JP2005224662A - Applicator, application method, coated substrate applied by the method and base material for display using the substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an application method and an applicator permitting application of a resin to improve quality of gas barrier surfaces, surfaces producing dark spots, heat-resistant surfaces, etc. so as to allow plastic boards to be used as supporting boards for light emitting elements composed of organic ELs. <P>SOLUTION: The applicator is for applying a coating material comprising a conductive resin to a substrate to be applied with in the form of mist, has a holding and rotating section holding and rotating the substrate, an applying section supplying a conductive coating material in the form of mist, an exhausting mechanism and a voltage-supplying source to apply a voltage necessary to form an electric field between the applying section and the holding and rotating section, and is grounded. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a coating method for coating a coating material on a substrate to be coated in the form of a mist, and an apparatus therefor, and in particular, a coating method and device for forming a gas barrier dense film on a display substrate. About.

In recent years, display display devices are increasingly required to be large and improve image quality, and various developments and improvements have been made to liquid crystal, plasma, and organic EL methods.
Under such circumstances, a gas barrier base material that uses a glass substrate as a support substrate for a display element and requires a gas barrier property is known.
However, since the glass substrate used is disadvantageous in that it is heavy, hard and fragile, it has been proposed to use a plastic substrate instead of the glass substrate in order to solve these problems.
However, plastic substrates are light, flexible, and difficult to break, but have poor gas barrier properties compared to glass substrates, and it is difficult to maintain the performance of display elements for a long time. As a result, there is a problem that the light emitting element comes into contact with moisture or oxygen to cause light emission deterioration.
For this reason, in the case of using a plastic substrate, it is necessary to improve the gas barrier property.

In addition, if the flatness of the display substrate is insufficient, there are pinholes, protrusions, etc., resulting in defects in gas barrier properties. As a result, dark spots are generated in the organic EL display. When applied as a support substrate, there is also this problem.
In general, when an organic EL element is provided, since it is necessary to go through a process step at a high temperature, it must be heat resistant. However, when a plastic substrate is applied as a support substrate for an organic EL light emitting element, Has a problem of heat resistance, and when the display itself is installed and used for a long time, it is affected by potential and temperature rise, so a plastic substrate is used as a support substrate for organic EL light-emitting elements. In this case, it is difficult to say that the display is stable in terms of light emission and generation of light modulation.

On the other hand, conventionally, the following proposals have been made in order to impart gas barrier properties to the resin substrate.
For example, Japanese Patent Application Laid-Open No. H7-16491 (Patent Document 1) provides an inorganic vapor deposition layer as a first layer on a substrate made of a polymer resin composition, and then (a) one or more types of alkoxide and / or its By applying a coating agent mainly composed of a hydrolyzate or (b) tin chloride or a water / alcohol mixed solution, followed by heating and drying, and laminating as a second layer a gas barrier coating. High gas barrier properties are expressed.
JP-A-7-268115 (Patent Document 2) provides an inorganic vapor deposition layer as a first layer on a substrate made of a polymer resin composition, and then (a) one or more alkoxides or hydrolysis thereof. By applying a coating agent mainly composed of a mixed solution of a product and an isocyanate compound having at least two or more isocyanate groups in the molecule, and then heating and drying the gas barrier film as a second layer. Expresses gas barrier properties.
Japanese Patent Application Laid-Open No. 11-222508 (Patent Document 3) discloses that heat resistance and mechanical properties can be obtained by including a component containing an alicyclic hydrocarbon skeleton bis (meth) acrylate, a mercapto compound, and a monofunctional (meth) acrylate. By providing an inorganic vapor-deposited layer made of silicon oxide on a substrate excellent in mechanical strength, particularly impact resistance, gas barrier properties are expressed.
Japanese Patent Laid-Open No. 7-164591 JP 7-268115 A However, Japanese Patent Application Laid-Open No. 7-164591 (Patent Document 1) and Japanese Patent Application Laid-Open No. 7-268115 (Patent Document 2) are limited in the packaging field of foods, pharmaceuticals, and the like. Further, the gas barrier property is such that the water vapor transmission rate (hereinafter referred to as WVTR) is about 0.1 g / m 2 / day, the oxygen transmission rate (hereinafter referred to as OTR) is about 0.3 cc / m 2 / day · atm, and JP-A-11-222508. In the publication (Patent Document 3), although there is a field of application in the display field, particularly in a liquid crystal display panel, gas barrier properties are expressed by providing an inorganic vapor deposition layer made of silicon oxide on a substrate. However, it is difficult to say that the moisture resistance is sufficient to prevent deterioration of a light emitting element such as an organic EL.

Conventionally, as a general coating method (hereinafter also referred to as application method) for coating a material (hereinafter also referred to as application method), a coating method and an apparatus by a spin coating method, a spray method, a blade coating method, a dip method, etc. are used as an apparatus. Are known.
For example, Japanese Patent Application Laid-Open No. 2002-264274 (Patent Document 4) describes a method of producing a laminated film by coating a material by spin coating, gravure coating, roll coating, or the like.
Japanese Patent Application Laid-Open No. 9-239297 (Patent Document 5) describes the coating of a vehicle body by spray coating, and in particular, the application to a vehicle body of a coating by electrostatic coating using a rotary atomization method. Describes a coating method under conditions where no electric field is formed.
Furthermore, JP-A-2002-105887 (Patent Document 6) mentions a paper container or the like by electrostatic coating by spray coating.
Here, the application of an electrostatic coating by forming an electric field describes the coating on a paper container.
JP 2002-264274 A JP-A-9-239297 As described above, as a method for coating a substrate, a spray coating method and an electrostatic coating method in which a potential is applied between the substrate and the material supply unit are known. However, in these methods, when a gas barrier material is formed on a plastic substrate as a support substrate for supporting a display element such as an organic EL element as described above, the film thickness is not uniform and is dense and uniform. It was not suitable as a coating method requiring a good quality film.

As described above, recently, the plastic substrate is also considered to be applied as a support substrate for an organic EL light emitting device. In this case, however, it is necessary to improve the gas barrier property, and a gas barrier material is applied to the surface of the plastic substrate. Even if the gas barrier property is improved by coating, the conventional coating method has no problem with a method of obtaining a dense film having a uniform film thickness that can withstand organic EL, and this has been a problem.
The present invention is corresponding to this, and in order to be able to apply a plastic substrate as a support substrate of an organic EL light emitting element, a gas barrier property surface, a dark spot generation surface, a heat resistance surface are included. Thus, an object of the present invention is to provide a coating method and a coating apparatus capable of coating a resin for improving quality.

