and formed in a strip shape by a wet coating method or the like.

The thickness of each color filter may be appropriately set depending on the type to be selected and the presence or absence of the formation of the cavity structure, and the thickness is generally in the range of 0.5 to 2 μm. It may have a portion that partially overlaps with each of the adjacent color filters, but preferably, a partition layer using photosensitive polyimide or the like is formed, and the red, green, and blue colors are separated so as to separate the color filters. Form a filter. The partition layer and the color filter may be either positive type or negative type. The bulkhead layer may be adjusted according to the thickness of the associated color filter and is formed with a thickness in the range of 0.5-5 μm. In particular, when the red, green, and blue color filters have different film thicknesses, it is preferable to use a partition wall because it is possible to suppress fluctuations in transmittance due to the thickness of the end portion.

Then, since the red, green, and blue color filters _{(CF R, CF G, CF} B) after forming a planarization treatment, to form a planarizing layer 19. The flattening layer 19 is used for the flattening treatment so as to have sufficient adhesion to the second adhesive layer 15 which is an adjacent layer.

For details of the method for forming the color filter unit, for example, Japanese Patent Application Laid-Open No. 2001-66414, Japanese Patent Application Laid-Open No. 2001-66415, WO2013 / 146903, and the like can be referred to.

[Wet coating method]
A wet coating method can be applied to the formation of the color filter unit according to the present invention, and at least the color filter layer is preferably formed by the wet coating method.

Examples of the wet coating method applicable to the present invention include a spin coating method, a casting method, a screen printing method, a die coating method, a blade coating method, a roll coating method, a spray coating method, a curtain coating method, and an LB method (Langmuir-bro). The jet method), the inkjet printing method, and the like are preferable from the viewpoint of easy to obtain a uniform thin film and high productivity.

(Inkjet printing method)
In the present invention, the inkjet printing method is preferable in that a uniform layer thickness can be formed with high accuracy with respect to a local region.

The outline of the inkjet printing method will be described below.

In the formation of the color filter unit according to the present invention, it is particularly preferable to apply the inkjet printing method to at least the formation of the color filter layer.

Hereinafter, the manufacturing flow of the inkjet head used in the inkjet printing method, the injection conditions of ink droplets, the inkjet recording method and recording apparatus, and the specific surface emitting panel inkjet printing method will be described with reference to the drawings.

<Inkjet head>
The inkjet head used in the inkjet printing method may be an on-demand method or a continuous method. The discharge method includes an electric-mechanical conversion method (for example, single cavity type, double cavity type, bender type, piston type, shared mode type, shared wall type, etc.) and an electric-heat conversion method (for example, thermal). Specific examples include an inkjet type, a bubble jet (registered trademark) type, etc.), an electrostatic attraction method (for example, an electric field control type, a slit jet type, etc.), and a discharge method (for example, a spark jet type, etc.). However, any discharge method may be used. Further, as the printing method, a serial head method, a line head method, or the like can be used without limitation.

<Ink drop size>
In forming the color filter layer, the volume of ink droplets ejected from the inkjet head is preferably in the range of 0.5 to 100 pL. From the viewpoint of less uneven coating of the color filter layer and high printing speed, the range is more preferably 2 to 20 pL. The volume of the ink droplet can be appropriately adjusted to a desired condition by adjusting the applied voltage or the like.

<Printing method>
The printing method by the inkjet printing method includes a one-pass printing method and a multi-pass printing method. The one-pass printing method is a method in which a plurality of inkjet heads are fixedly arranged in a predetermined printing area and printing is performed by one head scan. On the other hand, the multi-pass printing method (also referred to as a serial printing method) is a method of printing a predetermined print area by a plurality of head scans.

In the one-pass printing method, it is preferable to use a wide head in which nozzles are arranged side by side over a width equal to or larger than a desired coating pattern width. When forming a plurality of independent coating patterns whose patterns are not continuous with each other on the same substrate, a wide head having at least the width of each coating pattern may be used.

FIG. 3 is a schematic view showing an example of a method for forming a color filter using an inkjet printing method of a one-pass printing method.

FIG. 3 shows a material for forming a plurality of color filter CFs forming a color filter layer 18 (for example, a colorant, a quantum dot, a binder, etc.) on a second base material 17 using an inkjet printer provided with an inkjet head 30. ) Is sequentially ejected to form a plurality of independent forms of color filter CF.

As shown in FIG. 3, while continuously transporting the second base material 17, ink containing a color filter forming material is sequentially ejected as ink droplets by the inkjet head 30, and is composed of a desired color filter CF group. The color filter layer 18 to be formed is formed.

An ink jet liquid supply mechanism for ejection is connected to the inkjet head 30. The ink liquid is supplied by the tank 38A. In this example, the tank liquid level is kept constant so that the ink liquid pressure in the inkjet head 30 is always kept constant. As a method, the ink liquid overflows from the tank 38A and is returned to the tank 38B by natural flow. The ink liquid is supplied from the tank 38B to the tank 38A by the pump 31, and the liquid level of the tank 38A is controlled to be stable according to the injection conditions.

The ink liquid is returned from the pump 31 to the tank 38A after passing through the filter 32. As described above, it is preferable that the ink liquid is passed through a filter medium having an absolute filtration accuracy or a quasi-absolute filtration accuracy of 0.05 to 50 μm at least once before being supplied to the inkjet head 30.

Further, the ink liquid can be forcibly supplied from the tank 36 and the cleaning solvent from the tank 37 can be forcibly supplied to the inkjet head 30 by the pump 39 in order to perform the cleaning work and the liquid filling work of the inkjet head 30. Such tank pumps may be divided into a plurality of such tank pumps with respect to the inkjet head 30, a branch of a pipe may be used, or a combination thereof may be used. In FIG. 3, the pipe branch 33 is used. Further, in order to sufficiently remove the air in the inkjet head 30, the ink liquid is forcibly sent from the tank 36 to the inkjet 30 by the pump 39, and the ink liquid is withdrawn from the air bleeding pipe and sent to the waste liquid tank 34. There is also.

Examples of the inkjet head applicable to the present invention include Japanese Patent Application Laid-Open No. 2012-140017, Japanese Patent Application Laid-Open No. 2013-01227, Japanese Patent Application Laid-Open No. 2014-058771, Japanese Patent Application Laid-Open No. 2014-097644, and Japanese Patent Application Laid-Open No. 2015-142979. No., JP-A-2015-142980, JP-A-2016-002675, JP-A-2016-002682, JP-A-2016-107401, JP-A-2017-109476, JP-A-2017-177626 Etc., an inkjet head having the configuration described in the above can be appropriately selected and applied.

[Second adhesive layer]
In the display device of the present invention, the color filter unit 16 produced by the above method is second-bonded to the back surface of the first base material 2 constituting the organic EL unit D, as shown in FIGS. 1 and 2. It is bonded via the layer 15.

The adhesive material (adhesive amount) forming the second adhesive layer includes, for example, a heat-curable type in which fillers such as inorganic, organic, and hybrid are dispersed in an epoxy-based heat-curable resin, and a photoinitiator. UV-curable type, hydrophilic acrylic polymer adhesive typified by polyacrylic acid adhesive, polyvinyl acetal adhesive, polyvinyl alcohol adhesive, polyvinyl alcohol adhesive, vinyl acetate adhesive, rubber Adhesives (eg, natural rubber, synthetic rubber, styrene-isoprene-styrene block copolymer, isoprene rubber, polyisobutylene (PIB), styrene-butadiene-styrene block copolymer, styrene-butadiene rubber, polybutene, etc.) Can be mentioned.

The thickness of the second adhesive layer formed by the adhesive material is not particularly limited, but is preferably selected within the range of 0.1 to 10 μm.

<< TFT unit >>
As the TFT applicable to the TFT unit, as described above, amorphous Si type, oxide type, LTPS (low temperature polysilicon), HTPS (high temperature polysilicon), OTFT (organic thin layer transistor), etc. can be applied. can.

Regarding the method of forming the TFT on the first base material 2, for example, Sharp Technique No. 99 (November 2007), JP-A-6-202150, JP-A-2011-211003, JP-A-2014- You can refer to the methods described in Japanese Patent Application Laid-Open No. 078730, Japanese Patent Application Laid-Open No. 2014-146823, Japanese Patent Application Laid-Open No. 2014-168603, Japanese Patent Application Laid-Open No. 2016-162535, and the like.

For example, after forming a gate electrode on a base material, a gate insulating layer is formed, a source electrode and a drain electrode are formed on the gate insulating layer, and an organic semiconductor material layer is formed on the gate insulating layer between the source and drain electrodes. A method of forming a bottom gate type organic TFT by forming, or after forming a gate electrode on a base material, forming a gate insulating layer, forming an organic semiconductor material layer on the gate electrode, and then a source electrode and a drain. Examples thereof include a method of forming an electrode to form an organic TFT.

In the TFT unit 3, in addition to the TFT 4, a drawing electrode 6 from the first electrode 5 constituting the organic EL element OLED is arranged.

<< Light emitting element unit >>
In the display device of the present invention, for example, after forming the TFT unit 3 on the first base material 2 provided with the gas barrier layer, a light emitting element, for example, an OLED which is an organic EL element is formed on the TFT unit 3. The light emitting display unit D is configured.

Hereinafter, an example in which an organic EL element is used as the light emitting element will be described.

[Basic configuration of organic EL element]
FIG. 4 shows a typical schematic cross-sectional view of an organic EL element applicable as a light emitting element to the display device of the present invention.