  The coating device of the present invention is a coating device for applying a coating material made of a conductive resin in the form of a mist to a substrate to be coated, a holding rotating unit that holds and rotates the substrate to be coated, and A coating unit that supplies conductive coating material in the form of a mist, an exhaust mechanism, and a voltage supply source for applying a voltage necessary to form an electric field between the coating unit and the holding rotating unit. And further grounding.

The coating method of the present invention is a coating method for applying a coating material made of a conductive resin in the form of a mist onto a substrate to be coated, and is applied to a holding rotating unit that holds and rotates the substrate to be coated. With the coating substrate mounted and rotated, the conductive coating material is supplied in the form of a mist from the coating unit while being evacuated and applied, and a voltage is applied between the coating unit and the holding rotating unit. Then, the coating is performed.
And in the above application method, the voltage applied between the application part and the holding rotation part is:
It is a DC voltage or an AC voltage.
In addition, any one of the application methods described above is characterized in that either one of the application unit and the holding rotation unit is grounded.
In any of the above application methods, the resistance value of the application material is 1 × 10 ⁶ Ω · cm or less.

The coated substrate of the present invention is characterized in that the coating material is coated on the coated substrate by the coating method according to any one of claims 2 to 5.
And it is said application | coating base material, Comprising: A to-be-coated base material is any one of a film, a glass substrate, a wafer substrate, or these workpieces.
In addition, any one of the above-described coating base materials is characterized in that it has a gas barrier property having a water vapor barrier property and an oxygen barrier property by application of a coating material.
Further, in any one of the above-described coated substrates, the surface portion has a center line average roughness Ra (JISB0061) of 2 nm or less, and a mountain-valley is 20 nm or less. .
In addition, any one of the above-described coated substrates, which is used for a display.

The display substrate of the present invention is characterized in that a transparent conductive layer is provided on the coating material of the coating substrate described in claim 9.
Alternatively, the display substrate of the present invention comprises a transparent electrode layer, an organic EL light emitting element forming layer, and a counter electrode, which are patterned in order on the coating material of the coating substrate according to claim 9. It is an organic EL display element that is disposed.
Alternatively, the display substrate of the present invention comprises a transparent electrode layer, a liquid crystal display element forming layer, and a counter electrode, which are sequentially patterned on the coating material of the coating substrate according to claim 9. The liquid crystal display device is provided for use in a liquid crystal display device.

(Function)
The coating apparatus of the present invention has such a configuration, and in particular, a plastic substrate can be applied as a support substrate for an organic EL light emitting element. It is possible to provide a coating apparatus capable of performing a coating method capable of coating a resin for improving quality in terms of generation, heat resistance, and the like.
Specifically, it is a coating apparatus for applying a coating material made of a conductive resin in the form of a mist to a substrate to be coated, the holding rotating unit for holding and rotating the substrate to be coated, and a conductive material An application part for supplying the application material in a mist form, an exhaust mechanism, and a voltage supply source for applying a voltage necessary to form an electric field between the application part and the holding rotation part, This is achieved by further grounding.
Of course, the substrate to be coated is not limited to a plastic substrate, and may be a glass substrate or a wafer substrate.

In the coating method of the present invention, specifically, a plastic substrate can be applied as a support substrate for an organic EL light-emitting element by adopting such a configuration. It is possible to provide a coating method capable of coating a resin for improving the quality in terms of dark spot generation and heat resistance.
In the present invention, when a gas barrier substrate having a high gas barrier property has been intensively studied, a state in which a voltage is applied between the coating portion and the holding rotating portion in order to apply a predetermined coating material to the substrate to be coated. The coating material made of conductive resin is supplied in the form of a mist and applied to the substrate to be coated. Further, by rotating the substrate to be coated, the denseness, adhesion, and covering properties of the film As a result, it was found that a uniform coating can be achieved.
Specifically, it is a coating method for applying a coating material made of a conductive resin in the form of a mist to a substrate to be coated, and a substrate to be coated on a holding rotating unit that holds and rotates the substrate to be coated. The conductive coating material is supplied in the form of a mist from the coating unit while being exhausted in a rotated state, and a voltage is applied between the coating unit and the holding rotating unit. This is achieved by applying.
As a voltage applied between the coating unit and the holding rotating unit, a DC voltage or an AC voltage of a predetermined voltage is used depending on the conductivity of the coating material, and usually either the coating unit or the holding rotating unit is grounded. .
The reason for grounding is that insufficient grounding not only reduces the electrostatic effect, but also has a risk of fire from the contact area.
The magnitude of the voltage is about 40-100KV.

In the coating method of the present invention, the reason why a film with good denseness and good adhesion can be formed is not clear, but by applying a voltage to charge the droplets in a fog state, it is also possible to apply to the holding rotating part. By applying while exhausting in a state where the substrate is mounted and rotating, a film is formed by droplets in a high energy mist state, so that the film has good denseness and good adhesion It is considered that.
Since the coating material made of resin (coating resin) has electrical conductivity, the droplets of the mist-shaped coating material are charged and receive an electrostatic force in the direction of the electric field. The film thickness distribution is improved.
As a result, the gas barrier property and flatness of the substrate to be coated are improved.
Further, the resistance value of the coating material is determined from the adhesion efficiency in which the coating material is charged and applied without being exhausted by exhaust gas, and is preferably 1 × 10 ⁶ Ω · cm or less.

With this configuration, the coated substrate of the present invention can provide a coated substrate in which a film excellent in terms of denseness, adhesion, and covering properties is formed on the surface portion of the coated substrate. It is said.
Examples of the substrate to be coated include a film, a glass substrate, a wafer substrate, and any one of these workpieces.
The roughness of the surface portion of the coated substrate can be 2 nm or less and the peak-valley can be 20 nm or less in terms of centerline average roughness Ra (JISB0061).
Specifically, a coating substrate that is a gas barrier property having a water vapor barrier property and an oxygen barrier property by application of a coating material for a display.

Moreover, as the base material for display of this invention, what provided the transparent conductive layer on the coating material of the coating base material of Claim 9 is mentioned.
More specifically, a display for an organic EL display element, in which a transparent electrode layer, an organic EL light emitting element forming layer, and a counter electrode, which are patterned in order, are disposed on a coating material of a coating substrate. A display base for a liquid crystal display element, in which a transparent electrode layer, a liquid crystal display element forming layer, and a counter electrode are sequentially arranged on the base material for coating or the coating material of the coating base material Materials.

According to the present invention, the present invention relates to a display substrate such as a transparent touch panel, liquid crystal, inorganic electroluminescence (hereinafter EL) and organic EL, and a film substrate for packaging. It was possible to provide a gas-barrier laminated base material in which high gas barrier performance was imparted to the material.
And such a gas-barrier laminated base material shall be usable for a display use.
In particular, by using such a gas barrier laminate substrate, an organic EL display having a high gas barrier performance that can withstand a process step at a high temperature and further suppress the occurrence of dark spots is provided. It can be realized.
Furthermore, by applying the conductive resin by the coating method of the present invention, the coating liquid usage efficiency of the coating material (coating resin) is improved, the coating material can be saved, the cost can be reduced, and the working efficiency and working environment can be reduced. Get better.

Embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic configuration diagram of an example of an embodiment of a coating apparatus according to the present invention, and FIG. 2 is a diagram illustrating an example of a coating unit of FIG. 1, and FIGS. 3 (a) and 3 (b). FIG. 3 is a diagram showing a layer configuration of a coated substrate (also referred to as a gas barrier laminate substrate), and FIG. 3C and FIG. 3D are diagrams showing a layer configuration of a gas barrier laminate substrate using them. It is.
1, 2, and 3, 110 is an application unit, 110A is an atomization unit, 111 is a rotation unit (motor), 112 is a shaving nozzle, 112a is an air flow direction, 113 is a rotation shaft, and 114 is atomization. Head, 115 is an enclosure (housing), 116 is an air curtain nozzle, 116a is an air curtain, 120 is a holding rotating part, 125 is a rotating shaft, 130 is a voltage supply source, 135 is ground, 140 is a processing chamber, and 150 is ( A coating material (dropped), 180 is a substrate to be coated (or coated substrate), 310 is a film resin base material (hereinafter also referred to as a transparent resin film or a plastic substrate), and 320 is a resin layer (also referred to as a flattening layer). , 330 and 340 are transparent inorganic compound layers.

First, an example of an embodiment of a coating apparatus according to the present invention will be described with reference to FIG.
The coating apparatus of this example is a coating apparatus for applying a conductive coating material in the form of a mist to a substrate to be coated. Briefly, as shown in FIG. In addition, a voltage is applied between the holding rotation unit 120 that holds and rotates the substrate to be coated, the coating unit 110 that supplies the conductive coating material in the form of a mist, and the coating unit 110 and the holding rotation unit 120. The processing chamber 140 is provided with an exhaust port 141 for exhausting the exhaust gas over the entire periphery of the holding rotating unit 120.
In particular, this example is a coating apparatus used when forming a gas barrier film densely and with good adhesion on a glass substrate or film substrate for display.
In FIG. 1, a supply pipe for supplying the coating material to the coating unit 110, a tank for storing and supplying the coating material, and the like are omitted.

The coating apparatus of this example is a device for applying a coating material 150 made of conductive resin in the form of a mist to the surface of a substrate to be coated 180 mounted on a rotation holding unit. A predetermined voltage is applied between the holding rotating unit 120 and the atomizing unit 110A discharges and supplies the coating material 150 in the form of droplets.
The droplets of the coating material 150 released by the atomizing unit 110A are discharged in a charged state and applied to the surface of the substrate to be coated 180.
The atomizing unit 110A is a discharge electrode for charging droplets of the coating material to be atomized.
In addition, by applying a predetermined voltage between the coating unit 110 and the holding rotating unit 120 by the voltage supply source 130, an electric field is formed between the substrate to be coated 180 on the side grounded from the atomizing unit 110A. Is done.

The application unit 110 is provided with a mechanism for atomizing the application material and a mechanism for controlling the atomization state of the application material.
As the application part 110, the thing of a structure as shown in FIG. 2 is mentioned, for example.
The atomizing unit 110A supplies the coating material and atomizes it while rotating the atomizing head 114 by a rotating unit (motor), and is provided around the atomizing head 114 in the state of being atomized. The range of the atomization state is limited by air (or nitrogen or the like) from the shaving nozzle 112 and the air curtain nozzle 116 provided outside the shaving nozzle 112, and the drops of the outer mist-like coating material 150 Is controlled inside the thick dotted line 114a.
For example, the air flow direction 112a from the shaving nozzle 112 is as indicated by a one-dot chain line arrow, and the air flow direction from the air curtain nozzle 116 to the air curtain 116 is as indicated by a thick dotted line arrow.
In this case, the particle diameter of the atomized droplet depends on the rotation speed of the atomizing head 114.

The holding rotation unit 120 may be any member that can hold and rotate the substrate to be coated 180 with good flatness. In the case of a material such as a film substrate, it may be fixed using an adhesive or the like.
The voltage supply source 130 is for charging the droplets of the coating material to be atomized, and for forming an electric field between the atomized portion 110A and the substrate to be coated 180 on the side grounded. It is.
The voltage from the voltage supply source 130 for continuously charging the atomized droplets is the distance between the atomizing head 114 of the atomizing unit 110A that is a discharge electrode and the substrate to be coated 180 (or the holding rotating unit 120). Although it is determined in consideration of conditions such as the properties of the coating resin and the coating amount, the range of DC 40 KV to 100 KV is preferable.
In this example, the voltage supply source 130 is provided outside the application unit 110, but may be provided along with the application unit 110 side.
The processing chamber 140 is exhausted from the exhaust port 141 in a state of being blocked from outside air.

Next, an example of an embodiment of the coating method of the present invention will be briefly described with reference to FIG. The coating method of this example is a coating method in which a coating material made of a conductive resin is sprayed on one surface of the substrate to be coated 180 with the coating apparatus shown in FIG. The substrate to be coated 180 is mounted on the substrate 120, and in a rotated state, the conductive coating material 150 is supplied in the form of a mist from the coating unit 110 while being evacuated and coated. A voltage is applied to 120 to charge the coating material, and coating is performed in a mist state.
By charging the atomized droplets of the conductive coating material 150 and further holding and rotating the substrate to be coated 180 by the holding and rotating unit 120, the formed film is dense, excellent in adhesion, and has a surface coating. It can be applied uniformly within the substrate surface.
In the coating apparatus shown in FIG. 1, since a direct current voltage is applied between the coating unit 110 and the holding rotation unit 120, the holding rotation unit 120 is grounded, and the coating material (coating resin) has conductivity. In addition, the droplets of the mist-like coating material are charged, and the droplets are subjected to electrostatic force in the electric field flow direction. As a result, the conductive coating material (coating resin) 150 is applied to the substrate 180 to be coated. Adhesion is improved and film thickness distribution is also improved.
Further, by applying the conductive coating material in this way, the ratio of deposits of the mist-shaped coating material to the substrate to be coated 180 without being exhausted (this is also referred to as deposition efficiency here) is increased. be able to.
That is, the coating solution usage efficiency of the coating resin is improved, the coating resin is saved, the cost can be reduced, and the working efficiency and working environment are improved.