In the organic EL element OLED shown in FIG. 4, the configuration of the first electrode 5 to the second electrode 9 is shown, and the description of the sealing structure on the first electrode 5 to the second electrode 9 is omitted.

In FIG. 4, a first electrode 5 is provided on the first base material 2 and the TFT unit 3, and a leader electrode 6 is provided on an extension line thereof.

The organic functional layer group 7 is laminated on the first electrode 5. The organic functional layer group 7 can have various configurations except that it has at least a light emitting layer.

FIG. 4 shows a typical configuration of a typical organic functional group, and the hole injection layer 22, the hole transport layer 23, the light emitting layer 24, and the electron transport are performed on the first electrode 5 (anode). The layer 25 and the electron injection layer 26 are sequentially laminated to form the organic functional layer group 7, and the second electrode 8 (cathode) is arranged on the organic functional layer group 7.

[Constituent materials for organic EL devices]
The details of the configuration of the organic EL element, which is a light emitting element suitable for the display device of the present invention, will be described below.

As a configuration excluding the first base material, the TFT unit, and the sealing portion of the organic EL element according to the present invention, in addition to the configuration shown in FIG. 4, the following configuration can be given as an example. The light emitting layer applied to the present invention is preferably a white light emitting layer composed of a blue light emitting layer, a green light emitting layer and a red light emitting layer.

(I) 1st electrode / organic functional layer group (light emitting layer / electron transporting layer) / 2nd electrode (ii) 1st electrode / organic functional layer group (hole transporting layer / light emitting layer / electron transporting layer) / 2nd Electrode (iii) 1st electrode / organic functional layer group (hole transport layer / light emitting layer / hole blocking layer / electron transport layer) / 2nd electrode (iv) 1st electrode / organic functional layer group (hole transport layer) / Light emitting layer / Hole blocking layer / Electron transporting layer / 2nd electrode buffer layer) / 2nd electrode (v) 1st electrode / Organic functional layer group (anodic buffer layer / Hole transporting layer / Light emitting layer / Hole blocking Layer / electron transport layer / second electrode buffer layer) / second electrode,
And so on.

Next, each component of the organic EL element will be described.

(1st base material)
The first base material applied to the organic EL device according to the present invention is preferably a bendable flexible resin base material having flexibility.

Examples of the resin base material applicable to the present invention include polyesters such as polyethylene terephthalate (abbreviation: PET) and polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, and cellulose triacetate (abbreviation: TAC). ), Celluloacetate butyrate, cellulose acetate propionate (abbreviation: CAP), cellulose acetate phthalate, cellulose nitrate and other cellulose esters and their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene. , Polycarbonate (abbreviation: PC), norbornene resin, polymethylpentene, polyether ketone, polyimide, polyethersulfone (abbreviation: PES), polyphenylene sulfide, polysulfone, polyetherimide, polyetherketoneimide, polyamide, fluororesin, Examples thereof include nylon, polymethylmethacrylate, acrylic and polyarylates, cycloolefin resins such as Arton (trade name: manufactured by JSR) and Apel (trade name: manufactured by Mitsui Chemicals).

Among these resin substrates, films such as polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), and polycarbonate (abbreviation: PC) are flexible in terms of cost and availability. It is preferably used as a resin base material.

In the present invention, the thickness of the resin base material can be in the range of 3 to 200 μm, preferably in the range of 10 to 100 μm, and more preferably in the range of 20 to 50 μm.

The first base material according to the present invention can also be suitably used as a sealing member (transparent base material) for an organic EL element. Further, the resin base material may be an unstretched film or a stretched film.

The resin base material applicable to the present invention can be produced by a conventionally known general film forming method. For example, by melting the resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching it, it is possible to produce an unstretched resin base material that is substantially amorphous and not oriented. Further, the unstretched resin base material is subjected to a known method such as uniaxial stretching, tenter type sequential biaxial stretching, tenter type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc., to convey the resin base material in the transport direction (vertical direction). , MD direction), or in the direction perpendicular to the transport direction of the resin base material (horizontal axis direction, TD direction), the stretched resin base material can be produced. In this case, the draw ratio can be appropriately selected according to the resin used as the raw material of the resin base material, but is preferably in the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

<Gas barrier layer>
A gas barrier layer can be provided on the first substrate according to the present invention. The gas barrier layer is not particularly limited as long as it has a blocking effect on gas, moisture, etc., and a conventionally known gas barrier layer can be appropriately selected and applied.

The gas barrier layer may be not only an inorganic material coating, but also a coating made of a composite material with an organic material or a hybrid coating obtained by laminating these coatings. As for the performance of the gas barrier layer, the water vapor permeability (environmental conditions: 25 ± 0.5 ° C., relative humidity (90 ± 2)%) conforming to JIS (Japanese Industrial Standards) -K7129 (2008) is about 0. 01g ^/ m 2 · 24h or less, JIS-K7126 (2006 year) in oxygen permeability conforming approximately 0.01mL ^/ m 2 · 24h · atm or less, a resistivity of 1 × ^{10 12} Ω · cm or more, light transmittance Is preferably a light-transmitting insulating film having a gas barrier property, which is about 80% or more in the visible light region.

As the material for forming the gas barrier layer, any material can be used as long as it is a material that causes deterioration of the organic EL element and can suppress the infiltration of gas such as water or oxygen into the organic EL element.

For example, it can be composed of a film made of an inorganic material such as silicon oxide, silicon nitride, silicon nitride, silicon carbide, silicon carbide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, niobium oxide, and molybdenum oxide. Preferably, the configuration is mainly made of a silicon compound such as silicon nitride or silicon oxide.

As a method for forming the gas barrier layer, a conventionally known film forming method can be appropriately selected and used. For example, a vacuum vapor deposition method, a sputtering method, a magnetron sputtering method, a molecular beam epitaxy method, a cluster ion beam method, and an ion play method can be used. Ting method, plasma polymerization method, atmospheric pressure plasma polymerization method (see JP-A-2004-68143), plasma CVD (Chemical Vapor Deposition) method, laser CVD method, thermal CVD method, ALD (atomic layer deposition) method, and A wet coating method using polysilazane or the like can also be applied.

(1st electrode: anode)
Examples of the first electrode constituting the organic EL element according to the present invention include a metal such as Ag and Au, an alloy containing a metal as a main component, CuI, or an indium-tin composite oxide (ITO), SnO ₂ and ZnO. The metal oxide of the above can be mentioned, but it is preferably a metal or an alloy containing a metal as a main component, and more preferably an alloy containing silver or a silver as a main component.

When the first electrode is a transparent electrode, silver is the main component, and the purity of silver is preferably 99% or more. Further, palladium (Pd), copper (Cu), gold (Au) and the like may be added to ensure the stability of silver.

The first electrode is a layer composed mainly of silver, but specifically, it may be formed of silver alone or may be composed of an alloy containing silver (Ag). Examples of such alloys include silver-magnesium (Ag-Mg), silver-copper (Ag-Cu), silver-palladium (Ag-Pd), silver-palladium-copper (Ag-Pd-Cu), and silver. -Indium (Ag-In) and the like can be mentioned.

(Intermediate electrode)
The organic EL device according to the present invention has a structure in which two or more organic functional layer units are laminated between an anode (first electrode) and a cathode (second electrode), and two or more organic functional layers. The units can be separated by an intermediate electrode layer unit having independent connection terminals for obtaining an electrical connection.

(Organic functional group 7)
Next, each layer constituting the organic functional layer group will be described in the order of a charge injection layer, a light emitting layer, a hole transport layer, an electron transport layer, and a blocking layer.

<Charge injection layer>
The charge injection layer applicable to the present invention is a layer provided between the electrode and the light emitting layer in order to reduce the driving voltage and improve the emission brightness. The details are described in Chapter 2, "Electrode Materials" (pages 123 to 166) of Volume 2 of "30th, published by NTS Co., Ltd.", and there are a hole injection layer and an electron injection layer.

The charge injection layer is generally between the anode and the light emitting layer or the hole transport layer in the case of the hole injection layer, and between the second electrode and the light emitting layer or the electron transport layer in the case of the electron injection layer. Although it can be present, the present invention is characterized in that a charge injection layer is placed adjacent to the transparent electrode. When used as an intermediate electrode, at least one of the adjacent electron injection layer and hole injection layer may satisfy the requirements of the present invention.

The hole injection layer according to the present invention is a layer arranged adjacent to the anode, which is the first electrode, in order to reduce the driving voltage and improve the emission brightness. It is described in detail in Volume 2, Chapter 2, "Electrode Materials" (pages 123-166) of "November 30, published by NTS".

The details of the hole injection layer are also described in JP-A-9-45479, 9-2660062, 8-288609, etc., and examples of the material used for the hole injection layer include , Porphyrin derivative, phthalocyanine derivative, oxazole derivative, oxadiazole derivative, triazole derivative, imidazole derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, hydrazone derivative, stilben derivative, polyarylalkane derivative, triarylamine derivative, carbazole derivative, Indrocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, and polymer materials or oligomers with polyvinylcarbazole and aromatic amines introduced into the main and side chains, polysilanes, and conductivity. Examples thereof include polymers or oligomers (for example, PEDOT (polyethylene dioxythiophene): PSS (polystyrene sulfonic acid), aniline-based copolymers, polyaniline, polythiophene, etc.).

Examples of the triarylamine derivative include a benzidine type represented by α-NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl) and MTDATA (4,4', 4 ". Examples thereof include a starburst type represented by -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine), a compound having fluorene or anthracene in the triarylamine connecting core portion, and the like.