From the viewpoint that the mist-like coating material 150 is charged and the adhesion efficiency is good, the resistance value of the coating material 150 is preferably 1 × 10 ⁶ Ω · cm or less.
The roughness of the applied film can be 2 nm or less in terms of the average roughness Ra, and 20 nm or less in the mountain-valley.
The particle diameter of the coating material 150 to be atomized is determined from the adhesion efficiency (hereinafter also referred to as coating usage efficiency) of the coating material 150 to the substrate 180 to be coated. There is also a balance between the voltage between the coating unit 110 supplied from the source 130 and the holding rotating unit 120, the exhaust condition, and the like, and it is usually set in the range of 10 μm to 20 μmΦ.
The voltage between the coating unit 110 and the holding rotating unit 120 supplied from the voltage supply source 130 is also determined from the adhesion efficiency to the substrate 180 to be coated.
Note that the conductivity of the coating material 150 may be controlled by adding a conductive material.
The high voltage from the voltage supply source 130 for continuously charging the 150 atomized droplets of the coating material is generated by the atomizing head 114 of the atomizing unit 110A, which is a discharge electrode, and the substrate to be coated 180 (or holding rotation). Is determined in consideration of conditions such as the distance to the portion 120), the properties of the coating resin, and the coating amount, but a range of DC 40 KV to 100 KV is preferable.

Next, first, a coated substrate (hereinafter referred to as a gas barrier laminate substrate) obtained by the coating method of the present invention, and a substrate having various layer configurations using the coated substrate (also referred to as a gas barrier hereinafter). In addition, the layer structure and the like when these are used as a display substrate will be described. Further, a display substrate using such a gas barrier laminate substrate will be described. The actual production examples 1 to 4 of the base material such as materials and the comparative examples 1 to 8 corresponding thereto are given, and the base materials produced by these production examples and comparative examples are evaluated.
In addition, production examples 1 to 4 and comparative examples 1 to 8 are both conductive resins for improving the gas barrier property on the substrate to be coated by the above coating method using the coating apparatus shown in FIG. Was applied in an atomized form.

First, the example of the form of the application | coating base material (gas barrier laminated base material) obtained by the apply | coating method is given.
The first example has a layer structure shown in FIG. 3A, and is a resin layer made of a conductive resin or a conductive resin on one surface of a transparent resin film 310 as a supporting substrate. 320 is applied and formed.
The resin layer 320 flattens the protrusions and pinholes present in the transparent resin film 310, the oxygen permeability of the gas barrier substrate of the present invention is within 0.3 cc / m ² / day · atm, and the water vapor permeability is 0. It is possible to achieve a high gas barrier property so as to be within ³ g / m ² / day.
Such a resin layer 320 is also referred to herein as a planarization layer.
Since the coating substrate (gas barrier laminate substrate) having the layer structure shown in FIG. 3A of this example has a high gas barrier property as described above, it is moisture-proof and gas-resistant to the display element. Showing gender.
In particular, when the application base material (gas barrier laminate base material) of the first example is applied to an organic EL light emitting element that needs to avoid the intrusion of moisture and oxygen, the intrusion of moisture and oxygen is the cause. In addition, when a display is configured by providing an element on the coated substrate (gas barrier laminate substrate) of the first example, it can withstand process steps at high temperatures. And the occurrence of dark spots can be suppressed.

The second example has a layer structure shown in FIG. 3B, and a transparent inorganic compound layer 330 is provided on one surface of a transparent resin film 310 as a supporting substrate, and further, there is conductivity. A resin layer 320 made of a resin or a resin having conductivity is applied and formed.
In FIG. 3 (b), the transparent resin film 310 is the same as the transparent resin film 310, which is the support substrate having the basic layer structure in FIG. 3 (a), and is a transparent inorganic compound for the purpose of improving gas barrier properties. A layer 330 is provided, and a resin layer 320 is provided as a flattening layer for flattening on the transparent inorganic compound layer 330 by the coating method of the present invention.

As a modification of the coated substrate (gas barrier laminate substrate) of the first example and the coated substrate of the second example, the basic layer configuration shown in FIG. 3 (a) or FIG. 3 (b) above. In addition, various layers of the supporting substrate are added and a resin layer (corresponding to 320) is applied and formed by the coating method of the present invention, or in the layer configuration, other than the transparent resin film is used as the supporting substrate. And the like.
The illustration of the layer structure of said application | coating base material (gas barrier laminated base material) shows the example, and this invention is not limited by this.
Examples of modifications of the first example and the second example include various forms.

A gas barrier laminate substrate obtained by adding various layers using these coated substrates (gas barrier laminate substrates) can also be used.
For example, as necessary, as shown in FIG. 3C, a transparent inorganic compound layer 331 for preventing degassing is further provided on the resin layer 320 as a planarizing layer in FIG. Also good.
Further, for example, in the second example of the layer configuration of FIG. 3B, a transparent inorganic compound layer 340 is further provided on the resin layer 320 as the planarizing layer and the gas barrier property improving layer. Can be mentioned. (Fig. 3 (d))
In this case, the transparent inorganic compound layer 340 functions as a degassing prevention layer for containing degassing that may be generated from the resin layer 320 as a resin layer (flattening layer).
Alternatively, as another form example, in the basic configuration of the three-layer configuration pattern shown in FIG. 3B, the transparent inorganic compound layer and the planarization layer are further repeated n times on the resin layer 320 as the planarization layer. The thing of the form provided can also be mentioned.
In this case, the outermost surface layer is preferably a transparent inorganic compound layer in order to prevent degassing.
Practically, n is preferably 2 or 3.
Of course, in the above-mentioned coated substrate and gas barrier laminate substrate using the same, a layer structure in which an anchor layer, an overcoat layer, or another planarizing layer is added may be used as necessary.

When the gas barrier laminate substrates of the first example, the second example, and the modified examples are used as display substrates, a transparent conductive layer is usually provided on these gas barrier laminate substrates.
As a display substrate for an organic EL display, an organic EL light emitting element forming layer is provided on a transparent electrode layer formed by patterning the transparent conductive layer of the display substrate, and the organic EL light emitting element is further provided. A counter electrode is provided over the formation layer.

Next, each part (each layer) of the gas barrier laminate substrate of the present invention will be described.
<Supporting substrate made of resin>
In the gas barrier laminated substrate of the first example, the second example, or a modified example thereof using a transparent resin film as the supporting substrate, the supporting substrate is made of a transparent resin specified below, and the display As the base material for use, those having a linear expansion coefficient of 80 ppm or less and a total light transmittance of 85% or more are usually used.
The linear expansion coefficient in this specification is a sample having a width of 5 mm and a length of 20 mm, a constant load (2 g) is applied in the length direction, and the temperature range from 25 to 200 ° C. is 5 at the rate of temperature increase. This refers to the amount of dimensional variation measured in ° C / min.
The gas barrier laminate substrate of the first example, the second example, or a modification thereof using the transparent resin film 310 as the support substrate, or a gas barrier laminate substrate having various layer configurations using the same. By using the above, it is possible to satisfy the necessary conditions for the display substrate, further the organic EL display using the same, and the electronic component application.
That is, when a single film resin layer as a normal gas barrier substrate is used for these applications, the gas barrier substrate may be exposed to a process at about 200 ° C., and the transparent resin substrate in the gas barrier substrate may be exposed. When the linear expansion coefficient of the material film exceeds 80 ppm, the substrate dimensions are not stable when the gas barrier base material is passed through the temperature process, and the barrier performance deteriorates due to thermal expansion and contraction. Although the problem that the process cannot be endured is likely to occur, the gas barrier laminated base material of the first example, the second example, or the modified example using the transparent resin film as the holding base material of the present invention or When the gas barrier laminate substrate having various layers using this is used for display applications, the heat resistance is preferably 150 ° C. or higher, more preferably 200 ° C. or lower. , And most preferably it is realized at least 250 ° C..

As the transparent resin film 310 as the supporting substrate of such a gas barrier laminate substrate, a polar polymer having a cycloalkyl skeleton is preferably used, and a specific material is an acrylate having a cycloalkyl skeleton. -Too compounds or methacrylate compounds and their derivatives.
More preferably, a resin composition comprising a (meth) acrylate compound having a cycloalkyl skeleton (referred to herein as an acrylate compound or a methacrylate compound) having a cycloalkyl skeleton as shown in Patent Document 6 and a derivative thereof. Can be mentioned.
When such a gas barrier laminate substrate is a laminate having the aforementioned heat-resistant polar layer, the heat-resistant polar layer is preferably a polar polymer having a cycloalkyl skeleton, and further, It is desirable that the polar layer is a (meth) acrylate compound having a polarity or a derivative thereof.
For example, a methyl (meth) acrylate homopolymer or a copolymer obtained by polymerizing a mixture of methyl (meth) acrylate and another copolymerizable monomer having a vinyl group (this specification) (Meth) acryl in the book means acryl or methacryl.) Examples of copolymerizable monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, and 2, 2, 2-trifluoroethyl acrylate. , Methacrylates such as ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, vinyl compounds such as acrylonitrile and styrene, acid anhydrides such as maleic anhydride and itaconic anhydride, cyclohexylmaleimide And maleimide compounds such as phenylmaleimide.
These resins can be cured by ultraviolet (UV) irradiation.
In addition, one or more transparent resins other than the above resins (referred to as other transparent resins) are combined with the transparent resin film 310 as a supporting substrate of these gas barrier laminate substrates by bonding, etc. This can be used as a supporting substrate.
Examples of such other transparent resins include cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), and poly (meth) acrylic resins. Resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyurethane resins, fluorine resins, acetal resins, cellulose resins, polyether sulfone resins, etc. Various resin films or sheets such as can be used.

Further, instead of the film resin (transparent resin film 310) which is a support substrate of these gas barrier laminates, a support substrate of the gas barrier laminate (hereinafter also simply referred to as a substrate) is used on the transparent resin film. A filter provided with a color filter can be used.
The use of a color filter realizes full colorization by using a combination of a white light emitting layer and three color filters widely used in the field of liquid crystals.
When this color filter is used, for example, an RGB colored layer is formed by patterning on a light-transmitting substrate.
In addition, as said colored layer, a pigment and dye are generally used.
Corresponding to the RGB colored layer, an electrode is patterned, a white light emitting layer is formed so as to cover the electrode, and an electrode is further formed on the white light emitting layer to form an EL (electroluminescence) element. It can be a display device.
On the light emitting layer (EL layer) in this EL element, the said gas-barrier laminated base material can be laminated | stacked, and, thereby, deterioration of the light emitting property of an EL element, etc. can be suppressed.
As the support substrate for forming the transparent resin film (or sheet) 310 using the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and the extrusion method, cast molding method, T-die Method, cutting method, inflation method, other film-forming methods, film-forming each of the above-mentioned various resins alone, or multilayer co-extrusion using two or more types of various resins Using a method of forming a film, and further using two or more types of resin, and mixing and forming a film before forming a film, etc., a resin film or sheet of each layer is manufactured, and in addition, stretching is performed. When necessary, for example, by using a tenter method or a tubular method, it is possible to obtain and use various resin films or sheets obtained by stretching in a uniaxial or biaxial direction. .
In addition, the above-mentioned various resin films or sheets can be used together.

As mentioned above, when using a transparent resin film as a support base material, the thickness has preferable 10 micrometers-500 micrometers.
If the thickness is too thick, as the post-processing step proceeds, the impact resistance is inferior as in the case of glass.
On the other hand, if it is too thin, the mechanical suitability in the steps before and after the film formation is poor, and the gas barrier property against water vapor, oxygen gas, etc. is reduced.
In addition, when one or more of the above-mentioned various resins are used and the film is formed, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold releasability, flame retardancy, antifungal properties, electrical characteristics, strength, etc. Up to 10% can be arbitrarily added depending on the purpose.
In the above, as a general additive, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Further, an improving resin or the like can be used.