Hexaazatriphenylene derivatives as described in JP-A-2003-591432 and JP-A-2006-135145 can also be used as the hole transport material in the same manner.

The electron injection layer is a layer provided between the second electrode and the light emitting layer in order to reduce the driving voltage and improve the emission brightness, and when the second electrode is composed of the transparent electrode according to the present invention. Is provided adjacent to the transparent electrode, and is provided in "Organic EL Element and Its Industrial Frontline (Published by NTS Co., Ltd. on November 30, 1998)", Volume 2, Chapter 2, "Electrode Material" ( It is described in detail on pages 123 to 166).

The details of the electron-injected layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specific examples of materials preferably used for the electron-injected layer include , Metals typified by strontium, aluminum, etc., alkali metal compounds typified by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkali metal halide layers typified by magnesium fluoride, calcium fluoride, etc., fluoride Examples thereof include an alkaline earth metal compound layer typified by magnesium, a metal oxide typified by molybdenum oxide and aluminum oxide, and a metal complex typified by lithium 8-hydroxyquinolate (Liq). When the transparent electrode in the present invention is the second electrode, an organic material such as a metal complex is particularly preferably used. The electron injection layer is preferably a very thin film, and the layer thickness is preferably in the range of 1 nm to 10 μm, although it depends on the constituent materials.

In the present invention, examples of the method for forming the electron injection layer include a wet coating method such as a coating method, an inkjet method, a coating method and a dip method, a vapor deposition method (resistive heating, EB method, etc.), a sputtering method, a CVD method and the like. In the method for manufacturing the image display member of the present invention, a method of forming the image display member in the formed bank by a wet coating method is preferable, and further, the wet coating method is an inkjet printing method. The method is preferred.

<Light emitting layer>
The light emitting layer constituting the organic functional layer unit of the organic EL element according to the present invention preferably contains a phosphorescent light emitting compound as a light emitting material.

This light emitting layer is a layer in which electrons injected from the electrode or the electron transport layer and holes injected from the hole transport layer recombine to emit light, and the light emitting portion is in the layer of the light emitting layer. It may be the interface between the light emitting layer and the adjacent layer.

The configuration of such a light emitting layer is not particularly limited as long as the contained light emitting material satisfies the light emitting requirements. Further, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-luminescent intermediate layer between each light emitting layer.

The total thickness of the light emitting layer is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained. The total thickness of the light emitting layer is the thickness including the non-light emitting intermediate layer when there is a non-light emitting intermediate layer between the light emitting layers. When the plurality of laminated light emitting layers correspond to the respective light emitting colors of blue, green and red, the relationship between the thicknesses of the blue, green and red light emitting layers is not particularly limited.

The light emitting layer as described above uses known light emitting materials and host compounds described below, for example, vacuum deposition method, spin coating method, casting method, LB method (Langmuir Blodgett method), inkjet printing method and the like. Although it can be formed by a method, in the method for manufacturing an image display member of the present invention, a method of forming a light emitting layer in the formed bank by using a wet coating method is preferable, and further, the wet coating method is inkjet printing. The method is preferred.

Further, as the light emitting layer, a plurality of light emitting materials may be mixed, or a phosphorescent light emitting material and a fluorescent light emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light emitting layer. It is preferable that the light emitting layer contains a host compound (also referred to as a light emitting host or the like) and a light emitting material (also referred to as a light emitting dopant) and emits light from the light emitting material.

<Host compound>
As the host compound contained in the light emitting layer, a compound having a phosphorescent quantum yield of phosphorescent emission at room temperature (25 ° C.) of less than 0.1 is preferable. Further, the phosphorus photon yield is preferably less than 0.01. Further, among the compounds contained in the light emitting layer, the volume ratio in the layer is preferably 50% or more.

As the host compound, a known host compound may be used alone, or a plurality of types of host compounds may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of electric charges, and it is possible to improve the efficiency of the organic electroluminescent device. Further, by using a plurality of types of light emitting materials described later, it is possible to mix different light emitting materials, whereby an arbitrary light emitting color can be obtained.

The host compound used in the light emitting layer may be a conventionally known low molecular weight compound or a high molecular weight compound having a repeating unit, and a low molecular weight compound having a polymerizable group such as a vinyl group or an epoxy group (deposited polymerizable light emitting host). ) May be used.

Examples of the host compound applicable to the present invention include JP 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, and so on. 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002 -75645, 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002- No. 363227, No. 2002-231453, No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183 No., 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002-308837, US Patent Publication No. 2003/0175553, USA Publication No. 2006/0280965, US Patent Publication No. 2005/0112407, US Patent Publication No. 2009/0017330, US Patent Publication No. 2009/0030202, US Patent Publication No. 2005/238919 No., International Publication No. 2001/039234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796 No., International Publication No. 2007/063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898, Examples of the compounds described in International Publication No. 2012/023947, JP-A-2008-074939, JP-A-2007-254297, European Patent No. 2034538 and the like can be mentioned.

<Luminescent material>
Examples of the light emitting material that can be used in the present invention include a phosphorescent compound (also referred to as a phosphorescent compound, a phosphorescent material or a phosphorescent dopant) and a phosphorescent compound (also referred to as a phosphorescent compound or a phosphorescent material). ) Can be mentioned.

<Phosphorescent compound>
The phosphorescent compound is a compound in which light emission from the excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. It is defined as a compound of 0.01 or more, but a preferable phosphorescence quantum yield is 0.1 or more.

The phosphorus photon yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopy II of the 4th edition Experimental Chemistry Course 7. The phosphorescence quantum yield in a solution can be measured using various solvents, but when the phosphorescence luminescent compound is used in the present invention, the phosphorescence quantum yield in any of the solvents is 0.01 or more. Should be achieved.

The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL element, and preferably contains a metal of Group 8 to 10 in the periodic table of the element. It is a complex-based compound, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex-based compound) or a rare earth complex, and the most preferable is an iridium compound.

In the present invention, at least one light emitting layer may contain two or more kinds of phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer changes in the thickness direction of the light emitting layer. It may be in the above mode.

Specific examples of known phosphorescent compounds that can be used in the present invention include compounds described in the following documents.

Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19,739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17,1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Publication No. 2006/835469, US Patent Publication No. 2006/20202194. Examples of the compounds described in the specification, US Patent Publication No. 2007/0087321, US Patent Publication No. 2005/0244673, and the like can be mentioned.

In addition, Inorg. Chem. 40,1704 (2001), Chem. Mater. 16,2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86,153505 (2005), Chem. Lett. 34,592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42,1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Publication No. 2002/0034656, US Pat. No. 7,332232, US Patent Publication No. 2009/01087737, US Patent Publication No. 2009/00397776, US Patent No. 6921915, US Patent No. 6687266, US Patent Publication No. 2007/0190359, US Patent Publication No. 2006 0008670, US Patent Publication No. 2009/015846, US Patent Publication No. 2008/0015355, US Patent No. 7250226, US Patent No. 7396598, US Patent Publication No. 2006 / 0236635, US Patent Publication No. 2003/0138657, US Patent Publication No. 2003/0152802, US Patent No. 70090928, and the like can be mentioned.

In the present invention, preferred phosphorescent compounds include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.

The phosphorescent compound (also referred to as a phosphorescent metal complex) described above is described in, for example, Organic Letters, vol3, No. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Mol. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, 40, 7, 1704-1711 (2001), Inorganic Chemistry, 41, 12, 3055-3066 (2002). , New Journal of Chemistry. , Vol. 26, p. 1171 (2002), European Journal of Organic Chemistry, Vol. 4, p. 695-709 (2004), and the methods disclosed in the references described in these documents. Can be synthesized by applying.

<Fluorescent luminescent compound>
Fluorescent compounds include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, and stillbens. Examples thereof include system dyes, polythiophene dyes, rare earth complex phosphors and the like.

<Hole transport layer>
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer also have a function of a hole transport layer. The hole transport layer may be provided as a single layer or a plurality of layers.

The hole transporting material has either injection or transport of holes or an electron barrier property, and may be either an organic substance or an inorganic substance. For example, triazole derivatives, oxaziazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stillben derivatives, silazane derivatives, aniline-based copolymers, conductive polymer oligomers and thiophene oligomers.

As the hole transporting material, the above-mentioned ones can be used, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary amine compounds can be used. preferable.

Typical examples of aromatic tertiary amine compounds and styrylamine compounds are N, N, N', N'-tetraphenyl-4,4'-diaminophenyl, N, N'-diphenyl-N, N'-. Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p) -Trillaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) Quadriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4'-[4- (di-p-tolylamino) styryl] stilben, 4-N, N Examples thereof include −diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostillbenzene and N-phenylcarbazole.

Examples of the method for forming the hole transport layer include a wet coating method such as a coating method, an inkjet printing method, a coating method, and a dip method, and a dry method such as a vapor deposition method (resistive heating, EB method, etc.), a sputtering method, and a CVD method. Examples thereof include a method using a process, but in the method for manufacturing an image display member of the present invention, a method of forming the image display member in the formed bank by a wet coating method is preferable, and further, the wet coating method is an inkjet printing method. It is preferable to have.

The thickness of the hole transport layer is not particularly limited, but is usually in the range of about 5 nm to 5 μm, preferably in the range of 5 to 200 nm. The hole transport layer may have a one-layer structure composed of one or more of the above materials.