<Glass substrate>
As described above, instead of the film resin substrate as the support substrate of the gas barrier laminate substrate, a gas barrier laminate substrate using a transparent glass substrate can be mentioned.
In this case, as the transparent glass substrate, both alkali glass and non-alkali glass can be used.
When impurities are a problem, non-alkali glass such as Pyrex (registered trademark) glass is preferred.
Examples of the processed glass include a transparent glass substrate that has been applied or stepped.
The thing of the form which uses newly what provided the color filter on the glass substrate as a support base material as a support base material is also mentioned.
In this case, the use of a color filter realizes full color by using a combination of a white light emitting layer and three color filters widely used in the field of liquid crystal.
When this color filter is used, for example, an RGB colored layer is formed by patterning on a light-transmitting substrate.
In addition, as said colored layer, a pigment and dye are generally used.
Corresponding to the RGB colored layer, an electrode is patterned, a white light emitting layer is formed so as to cover the electrode, and an electrode is further formed on the white light emitting layer to form an EL (electroluminescence) element. It can be a display device.
Such a gas barrier laminate can be laminated on the light emitting layer (EL layer) in this EL element, and deterioration of the light emitting property of the EL element can be suppressed.
The thickness of the glass is preferably 30 μm to 2 mm, preferably 30 μm to 60 μm when used as a flexible substrate, and preferably 60 μm to 2 mm when used as a rigid substrate.
When a glass substrate is used as the support substrate, the gas barrier property is higher than when a resin substrate (film resin substrate) is used, but without using a glass substrate as a support substrate. The reason why the resin base material is applied to the gas barrier laminate base material is that the glass substrate used for such a display is used for gas permeation as the glass substrate becomes thinner and the organic EL display becomes more precise. This is because it has reached a situation where it cannot be ignored.
Here, as glass substrate materials, there are so-called soda glass, lead glass, hard glass, quartz glass, liquid crystal glass, etc. ("Chemical Handbook", Basic edition, P.I-537, The Chemical Society of Japan). ), Silicate glass containing strontium (St) or barium (Ba) is preferably used as the CRT, and alkali-free glass is preferably used in the liquid crystal display device, but the present invention is not limited thereto.

<Transparent inorganic compound layer>
The purpose of providing the transparent inorganic compound layers 330, 331, and 340 is to provide a further high gas barrier function as a gas barrier layer for blocking the permeation of water vapor and oxygen in the transparent gas barrier film.
The transparent inorganic compound layer can be formed by a physical vapor deposition method (Physical Vapor Deposition method) such as a vacuum deposition method, a sputtering method, or an ion plating method, a plasma chemical vapor deposition method (Chemical Vapor Deposition method), or the like. .
The transparent inorganic compound layer is preferably selected from a transparent inorganic oxide film, a transparent inorganic oxynitride film, a transparent inorganic nitride film, or a transparent metal film. The inorganic substance of the transparent inorganic compound layer is preferably one or more selected from silicon, aluminum, magnesium, titanium, tin, indium and cerium. When the transparent inorganic compound is a transparent inorganic oxide film, for example, a silicon oxide film, a silicon oxynitride film, an aluminum oxide film, a magnesium oxide film, a titanium oxide film, a tin oxide film, and an indium alloy oxide film are preferable, and transparent In the case of an inorganic nitride film, a silicon nitride film, an aluminum nitride film, and a titanium nitride film are preferable, and in the case of a transparent metal film, an aluminum film, a silver film, a tin film, a chromium film, a nickel film, and a titanium film Is preferred.

The film thickness of the transparent inorganic oxide film, transparent inorganic oxynitride film, transparent inorganic nitride film, or transparent metal film as described above varies depending on the type of inorganic material used.
For example, the range of 5-5000 nm is preferable, More preferably, it is 5-500 nm.
In the case of a deposited film of aluminum oxide or silicon oxide, the range of 10 to 300 nm is desirable.
If the film thickness is smaller than the above range, the gas barrier property against water vapor, oxygen gas, etc. is reduced, and if it is larger than the above film thickness range, the cracks in the deposited film will progress as the post-processing step proceeds. It is not preferable because deterioration of gas barrier properties against water vapor, oxygen gas, etc. is observed due to the above.
Further, the deposited film may be laminated not only in one layer but also in two or more layers, and the combination may be the same or different.
Here, as a method for forming a transparent inorganic oxide film, a transparent inorganic oxynitride film, a transparent inorganic nitride film or a transparent metal film, an inorganic oxide or inorganic nitride, an inorganic oxynitride or a metal is used as a raw material and heated. Vacuum deposition method for vapor deposition on the substrate, or oxidation by using an inorganic oxide or inorganic nitride, inorganic oxynitride or metal as a raw material, oxidizing by introducing oxygen gas, and vapor deposition on the substrate Reaction deposition method, sputtering method, inorganic oxide using inorganic oxide or inorganic nitride, inorganic oxynitride or metal as a target raw material, argon gas, oxygen gas is introduced and sputtered by sputtering Alternatively, inorganic nitride, inorganic oxynitride, or metal is heated by a plasma beam generated by a plasma gun and deposited on a substrate. Plating, also case of forming a deposited film of silicon oxide, plasma enhanced chemical vapor deposition using an organic silicon compound as a raw material (Chemical Vapor Deposition method).

Here, as the silicon oxide thin film used as the inorganic oxide, a vapor deposition film formed using an organosilicon compound as a raw material and using a low temperature plasma chemical vapor deposition method can be used. For example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, Tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. In the present invention, among the organosilicon compounds as described above, it is preferable to use tetramethoxysilane (TMOS) or hexamethyldisiloxane (HMDSO) from the viewpoints of handleability and vapor deposition film characteristics.
In addition, in the gas barrier laminate substrate described above, even when a transparent inorganic compound layer is further formed on the flattening layer (resin layer 320) to prevent degassing, it is described above. The deposited film and the deposited method are applied.

<Planarization layer (resin layer 320)>
The reason why the flattening layer is provided on the resin film 310 which is the gas barrier substrate shown in FIG. This is to achieve a high gas barrier property within day · atm and with a water vapor transmission rate within 0.1 g / m 2 / day.
The roughness of the surface portion of the planarization layer can be 2 nm or less in terms of centerline average roughness Ra (JISB0061), and the peak-valley can be 20 nm or less.
In general, the resistance is set to a resistance of 1 × 10 ⁶ Ω · cm or less.
When the coating agent for forming the planarizing layer is a non-conductive resin, a conductive material is added to make a conductive resin having conductivity. Any conductive material may be used as long as a surface resistance of 10 6 Ω · cm or less can be obtained by adding it to a nonconductive resin. For example, it is preferable to use a conductive material containing conductive carbon, preferably a stearamide dimethylhydroxyethylammonium nitrate compound.
The material used for the planarization layer can be composed of a conductive thermosetting resin or photo-curing resin, and the thermosetting resin is cured by the addition of heat energy and transparent after curing. In addition, there can be mentioned those capable of forming a flat surface.
For those with low or no conductivity, it is possible to add conductivity by adding a conductive material.