Further, the p property can be enhanced by doping the material of the hole transport layer with impurities. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, and J. Am. Apple. Phys. , 95, 5773 (2004) and the like.

As described above, it is preferable to increase the p property of the hole transport layer because a device having lower power consumption can be manufactured.

<Electronic transport layer>
The electron transport layer is composed of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single-layer structure or a multi-layer laminated structure.

In the electron transport layer having a single layer structure and the electron transport layer having a laminated structure, as an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer, electrons injected from the cathode are used as the light emitting layer. It suffices if it has a function of transmitting. As such a material, any one can be selected and used from conventionally known compounds. Examples thereof include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, freolenidene methane derivatives, anthracinodimethanes, antron derivatives and oxadiazole derivatives. Further, among the above oxadiazole derivatives, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is replaced with a sulfur atom, and a quinoxalin derivative having a quinoxalin ring known as an electron-withdrawing group can also be used as a material for the electron transport layer. can. Further, a polymer material in which these materials are introduced into a polymer chain or a polymer material in which these materials are used as a polymer main chain can also be used.

Also, metal complexes of 8-quinolinol derivatives, such as tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-). Kinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc. and the central metal of these metal complexes A metal complex replaced with In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as a material for the electron transport layer.

The electron transport layer can be formed by thinning the material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet printing method, and an LB method. In the method for producing an image display member of the present invention, a method of forming an electron transport layer in the formed bank by using a wet coating method is preferable, and further, the wet coating method is preferably an inkjet printing method.

The thickness of the electron transport layer is not particularly limited, but is usually in the range of about 5 nm to 5 μm, preferably in the range of 5 to 200 nm. The electron transport layer may have a single structure composed of one or more of the above materials.

<Blocking layer>
Examples of the blocking layer include a hole blocking layer and an electron blocking layer, which are layers provided as needed in addition to the constituent layers of the organic functional layer unit 3 described above. For example, it is described in JP-A-11-204258, No. 11-204359, and page 237 of "Organic EL Element and Its Industrialization Frontline (November 30, 1998, published by NTS)". Examples include a hole blocking (hole block) layer.

The hole blocking layer has a function of an electron transporting layer in a broad sense. The hole blocking layer is made of a hole blocking material having a function of transporting electrons and a significantly small ability to transport holes, and recombination of electrons and holes by blocking holes while transporting electrons. The probability can be improved. In addition, the structure of the electron transport layer can be used as a hole blocking layer, if necessary. The hole blocking layer is preferably provided adjacent to the light emitting layer.

On the other hand, the electron blocking layer has a function of a hole transporting layer in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes and has a significantly small ability to transport electrons, and improves the recombination probability of electrons and holes by blocking electrons while transporting holes. Can be made to. In addition, the structure of the hole transport layer can be used as an electron blocking layer, if necessary.

Each blocking layer according to the present invention can be formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet printing method, and an LB method. In the method for producing an image display member of the present invention, a method of forming a blocking layer by using a wet coating method in the formed bank is preferable, and further, the wet coating method is preferably an inkjet printing method.

The layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.

(Cathode: 2nd electrode)
The cathode (second electrode) is an electrode film that functions to supply holes to the organic functional layer unit, and a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof is used. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TIO Examples thereof include oxide semiconductors such as ₂ and SnO _2.

The second electrode can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering. The sheet resistance as the second electrode is several hundred Ω / sq. The following is preferable, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 to 200 nm.

When the organic EL element is of the top emission method in which the emitted light L is extracted from the second electrode side, a forming material having good light transmission as described in the first electrode is selected, and the second electrode is used. Should be formed.

[Sealing member]
Next, the sealing member constituting the light emitting device of the present invention will be described.

In the first sealing layer 9 and the second sealing layer 10 shown in FIGS. 1 and 2, since the light emitting layer forms non-light emitting parts such as dark spots and shrinks due to moisture, it is for blocking moisture and oxygen. It is a functional layer. The optical characteristics such as the transmittance required for the sealing member vary depending on whether the light emitting layer is a bottom emission type or a top emission type.

Normally, the performance of the sealing layer is such that the water vapor transmission rate (environmental conditions: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is about 0.01 g / (m ² · day) or less, and oxygen permeation. A transparent insulating film having a degree of about 0.01 cm ³ / (m ² · day · atm) or less, a resistivity of 1 × 10 ¹² Ω · cm or more, and a gas barrier property is preferable. In particular, the oxygen permeability is 0.0001 cm ³ / (m ² · day · atm) or less, and the water vapor transmission rate is about 0.0001 g / (m ² · day) or less. It is preferably composed of a barrier-type multilayer film. The "water vapor permeability" is a value measured by an infrared sensor method based on JIS (Japanese Industrial Standards) -K7129 (1992), and the "oxygen permeability" is JIS-K7126 (1987). It is a value measured by a coulometric method based on (year).

As the material for forming the sealing layer described above, any material can be used as long as it is a material that causes deterioration of the organic light emitting layer and can suppress the infiltration of gas such as water or oxygen into the organic light emitting layer.

For example, the composition of the first sealing layer includes, for example, silicon oxide, silicon nitride, silicon nitride, silicon carbide, silicon carbide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, niobium oxide, molybdenum oxide and the like. It can be composed of a film made of an inorganic material. In the organic light emitting layer, the sealing layer is composed of an inorganic material coating containing a silicon compound such as silicon nitride or silicon oxide as a main raw material in consideration of gas barrier property, transparency, splitting property at the time of division, and the like. Is preferable.

In order to improve the brittleness of the sealing layer, not only the above-mentioned inorganic material coating, but also a coating made of a composite material with an organic material or a hybrid coating obtained by laminating these coatings may be formed together. good. In this case, the stacking order of the inorganic layer made of the inorganic material and the organic layer made of the organic material is arbitrary, but even in the configuration of the organic layer / inorganic layer, a plurality of organic layers and the inorganic layers are alternately laminated. May be good.

This makes it possible to obtain a sealing layer having a good barrier function for avoiding damage to the organic light emitting layer due to moisture or oxygen.

As the second sealing layer 10 shown in FIGS. 1 and 2, a second sealing layer 10 that further blocks moisture may be provided on the upper layer of the first sealing layer 9. In particular, in the case of a bottom emission type organic EL panel, a color filter layer having moisture resistance is provided at a position facing the light emitting direction, so that optical characteristics such as metal foil (for example, alpet) can be obtained. It is preferable to form the second sealing layer 10 having a structure that does not need to be considered. Examples of the metal layer include aluminum foil, duralumin foil, titanium foil, copper foil, phosphor bronze foil, SUS304 foil, inverse foil, magnesium alloy foil, and mixed foils thereof. Normally, if these metal foil foils are thin, they have defects such as pinholes. Therefore, by making them thicker, it is possible to prevent these sealing defects. The preferable thickness is in the range of 5 to 50 μm, and it is possible to prepare a foil from which pinholes and defects of the metal foil have been removed.

As shown in FIGS. 1 and 2, Alpet 12 can also be applied as the second sealing layer 10. The alpette 12 has a structure in which an aluminum foil 13 is provided on a protective film 14.

Examples of the Alpet 12 which is a polyethylene terephthalate film on which aluminum 13 applicable to the present invention is deposited include Alpet 12/34 manufactured by Asia Aluminum Co., Ltd. and 9-100 (aluminum foil: 9 μm, PET) manufactured by Panac Co., Ltd. : 100 μm), 9-125K (aluminum foil: 9 μm, PET: 125 μm), 10-75 (aluminum foil: 10 μm, PET: 75 μm), 12-50 (aluminum foil: 12 μm, PET: 50 μm), 12-188 ( Aluminum foil: 12 μm, PET: 188 μm), 20-75 (aluminum foil: 20 μm, PET: 75 μm), 20-100 (aluminum foil: 20 μm, PET: 100 μm), 30-188 (aluminum foil: 30 μm, PET: 188 μm) ), "Alpet 1N30" manufactured by Tokai Toyo Aluminum Sales Co., Ltd., "Alpet 3025" manufactured by Fukuda Metal Co., Ltd., "ALPET 1025" manufactured by Daido Kako Co., Ltd. and the like.

[Surface protection film]
Further, in the present invention, a protective film having an insulating property may be arranged on the second sealing layer 10 for the purpose of ensuring the electrical insulating property in the opposite direction of the first sealing layer 9 and preventing trauma. preferable.

Specifically, a flexible resin film is preferable, for example, polyolefins such as polyethylene, polypropylene and cyclic olefin copolymer (COP), polyamide, polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and the like. Polyester, cellophane, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), triacetyl cellulose (TAC), cellulose esters such as cellulose nitrate, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol Polymer (EVOH), syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone (PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, fluororesin , Acrylic resins such as polymethylmethacrylate (PMMA), materials such as polyarylates, and resin films composed of derivatives thereof. Further, for example, a cycloolefin resin called Arton (registered trademark: manufactured by JSR Corporation) or Apel (registered trademark: manufactured by Mitsui Chemicals, Inc.) can also be used.

Further, the second sealing layer 10 and the first sealing layer 9 are preferably connected via the first adhesive layer 11, and examples thereof include a thermosetting resin and an ultraviolet curable resin. 2 When a metal foil such as alpette is applied to the sealing layer 10, a thermosetting resin is preferable, and since there is moisture intrusion from the bulk of the adhesive layer, the adhesive preferably delays the diffusion of water. It is preferable that the material contains such a material or a filler.

"Polarizer"
The organic EL element is caused by the work function of the electrode, and in order to efficiently output the emitted photons to the outside, especially in the bottom emission type organic EL element, a metal material such as Al, Ag, an alloy, or a laminate is used for the second electrode. In the top emission type, which is often used, a reflective electrode is formed in the lower layer such as ITO of the anode in order to efficiently output photons to the outside when forming the TFT. Therefore, when the organic EL panel is formed, external light is reflected. Therefore, it is common to attach a circularly polarizing plate to eliminate the external light reflection and express the black color of the non-light emitting portion. Also in the display device of the present invention, a circularly polarizing plate 20 is attached to the outside of the color filter unit 16 to display black.

The circularly polarizing plate may include a λ / 4 plate, and is not limited to a liquid crystal type or a film type. The circularly polarizing plate is attached to the color filter unit via an optical adhesive.

For details of the polarizing plate applicable to the present invention, for example, Japanese Patent Application Laid-Open No. 2013-097279, Japanese Patent Application Laid-Open No. 2013-156391, Japanese Patent Application Laid-Open No. 2014-240906, Japanese Patent Application Laid-Open No. 2016-018021 and Japanese Patent Application Laid-Open No. 2017- The contents described in Japanese Patent Application Laid-Open No. 11164 and the like can be referred to.

《Attachment of each component unit of the display device》
The color filter unit and the light emitting display unit D are bonded to each other via the second adhesive layer 15. The second adhesive layer 15 includes, for example, a thermosetting type in which fillers such as inorganic, organic, and hybrid are dispersed in an epoxy-based thermosetting resin, and a type in which a photoinitiator is contained and cured by UV light. You may use. The thickness is usually about 1 to 30 μm, and can be adjusted by the viscosity and the size of the contained filler. Further, it is preferable to make the material thinner to prevent moisture from entering from the side and to bond the materials without impairing the sealing function.

In the display device of the present invention, a bottom emission type organic EL type light emitting display unit is manufactured, and the display device 1 separately manufactures the color filter unit 16 and the light emitting display unit D as the second adhesive layer 15. It is bonded using a thermosetting adhesive.

From the viewpoint of preventing the intrusion of moisture from the end portion, it is preferable that the second adhesive layer 15 uses a thermosetting adhesive and contains a filler or the like to suppress moisture diffusion, and in the present invention, the second adhesive layer 15 is thermosetting to which they are applied. Uses mold adhesive.

Further, in the top emission type or the like, the color filter unit may be formed directly above the sealing layer after the sealing layer is formed by the CVD method or the like. In that case, a color filter unit is formed by applying a color filter layer to the upper layer of the sealing layer in a patterning manner by, for example, an inkjet method, and then forming a flattening layer according to the present invention by a spin method, an inkjet method, or the like. .. In that case, since it is not necessary to use a thermosetting adhesive, it can be easily determined that further improvement in reliability can be expected.

<< Display device >>
As the display device of the present invention, in addition to the organic light emitting element using the organic EL element described as the above typical example, an inorganic light emitting element or a color electronic paper can be used.

Further, it is preferable that the organic light emitting device is the organic electroluminescence device described above or a quantum dot-containing organic light emitting device.

Further, the inorganic light emitting element is preferably a quantum dot-containing inorganic light emitting element or a micro LED.

In the present invention, the details of the display device provided with the organic EL element as the light emitting element have been described, but as other display devices, as the quantum dot-containing organic light emitting element (QD-OLED), for example, Japanese Patent Application Laid-Open No. 2014- You can refer to the configurations described in Japanese Patent Application Laid-Open No. 077046, Japanese Patent Application Laid-Open No. 2014-07380, Japanese Patent Application Laid-Open No. 2014-078381, Japanese Patent Application Laid-Open No. 2017-101128, and the like.

Further, as the inorganic light emitting device (QLED) containing quantum dots, for example, the contents described in JP-A-2015-156637 and JP-A-2018-0782279 can be referred to.

Further, as the micro LED (μLED), the configurations described in Japanese Patent Application Laid-Open No. 2014-550762, Japanese Patent Application Laid-Open No. 2017-535966, Japanese Patent Application Laid-Open No. 2018-014481 and the like can be referred to.

Further, as the color electronic paper, it is described in JP-A-2016-170260, JP-A-2016-170313, JP-A-2016-167295, JP-A-2017-073554, JP-A-2018-059999 and the like. You can refer to the configured configuration.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, the indication of "parts" or "%" is used, but unless otherwise specified, it indicates "parts by mass" or "% by mass".

<< Manufacturing of display device >>
[Manufacturing of display device 1]
In a bottom emission type organic EL light emitting panel according to the following method, the color filter layer is formed of a colorant, and an organic metal oxide having a structure represented by the general formula (1) according to the present invention is used as a flattening layer. A display device 1 (the present invention) including the color filter unit 1 having the added configuration was produced.

[Manufacturing of organic EL unit]
(Preparation of the first base material)
As the first base material 2, as a film base material having a flexibility of 30 cm × 40 cm, a carrier glass having a t = 0.7 mm was spin-coated with a varnish having a thickness of 50 μm, and then post-baked at 200 ° C. for 20 minutes. By doing so, the first base material was prepared.

Next, the following polysilazane-containing coating liquid is applied onto the varnish substrate using a wire bar so that the average film thickness after drying is 300 nm, and heated in an atmosphere of a temperature of 85 ° C. and a humidity of 55% RH for 1 minute. Treated and dried. Next, it was held for 10 minutes in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.), and dehumidified to form a polysilazane-containing layer on the varnish substrate.

Next, the varnish substrate on which the polysilazane-containing layer was formed was fixed on the operating stage of the excimer irradiation device MECL-M-1-200 (manufactured by MD.com Co., Ltd.), and modified under the following modification treatment condition 1. Quality treatment was performed to form a polysilazane modified layer having a layer thickness of 300 nm as a gas barrier layer, and a first base material with a gas barrier layer was prepared.

<Preparation of coating liquid containing polysilazane>
As a polysilazane-containing coating solution, a 10% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, catalyst-free type, manufactured by Merck Group, Inc.) was prepared.

<Modification treatment conditions>
Irradiation wavelength: 172 nm
Lamp-filled gas: Xe
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between polysilazane-containing layer and light source: 1 mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiator: 0.5% by volume
Excimer lamp irradiation time: 5 seconds <Cleaning of the first base material>
Subsequently, the first base material with the gas barrier layer prepared above was cleaned by a wet cleaning method.

A detergent solution obtained by diluting an alkaline detergent to 5% by mass is heated to 60 ° C., the first base material is immersed in the detergent solution at 60 ° C., scrubbing is performed on the first base material, and the first base material is subjected to scrubbing. The attached foreign matter was removed. Subsequently, the first substrate was subjected to ultrasonic cleaning treatment, pure water rinsing, nitrogen gas blowing and IR (Infra Red) drying in that order. Next, UV (Ultra Violet) irradiation was performed on the first base material to remove organic substances adhering to the surface of the first base material. Subsequently, the first substrate was dried using an oven.

(Formation of TFT)
First, a SiO film was formed on the base layer by CVD to form a gate electrode, and then a gate insulating film, an a-Si: H film as a channel layer, and an n ⁺ a-Si: H film were formed at any time by the CVD method. ..

Then, it was processed into a desired shape pattern by dry etching.

Next, after forming the source electrode and the drain electrode, a passivation film is formed, and an a-Si TFT having an electrode width of 100 μm and a thickness of 200 nm, a channel width of W = 3 mm, and a channel length of L = 20 μm is used as a color filter described later. It was formed at a position corresponding to each color filter of the layer.

At the same time, the extraction electrode of the first electrode was formed using ITO to prepare a TFT unit.

(Formation of organic EL element)
Next, a white tandem organic EL element was formed on the first base material and the TFT unit.

In the fabrication of the TFT unit, ITO was used as a lead electrode for the organic EL element, and the ITO was formed as the first electrode (anode) in the organic EL element (OLED).

Then, according to the method described in paragraphs (0201) to (0219) in Examples of JP-A-2015-201508, the first hole transport layer / first light emitting layer / first electron transport layer / intermediate connector. An organic functional layer group (7) composed of a layer / a second hole transport layer / a second light emitting layer / a second electron transport layer was formed.

Next, aluminum was vapor-deposited to a thickness of 150 nm to form a second electrode (cathode). In the produced organic EL element, the light emitting layer was appropriately adjusted so that the CIE illuminant of the light emitting layer under the condition of emitting light without passing through the color filter according to the present invention is the same as the light emitting condition of the D65 standard light source. Further, as a method for forming each of the above layers constituting the organic EL element, the organic EL element was formed by using the inkjet printing method shown in FIG.

(Formation of first sealing layer)
Next, a silicon nitride film having a thickness of 500 nm was formed by a plasma CVD method by supplying silane gas and ammonia gas on the second electrode under a film forming pressure condition of 50 Pa as a sealing layer. 1 Sealing layer was used.

Specifically, the first base material formed up to the second electrode ^{is placed in a vacuum chamber reduced to 1 × 10 -4} Pa or less, the temperature of the first base material is adjusted to about 70 ° C., and the reaction gas is used. , SiH ₄ gas, NH ₃ gas, and H ₂ gas were introduced into the vacuum chamber at a ratio of 2: 1: 4, and the film was formed by a plasma CVD method having a high frequency power supply of 13.56 MHz while reducing the pressure to 50 Pa. .. Although the temperature of the first base material rises during film formation, the film was formed by controlling the temperature of the first base material while cooling it so as to reach 70 ° C. As a result, a first sealing layer composed of SiN having a thickness of 500 nm was formed.