（ただし、Ａ1 はアルキレン基を表す。Ｒ3 は水素原子、低級アルキル基、または、次の一般式、（ｂ））

(ただしＡ2 は直接結合またはアルキレン基を表し、Ｒ7 、Ｒ8 は水素原子または低級アルキル基を表す) で表される基を表す。
Ｒ⁴ は水素原子または低級アルキル基を表す。
Ｒ⁵ は炭素数１〜４のアルキル基、アリール基または不飽和脂肪族残基を表す。
分子中にＲ⁵ が存在する場合、それらは互いに同一であっても異なっていてもよい。
Ｒ⁶ は水素原子、炭素数１〜４のアルキル基またはアシル基であることが好ましい。
分子中にＲ⁶ が存在する場合、それらは互いに同一であっても異なっていてもよい。
ただし、Ｒ³ 、Ｒ⁴ 、Ｒ⁷ 、Ｒ⁸ のうち少なくとも一つが水素原子である。
ｗは０、１、２のいずれかであり、ｚは１〜３の整数であり、かつｗ＋ｚ＝3 である。 上記の式（ａ）で表されるアミノアルキルジアルコキシシラン、もしくはアミノアルキルアルコキシシランの具体例としては、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリイソプロポキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリブトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルイソプロポキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルブトキキシラン、Ｎ−β（アミノエチル）γ−アミノプロピルエチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルエチルジエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルエチルイソプロポキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルエチルブトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノプロピルトリブトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルメチルジイソプロポキシシラン、γ−アミノプロピルメチルジブトキシシラン、γ−アミノプロピルエチルジメトキシシラン、γ−アミノプロピルエチルジエトキシシラン、γ−アミノプロピルエチルジイソプロポキシシラン、γ- アミノプロピルエチルジブトキシシラン、γ−アミノプロピルトリアセトキシシラン等が挙げられ、これらの１種または２種以上を用いることができる。 前記シランカップリング剤が有する有機官能基と反応する有機官能基を有する架橋性化合物（単に、架橋性化合物と言うことがある。）には、次の化合物が挙げられる。
アミノ基と反応しうる官能基である、グリシジル基、カルボキシル基、イソシアネート基、もしくはオキサゾリン基等を有するもので、具体例としては、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、テトラエチレングリコールジグリシジルエーテル、ノナエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、アジピン酸ジグリシジルエーテル、ｏ−フタル酸ジグリシジルエーテル、グリセロールジグリシジルエーテル等のジグリシジルエーテル類；グリセロールトリジグリシジルエーテル、ジグリセロールトリグリシジルエーテル、トリグリシジルトリス（2-ヒドロキシエチル）イソシアヌレ- ト、トリメチロールプロパントリグリシジルエーテル等のトリグリシジルエーテル類；ペンタエリスリトールテトラグリシジルエーテル等のテトラグリシジルエーテル類；その他ポリグリシジルエーテル類あるいはグリシジル基を官能基として有する重合体類；酒石酸、アジピン酸等のジカルボン酸類；ポリアクリル酸等の含カルボキシル基重合体；ヘキサメチレンジイソシアネート、キシリレンイソシアネート等ノイソシアネート類；オキサゾリン含有重合体；脂環式エポキシ化合物等が挙げられ、これらのうち１種または２種以上を用いることができるが、反応性の面からグリシジル基を２個以上有している化合物が好ましく用いられる。
上記の架橋性化合物の使用量は、シランカップリング剤に対して０．１〜３００％（質量基準、以降も同じ）が好ましく、より好ましくは１〜２００％である。架橋性化合物が０．１％未満であると、塗膜のフレキシビリティが不十分となり、３００％を超えて使用すると、ガスバリア性が低下する恐れがある。シランカップリング剤と架橋性化合物とは、必要に応じて過熱しつつ攪拌して、塗料組成物とする。
前記シランカップリング剤および架橋性化合物を原料とする塗料組成物を薄膜層上に塗工、乾燥することで、シランカップリング剤の加水分解・縮合反応と、架橋性化合物による架橋反応とが進行し、架橋構造を有するポリシロキサンの被平坦化層の塗膜が得られる。例えば、平坦化層が、アミノアルキルジアルコキシシラン又はアミノアルキルトリアルコキシシランと、架橋性化合物を用い、加水分解、縮合、架橋反応により形成された架橋構造を有するポリシロキサン塗膜であることが望ましい。
上記の組成物は、さらに、加水分解基を有し、且つアミノ基等の有機官能基を有しないシラン化合物を含有してもよく、具体的には、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポシラン、テトラブトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン、メチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリイソプロポキシシラン、エチルトリブトキシシラン、ジメチルジメトキシシラン、ジメチルジイソプロポキシシラン、ジメチルジブトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジイソプロポキシシラン、ジエチルジブトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドプロピルトリメトキシシラン、γ−グリシドプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン等が挙げられ、これらの１種または２種以上を用いることができる。
上記の加水分解基を有し、且つアミノ基等の有機官能基を有しないシラン化合物を含有するときは、アミノ基等の有機官能基と加水分解基を有するシランカップリング剤との共加水分解・縮合と、架橋性化合物による架橋とが進行し、架橋構造を有するポリシロキサンの塗膜が得られる。
前記平坦化層を形成するための塗料組成物は、さらに分子内に少なくとも１つ以上のアミノ基等の有機官能基と加水分解基を有するシランカップリング剤および／または加水分解縮合化合物を含有していてもよい。
このほか塗料組成物には、上記以外のシラン化合物、溶媒、硬化触媒、濡れ性改良剤、可塑剤、消包剤、増粘着剤等の無機、有機系の各種添加剤を必要に応じて添加することができる。
本シランカッツプリング剤を用いると、ガスバリア性積層基材としてイオンプレーティング法で形成された透明無機化合物層を設けた場合には平坦化層との組み合わせにより、平坦化層が有する水酸基が加水分解反応を促進させることによりガラスライクな酸化度の高い膜となり、また、ガスバリア性積層基材としてスパッタリング法で形成された透明無機化合物層を設けた場合には平坦化層との組合せにより、透明無機化合物層の微細なピンホール等の穴埋め効果を促進し、更にガスバリア性積層基材としてプラズマ化学気相成長法で形成された透明無機化合物層を設けた場合には平坦化層との組み合わせにより、２層の有機的親和性を促進させるこのが可能である。
この場合の平坦化層の形成方法に関しては、特に制限されるものではないが、平坦化層はスピンコーティング法、スプレー法、ブレードコーティング法、ディップ法等によるウェットコーティング法、或いはドライコーティング法による蒸着法のいずれであってもよい。
上記に挙げたような熱硬化性樹脂または光硬化性樹脂に導電性を持たせるために導電性材料を添加する以外に必要に応じて、酸化防止剤、紫外線吸収剤、可塑剤等の添加剤を加えることができる。
また、いずれの平坦化層においても、成膜性向上及び膜のピンホール防止等のため適切な樹脂や添加剤を使用しても良い。
更に平坦化層を形成する際に、エタノール、クロロホルム、テトラヒドロフラン、ジオキサン等の適切な希釈溶媒に溶解または分散させて薄膜を形成するが、その溶媒はいずれであっても良い。
平坦化層の厚みは、薄すぎると、下層に位置する透明無機化合物層のピンホールや突起を埋めるに際して適さず、また厚すぎると熱処理の際に生じる出ガス量が増加するため、ウェットコーティング法で形成される平坦化層では０．５μｍ〜２０μｍ、ドライコーティング法で形成される平坦化層では、５ｎｍ〜５μｍ位の範囲が好ましく、特にウェットコーティング法で形成される平坦化層では１μｍ〜５μｍ、ドライコーティング法で形成される平坦化層では１０ｎｍ〜１μｍが望ましい。 Typical examples of the material used for the planarizing layer (resin layer 320) include polycarbonate, polymethyl methacrylate, polyacrylate, methyl phthalate homopolymer or copolymer, polyethylene terephthalate, polystyrene, diethylene glycol bisallyl carbonate, acrylonitrile. / Styrene copolymer, poly (-4-methylpentene-1), phenol resin, epoxy resin, cyanate resin, maleimide resin, polyimide resin, fluorene skeleton-containing resin, etc., and these include polyvinyl butyral and acrylonitrile. -Modified with butadiene rubber, polyfunctional acrylate compound, etc., crosslinked polyethylene resin, crosslinked polyethylene / epoxy resin, crosslinked polyethylene / cyanate resin, polyphenylene ether / ether Carboxymethyl resins, such as thermoplastic resin modified with a thermosetting resin of the polyphenylene ether / cyanate resin and the like. Further, a plurality of types of resins as listed above may be used in combination.
In addition, as the photocurable resin in the planarization layer, a resin composition composed of an acrylate compound having a radical reactive unsaturated compound, a resin composition composed of an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate And a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer. It is also possible to use a mixture of the resin compositions as listed above.
For materials with low or no conductivity, it is possible to add conductivity by adding a conductive material to the above materials. The conductive material can be added to a non-conductive resin and 10 6 Ω · cm or less. It is sufficient if surface resistance can be obtained. For example, it is preferable to use a conductive material containing conductive carbon, preferably a stearamide dimethylhydroxyethylammonium nitrate compound.
In addition, the material used for the planarization layer is a silane coupling agent having an organic functional group and a hydrolyzable group (hereinafter, sometimes simply referred to as a silane coupling agent), or a conductive material is added to this material. Thus, it is possible to use a silane coupling agent having conductivity. Examples of such silane coupling agents include silane coupling agents having at least one amino group in the molecule. For example, in the following general formula (a) disclosed in JP-A-2001-207130 Examples include aminoalkyl dialkoxysilanes and aminoalkyltrialkoxysilanes.