(Formation of second sealing layer)
Next, a second sealing layer was formed. AlPET to which a thermosetting adhesive was applied was bonded onto the first sealing layer formed above. AlPET is for preventing moisture attack on the SiN film constituting the first sealing layer. In such bonding, an organic EL unit was formed by curing the thermosetting adhesive by performing a heat treatment at 100 ° C. for 30 minutes.

[Manufacturing of color filter unit 1]
(Preparation of second base material)
As the second base material, a 0.5 mm glass substrate (EagleXG manufactured by Corning Inc.) was alkaline-cleaned by the same cleaning method as applied when the first base material was produced, and then photosensitive polyimide (Merck & Co., Inc.) was used. Was applied by a spin coating method, and a ring was prebaked at 60 ° C. for 120 seconds. Next, the pattern was exposed in a photo step, developed with tetramethylammonium hydroxide (abbreviation: TMAH), and purely rinsed to form a bank having a color filter forming portion as an opening.

(Preparation of color filter layer 1)
Next, each colorant-containing ink solution prepared by the following method was applied to the prepared bank by an inkjet printing method to prepare a color filter layer 1 having red, green, and blue color filters.

1) Preparation of Colorant-Containing Ink A dispersion was prepared by kneading a red pigment (CI Pigment Red 177) in diethylene glycol monoethyl ether acetate (boiling point 210 ° C.) with a solid content of 20%. 15 parts of melamine resin (MW-22, manufactured by Sanwa Chemical Co., Ltd.) and 55 parts of diethylene glycol monoethyl ether acetate were mixed with 30 parts of this dispersion to prepare an ink for forming a red color filter. Similarly, a blue pigment (Pigment Blue 15) and a green pigment (Pigment Green 7) were used to prepare an ink for forming a blue color filter and an ink for forming a green color filter.

2) Formation of a color filter layer An inkjet printing device (manufactured by Seiko Instruments Inc.) equipped with an inkjet head (manufactured by Seiko Instruments) with a discharge rate of 12 pL and a nozzle resolution of 180 dpi is mounted on a glass substrate having a plurality of banks formed thereof. Using the contained ink, ink droplets of each color were ejected to form red, green, and blue color filters to prepare a color filter layer 1.

As a result of measuring the refractive index of each color filter according to the method described later, the refractive index was 1.7 in each case.

(Formation of flattening layer 1)
Next, a flattening layer 1 containing an organometallic oxide having a structure represented by the general formula (1) according to the present invention was formed on the color filter layer 1.

Specifically, a 10 mass% dehydrated tetrafluoropropanol (exemplified compound F-1) solution of _{titanium tetraisopropoxide (Ti (OiPr) 4} ) is placed in a glove box under a dry nitrogen atmosphere having a water concentration of 1 ppm or less. The solution was prepared, opened to the atmosphere at a humidity of 30% for 1 minute, and immediately returned to the glove box to prepare a sol-gel solution 1. As a result of measuring F / (C + F) represented by the formula (a) in the sol-gel solution 1 by the following method, it was 0.20.

The method for measuring F / (C + F) of the sol-gel solution 1 is shown below.

First, the sol-gel solution 1 is applied onto a silicon wafer to form a thin film. The formed thin film is subjected to elemental analysis by SEM / EDS (Energy Dispersive X-ray Spectroscopy: Energy Dispersive X-ray Analyzer) to measure the number of carbon atoms and fluorine atoms, and the value of the following formula (a) is obtained. rice field. A JSM-IT100 (manufactured by JEOL Ltd.) was used as the SEM / EDS apparatus.

Equation (a) F / (C + F)
Next, the sol-gel solution 1 was applied by an inkjet printing method under the condition that the dry film thickness was 10 μm, prebaked at 60 ° C. for 2 minutes, and then post-baked at 110 ° C. for 30 minutes. The flattening layer 1 was formed by irradiating with a low-pressure mercury lamp for 10 minutes to prepare a color filter unit 1. The refractive index of the formed flattening layer 1 was 1.9.

For the refractive index of the color filter layer 1 and the flattening layer 1, a separate constituent layer was formed by the same method as the formation conditions of each target layer, and a sample for measuring the refractive index was prepared. Next, using a spectrophotometer U-4100 (manufactured by Shimadzu Corporation), the specular reflectance of the incident light at an incident angle of 5 ° with respect to the normal direction of each layer was measured at a wavelength of 560 nm. Next, the refractive index was measured using the thin film calculation software "Essential Macleod" manufactured by SIGMA KOKI.

[Attachment of color filter unit 1 and organic EL unit]
Next, a second adhesive layer is formed on the flattening layer 1 of the produced color filter unit 1 using the thermosetting adhesive used for forming the second sealing layer of the organic EL unit, and then the organic EL is formed. After peeling off the carrier glass of the first base material of the unit by laser irradiation, the first base material surface of the organic EL unit whose varnish surface is exposed and the color filter unit 1 are bonded to each other for 30 minutes at 100 ° C. After heat treatment, the color filter unit 1 and the organic EL unit were bonded together.

[Giving a circularly polarizing plate]
Next, an optical film was prepared according to the methods described in paragraphs (0165) to (0167) of WO2014 / 091759, and then a circularly polarizing plate was prepared according to the following method.

(Making a polarizer)
A long polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched under the conditions of a stretching temperature of 110 ° C. and a stretching ratio of 5 times. The obtained film was immersed in an aqueous solution consisting of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. consisting of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. .. The obtained film was washed with water and dried to obtain an elongated polarizer having a thickness of 20 μm.

(Preparation of circularly polarizing plate)
The surface of the optical film produced by the above method to be bonded to the polarizer was subjected to alkali saponification treatment. Next, an optical film was attached to one surface of the elongated polarizing element via a fully saponified polyvinyl alcohol 5% aqueous solution as an adhesive. The bonding was performed by aligning the longitudinal direction of the polarizer with the longitudinal direction of the optical film so that the transmission axis of the polarizer and the slow axis of the optical film form 45 °.

On the other hand, Konica Minolta Tack Film KC4UA (manufactured by Konica Minolta Co., Ltd.) was prepared, and the surface to be bonded to the polarizer was subjected to alkali saponification treatment. Then, KC4UA (manufactured by Konica Minolta Co., Ltd.) was attached to the other surface of the polarizer via a fully saponified polyvinyl alcohol 5% aqueous solution in the same manner as described above. As a result, a circularly polarizing plate was obtained.

The circularly polarizing plate produced above was bonded to the back surface side of the second base material constituting the color filter unit via an adhesive layer to produce a display device 1.

[Manufacturing of display device 2]
In the production of the display device 1, the display device 2 was produced in the same manner except that the color filter unit 2 produced by the following method was used instead of the color filter unit 1.

[Manufacturing of color filter unit 2]
In the produced color filter unit 1, the color filter unit 2 was produced in the same manner except that the color filter layer 1 was changed to the following color filter layer 2 and the flattening layer 1 was changed to the following flattening layer 2. ..

(Preparation of color filter layer 2)
A 10 mass% dehydrated tetrafluoropropanol (exemplary compound F-1) solution of _{titanium tetraisopropoxide (Ti (OiPr) 4} ) is prepared in a glove box under a dry nitrogen atmosphere having a water concentration of 1 ppm or less, and the humidity is adjusted. The solution that was opened to 30% air for 1 minute and immediately returned to the glove box was designated as sol-gel solution 1.

Next, 10.0% by mass of a dispersion in which a red pigment (CI Pigment Red 177) was kneaded in the diethylene glycol monoethyl ether acetate (boiling point of 210 ° C.) with a solid content of 20% was added to the sol-gel solution 1. A sol / gel liquid for forming a red color filter layer containing a colorant was prepared by adding at a solid content concentration.

Similarly, the sol gel liquid 1 for forming a blue color filter containing a colorant is colored by using a blue pigment (Pigment Blue 15) and a green pigment (Pigment Green 7) as colorants in the sol gel liquid 1. A sol-gel solution for forming a green color filter containing an agent was prepared.

Next, each of the above sol-gel liquids was ejected onto the second base material by an inkjet printing method so as to have the pattern shown in FIG. 1 to form the color filter layer 2.

Specifically, first, a colorant-containing blue color filter layer-forming sol / gel solution is ejected onto a second substrate according to the inkjet printing method shown in FIG. 3, and prebaked at 60 ° C. for 2 minutes. After that, post-baking was performed at 110 ° C. for 30 minutes, and a low-pressure mercury lamp was irradiated for 10 minutes to form a _{color filter CF B1 containing a blue colorant having a layer thickness of 5 μm.} Next, a 0.5 μm space was provided so that the colorant-containing green color filter layer-forming sol / gel solution _{did not overlap the end of the formed blue colorant-containing color filter (CF B1} ), and an inkjet printing method was performed. After performing pre-baking at 60 ° C for 2 minutes, then post-baking at 110 ° C for 30 minutes, and then irradiating with a low-pressure mercury lamp for 10 minutes, a green colorant having a layer thickness of 6 μm. A color filter CF _G1 containing the above was formed. Similarly, the layer thickness to form a color filter CF _R1 containing a red colorant of 7 [mu] m, to form a color filter layer 2.

The refractive index of each of the color filters containing each of the formed colorants was 1.90.

(Preparation of flattening layer 2)
Next, on the formed color filter layer 2, a flattening layer 2 having a refractive index of 1.60 was applied using a polyester acrylate resin under the condition that the layer thickness after drying was 5 μm by a spin coating method. Drying was performed to form a flattening layer 2, and a color filter unit 2 was produced.

[Manufacturing of display device 3]
In the production of the display device 2, the display device 3 was produced in the same manner except that the color filter unit 3 produced by the following method was used instead of the color filter unit 2.

[Manufacturing of color filter unit 3]
In the produced color filter unit 2, the color filter unit 3 was produced in the same manner except that the color filter layer 2 was changed to the following color filter layer 3.

(Preparation of color filter layer 3)
A 10 mass% dehydrated tetrafluoropropanol (exemplary compound F-1) solution of _{titanium tetraisopropoxide (Ti (OiPr) 4} ) is prepared in a glove box under a dry nitrogen atmosphere having a water concentration of 1 ppm or less, and the humidity is adjusted. The solution that was opened to 30% air for 1 minute and immediately returned to the glove box was designated as sol-gel solution 1. The F / (C + F) represented by the formula (a) in the sol-gel solution 1 is 0.20.

Next, core-shell semiconductor quantum dots made of InP / ZnS as quantum dots emitting red light were added to the sol-gel solution 1 at a solid content concentration of 10.0% by mass, and a quantum dot-containing red color filter layer was added. A sol / gel solution for formation was prepared.

Similarly, in the sol-gel solution 1, 10.0% by mass of core-shell type semiconductor quantum dots composed of InP / GaP / ZnS as green emitting quantum dots and tri-n-octylphosphine as a surface modifier are added. 0.1% by mass of oxide (abbreviation: TOPO, manufactured by Kanto Chemical Co., Inc.) was added to prepare a sol-gel solution for forming a green color filter layer containing quantum dots.

Similarly, 10.0% by mass of core-shell type semiconductor quantum dots made of CdS / ZnS as blue emitting quantum dots and 0.1% by mass of TOPO as a surface modifier are added to the sol-gel solution 1. Then, a sol-gel solution for forming a blue color filter layer containing quantum dots was prepared.

Next, each of the above sol-gel liquids was ejected onto the second base material by an inkjet printing method so as to have the pattern shown in FIG.

Specifically, first, a sol-gel solution for forming a blue color filter layer containing quantum dots is ejected onto a second substrate according to the inkjet printing method shown in FIG. 3, and prebaking is performed at 60 ° C. for 2 minutes. after performs post-baked for 30 minutes at 110 ° C., and then by irradiating the low-pressure mercury lamp for 10 minutes, the layer thickness was formed a color filter CF _B2 containing quantum dots QD _B of the blue emission of 5 [mu] m. Then, the quantum dot-containing green color filter layer forming a sol-gel solution, a 0.5μm space so as not to overlap the end portions of the color filter CF _B2 containing quantum dots QD _B of the forming the blue light emitting The layer thickness is increased by providing, applying by an inkjet printing method, prebaking at 60 ° C. for 2 minutes, then post-baking at 110 ° C. for 30 minutes, and then irradiating with a low-pressure mercury lamp for 10 minutes. to form a color filter _{CF G2} containing the quantum dots QD _G green light of 6 [mu] m. Similarly, the layer thickness to form a color filter CF _R2 containing the quantum dots QD _R of red light 7 [mu] m, to form a color filter layer 3.

The refractive index of each of the color filters containing each of the formed quantum dots was 1.90.

[Manufacturing of display device 4]
In the production of the display device 3, the display device 4 was produced in the same manner except that the color filter unit 4 produced by the following method was used instead of the color filter unit 3.

[Manufacturing of color filter unit 4]
In the color filter unit 3 used for manufacturing the display device 3, the general formula according to the present invention is the same except that the flattening layer 2 is changed to the flattening layer 1 used for manufacturing the color filter unit 1. A color filter unit 4 containing an organic metal oxide having the structure represented by 1) in the color filter layer and the flattening layer was produced.

In the color filter unit 4, the refractive index of the color filter layer and the refractive index of the flattening layer are both 1.9, and light having a blue peak wavelength of 460 nm, a green peak wavelength of 550 nm, and a red peak wavelength of 640 nm. It was possible to form a color filter layer that maximizes the light extraction efficiency so that each of them strengthens each other.

[Manufacturing of display device 5]
In the production of the display device 4, the display device 5 was produced in the same manner except that the color filter unit 5 produced by the following method was used instead of the color filter unit 4.

[Manufacturing of color filter unit 5]
In the production of the color filter unit 4, a sol-gel solution for forming an organic metal oxide having a structure represented by the general formula (1) used in the color filter layer 3 and the flattening layer 1 is used as a titanium tetraisopropoxy. A color filter unit 5 was prepared in the same manner except that the solution (Ti (OiPr) ₄ ) was changed to a 10 mass% dehydrated octafluoropropanol (exemplified compound F-5) solution (sol-gel solution 2).

As a result of measuring F / (C + F) in the sol-gel solution 2 by the above method, it was 0.42, and the refractive index of each formed layer was 1.70.

Further, it was confirmed that the refractive index of the sol-gel liquid 1 was 1.9 and the refractive index of the sol-gel liquid 2 was 1.7, and the refractive index could be freely controlled by the amount of fluorine in the alcohol solvent. did it.

[Manufacturing of display device 6]
A display device 6 provided with a liquid crystal display device as a light emitting display unit was produced according to the following method.

[Manufacturing of color filter unit 6]
In the production of the color filter unit 1, the color filter unit 6 was produced in the same manner except that the color filter layer 6 was produced by the following method.

(Preparation of color filter layer 6)
As the second base material, the color filter layer 5 was produced in the same manner except that the black matrix was formed on a 0.5 mm glass substrate (EagleXG manufactured by Corning Inc.) by the photolith method.

As the black matrix material, a black matrix material manufactured by Toppan Printing Co., Ltd. was used and formed. The black matrix material was spin-coated on the second substrate, temporarily dried at a prebake temperature of 100 ° C. for 2 minutes, and then photopatterned in a photo process.

Then, development was carried out with 3% by mass tetramethylammonium hydroxide (abbreviation: TMAH), and pure water was rinsed. Then, post-baking was performed at 250 ° C. for 45 minutes to form a black matrix having a thickness of about 3 μm.

Next, a colorant-containing ink liquid was applied to the prepared black matrix by an inkjet printing method to prepare a color filter layer 6 having red, green, and blue color filters.

1) Preparation of Colorant-Containing Ink A dispersion was prepared by kneading a red pigment (CI Pigment Red 177) in diethylene glycol monoethyl ether acetate (boiling point 210 ° C.) with a solid content of 20%. 30 parts of this dispersion, 15 parts of melamine resin (MW-22, manufactured by Sanwa Chemical Co., Ltd.), and 55 parts of diethylene glycol monoethyl ether acetate were mixed to prepare an ink for forming a red color filter. Similarly, a blue pigment (Pigment Blue 15) and a green pigment (Pigment Green 7) were used to prepare an ink for forming a blue color filter and an ink for forming a green color filter.

2) Formation of color filter layer An inkjet printing device (manufactured by Seiko Instruments Inc.) equipped with an inkjet head (manufactured by Seiko Instruments) with a discharge rate of 12 pL and a nozzle resolution of 180 dpi on a glass substrate having a plurality of banks formed therein. Using the contained ink, each color ink droplet was ejected to form a color filter to prepare a color filter layer 6.

(Manufacturing of liquid crystal display device)
The color filter is peeled off from the liquid crystal cell constituting the BRAVIA KDL-46HX800 manufactured by Sony Corporation according to the method described in paragraphs (0232) to (0261) of Examples of JP2012-230154A. Instead, the display device 6 was manufactured in the same manner except that the color filter unit 6 manufactured above was mounted.

[Manufacturing of display device 7]
In the production of the display device 1, the display device 7 (organic EL display device) of the comparative example was produced in the same manner except that the color filter unit 7 produced by the following method was used instead of the color filter unit 1. ..

(Manufacturing of color filter unit 7)
In the color filter unit 1 used for manufacturing the display device 1, the general formula according to the present invention is the same except that the flattening layer 1 is changed to the flattening layer 2 used for manufacturing the color filter unit 2. A color filter unit 7 composed of a color filter layer and a flattening layer containing no organic metal oxide having the structure represented by 1) was produced.

[Manufacturing of display device 8]
An organic metal having a structure represented by the general formula (1) according to the present invention is similarly produced except that the produced color filter unit 7 is used instead of the color filter unit 6 in the production of the display device 6. A color filter unit 7 composed of a color filter layer and a flattening layer containing no oxides was produced, and a display device 8 (liquid crystal display device) of a comparative example was produced using the color filter unit 7.

<< Evaluation of display device >>
The following evaluations were performed on each of the above-produced display devices.

[Evaluation of initial appearance]
With a current applied to each display device so that the initial emission brightness was 300 cd / m ² , the brightness, pixel shrinkage, and the presence or absence of dark spots were visually observed, and the initial appearance was evaluated according to the following criteria. ..

The emission brightness was measured using a spectral radiance meter CS2000 (manufactured by Konica Minolta).
◯: High brightness, no pixel shrink or dark spots are observed Δ: Light emission brightness is slightly low, weak pixel shrinks or dark spots are observed in some areas, but there is no problem in practical use ×: Light emission The brightness is low, and pixel shrink and dark spots are observed, which is a practical problem.

[Measurement of initial brightness]
For each display device, the front luminance was measured using a spectral radiance meter CS2000 (manufactured by Konica Minolta) in an environment of 23 ° C., and the front luminance of the display device 7 was displayed as a relative luminance of 1.00. Moreover, the initial brightness was evaluated according to the following evaluation ranks.
⊚: Brightness value in which the initial brightness value is + 10% or more than the normal design value ○: Brightness value in which the initial brightness value is + 5% or more and less than + 10% than the normal design value −: The initial brightness value is 300 cd than the normal design value Luminance value of / m ² or more and less than + 5% ×: Luminance value whose initial brightness value is less than ^{300 cd / m 2 than the normal design value}

[Evaluation of light resistance]
The light resistance test was performed with a sample size of 3 (n = 3), a carbon arc test was performed in an environment with a black panel temperature of 65 ° C. and 55% RH according to a method compliant with JIS D 0205, and a color was subjected to UV light irradiation. Since the moisture from the filter unit diffuses and damages the light emitting element, the light emission unevenness, bright spots, blind spots, dark spots, etc. at the time of light emission were visually observed, and the light resistance was evaluated according to the following criteria.
⊚: No uneven emission, bright spots, or dark spots are observed at all of n = 3. ○: No uneven emission, bright spots, or dark spots are observed at n = 2. Δ: When n = 2, weak occurrence is observed in one of the light emission unevenness, bright spot, and dark spot, but there is no practical problem. ×: In the sample of n = 1 or more, light emission unevenness, bright spot, Of the dark spots, strong occurrence of two or more items was observed, and there is a practical problem.

[Evaluation of high temperature and high humidity resistance]
After each display device is left for 500 hours in a high temperature and high humidity environment of 90% RH at 60 ° C. with a sample number of 3 (n = 3), there are uneven emission, bright spots, blind spots, and dark spots during light emission. The resistance to high temperature and high humidity was evaluated according to the following criteria by visually observing the above.

⊚: No uneven emission, bright spots, or dark spots are observed at all of n = 3. ○: No uneven emission, bright spots, or dark spots are observed at n = 2. Δ: When n = 2, weak occurrence is observed in one of the light emission unevenness, bright spot, and dark spot, but there is no practical problem. ×: In the sample of n = 1 or more, light emission unevenness, bright spot, Of the dark spots, strong occurrence of two or more items was observed, and there was a practical problem. The results obtained as described above are shown in Table I.

As is clear from the results shown in Table I, there was no problem with any of the display elements regarding the initial light emission characteristics related to the basic quality of the display device.

Further, in the brightness improvement represented by the initial brightness, the initial brightness is higher in all of the display devices 1 to 5 of the present invention as compared with the display device 7 which is a comparative product, and the light extraction efficiency due to the high bending rate is improved. You can see that. Further, in the display device 6 which is a liquid crystal display device type, the brightness is improved as compared with the display device 8 which is the comparison, and the contrast ratio of 1.1 times or more can be obtained from the viewpoint of the contrast ratio. I was able to confirm.

Further, in this evaluation, the life test as a display device is not carried out, but it is also clear that the life of the light emitting element itself under the same brightness is improved because the light extraction efficiency is improved. ..

In the evaluation of light resistance, dark spots were generated in the display device 7 which is a comparative example, but it is presumed that there was a defect in the barrier sealing and DS was generated by the invasion of water from the same part. .. In the display device 7, the dark spot generation rate was about 2% in terms of the light emitting area and the DS area ratio, and it was found that the same degree of defects were generated. Conventional color filters and conventional flattening films contain a large amount of water, which is released by a light resistance test and propagates to the light emitting element through the same defect. Further, in the display device 8 which is a liquid crystal display system, the occurrence of shrinks and dark spots was observed.

Although not described in this embodiment, the same applies to the top emission type, and the cause of the defect is often a foreign substance mainly composed of foreign adhesions, and the occurrence is almost the same regardless of whether it is a substrate or a seal. Since it is a rate, it is estimated that TFE, which is a recent sealing technology, has a similar defect occurrence rate. Therefore, it is presumed that the quality defect caused by moisture due to the same defect regardless of whether the light emission method is bottom emission or top emission is improved by the trap function of water molecules by molecular conversion.

Next, as a forced damage evaluation due to the moisture held by the color filter unit, a high temperature and high humidity test at 60 ° C. and 90% RH is carried out. It was occurring. Specifically, in the display device 6, when the number of samples is 3, dark spots were generated in an area of about 3% in the plane in all the samples.

Similarly, in the display device 7, shrinkage occurs and moisture is propagated from the color filter, but moisture permeates from the panel edge of the optical adhesive or the flattening film of the color filter, and the moisture is oversaturated. It is presumed that the water is diffused toward the substrate without being trapped by the color filter, causing shrinkage.

On the other hand, in the display devices 1 to 5 (organic EL panel) to which the color filter unit having the configuration specified in the present invention is applied, the color filter or the flattening film absorbs water, so that the water reaches the light emitting layer. However, it was found that an organic EL panel that does not shrink can be obtained. Further, the light extraction efficiency is also improved as compared with the comparative example, and it is clear that the refractive index can be controlled.

In the display device of the present invention, the water content generated from the color filter layer is considered to be 1000 ppm or more, but the color filter layer or flatness containing an organic metal oxide having a structure represented by the general formula (1). It is considered that the chemical layer undergoes molecular conversion and adsorbs water molecules, so that it is possible to prevent the permeation of water into the organic light emitting layer.

Further, in the display device 3, a color filter layer having a molecular conversion function can be produced even in a color filter layer containing an organic metal oxide having a structure represented by the general formula (1) by applying quantum dots. As a result, it was confirmed that even a color filter material using quantum dots with inferior water resistance can suppress deterioration and can produce a color filter unit with improved quality.

Further, in the above embodiment, evaluation and verification are mainly performed using an organic EL panel and a liquid crystal display device, but the same effect can be obtained with other types of display devices, particularly electronic devices using organic materials. It is clear that this is also effective, for example, in electronic devices using QD-OLEDs, QLEDs, and OTFTs, electronic papers and electronic devices using microcapsules, and micro LEDs using color filters.

The display device of the present invention is a high-quality display device having high light extraction efficiency and improved light resistance and moisture heat resistance, and can be suitably used for organic light emitting elements, inorganic light emitting elements, color electronic paper and the like.

1 Display device 2 1st base material 3 TFT unit 4 TFT
5 1st electrode 6 Drawer electrode 7 Organic functional layer group 8 2nd electrode 9 1st sealing layer 10 2nd sealing layer 11 1st adhesive layer 12 Alpet 13 Aluminum foil 14 Protective film 15 2nd adhesive layer 16, 16A , 16B Color filter unit 17 2nd base material 18 Color filter layer 19 Flattening layer 20 Plate plate 22 Hole injection layer 23 Hole transport layer 24 Light emitting layer 25 Electron transport layer 26 Electron injection layer 31, 39 Pump 32 Filter 33 Piping Branch 34 Waste liquid tank 35 Control unit 36, 37, 38A, 38B Tank CF _R1 , CF _G1 , CF _B1 , CF _R2 , CF _G2 , CF _B2 , F color filter D light emission display unit, organic EL unit LA light emission area _LR , L _{G, L B} emitting light OLED organic EL element _{QD R,} QD G, QD _B quantum dot TFT TFT unit

Claims (13)

A display device including a color filter unit, wherein the color filter unit is composed of at least a base material, a color filter layer, and a flattening layer, and the color filter layer or at least one layer of the flattening layer is described below. A display device containing an organic metal oxide having a structure represented by the general formula (1).
General formula (1) R- [M (OR ₁ ) _y (O-) _xy ] _n- R
(In the formula, R represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group, where R represents fluorine as a substituent. It may be a carbon chain containing an atom. M represents a metal atom. OR ₁ represents a fluorinated alkoxy group. X represents the valence of the metal atom, and y represents an arbitrary integer between 1 and x. Represents the degree of polycondensation.) The display device according to claim 1, further comprising a light emitting layer. The value of the ratio of fluorine atoms to the total number of carbon atoms and fluorine atoms of the organometallic oxide contained in the color filter layer or the flattening layer satisfies the condition defined by the following formula (a). The display device according to claim 1 or 2.
Equation (a) 0.05 ≤ F / (C + F) ≤ 1.00 According to any one of claims 1 to 3, wherein the metal atom (M) contained in the organometallic oxide is Ti, Zr, Sn, Ta, Fe, Zn, or Al. The display device described. The display device according to any one of claims 1 to 4, wherein the refractive index of the flattening layer is in the range of 1.6 to 1.9. The display device according to any one of claims 1 to 5, wherein the absolute value of the difference in refractive index between the flattening layer and the color filter layer is less than 0.1. The display device according to any one of claims 1 to 6, wherein the color filter unit contains quantum dots. The display device according to any one of claims 1 to 7, wherein the display device is an organic light emitting element, an inorganic light emitting element, or color electronic paper. The display device according to claim 8, wherein the organic light emitting element is an organic electroluminescence element or a quantum dot-containing organic light emitting element. The display device according to claim 8, wherein the inorganic light emitting element is a quantum dot-containing inorganic light emitting element or a micro LED. A method for manufacturing a display device, which manufactures a display device including the color filter unit according to any one of claims 1 to 10.
A method for manufacturing a display device, which comprises forming a color filter layer constituting the color filter unit by using a mixed solution of a metal alkoxide or a metal carboxylate and a fluoroalcohol. The method for manufacturing a display device according to claim 11, wherein the color filter layer is formed by a wet coating method. The method for manufacturing a display device according to claim 12, wherein the wet coating method is an inkjet printing method.

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