(However, A1 represents an alkylene group. R3 represents a hydrogen atom, a lower alkyl group, or the following general formula (b)).

Wherein A2 represents a direct bond or an alkylene group, and R7 and R8 represent a hydrogen atom or a lower alkyl group.
R ⁴ represents a hydrogen atom or a lower alkyl group.
R ⁵ represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or an unsaturated aliphatic residue.
When R ⁵ is present in the molecule, they may be the same or different from each other.
R ⁶ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group.
When R ⁶ is present in the molecule, they may be the same or different from each other.
However, at least one of R ³ , R ⁴ , R ⁷ and R ⁸ is a hydrogen atom.
w is 0, 1, or 2, z is an integer of 1 to 3, and w + z = 3. Specific examples of the aminoalkyl dialkoxysilane represented by the above formula (a) or aminoalkylalkoxysilane include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ. -Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ-aminopropyltributoxysilane, N-β (aminoethyl) γ-aminopropyldimethoxy Silane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethylisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethylbutoxysilane, N-β (aminoethyl) γ-aminopropylethyldimethoxysilane, N β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylethylisopropoxysilane, N-β (aminoethyl) γ-aminopropylethylbutoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyl Diethoxysilane, γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldi Propoxysilane, .gamma.-aminopropyl ethyl dibutoxy silane, .gamma.-aminopropyl triacetoxysilane, and the like, may be used alone or two or more thereof. Examples of the crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent (simply referred to as a crosslinkable compound) include the following compounds.
It has a functional group capable of reacting with an amino group, such as glycidyl group, carboxyl group, isocyanate group, or oxazoline group. Specific examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl. Ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol di Glycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, glycerol diglycidyl Diglycidyl ethers such as ether; triglycidyl ethers such as glycerol tridiglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, trimethylolpropane triglycidyl ether; pentaerythritol tetraglycidyl ether Tetraglycidyl ethers such as polyglycidyl ethers or polymers having a glycidyl group as a functional group; dicarboxylic acids such as tartaric acid and adipic acid; carboxyl-containing polymers such as polyacrylic acid; hexamethylene diisocyanate and xylylene Nonisocyanates such as isocyanate; oxazoline-containing polymers; alicyclic epoxy compounds and the like, and one or more of these can be used. , Compounds having a glycidyl group 2 or more from the standpoint of reactivity is preferably used.
The amount of the crosslinkable compound used is preferably 0.1 to 300% (mass basis, the same applies hereinafter) with respect to the silane coupling agent, and more preferably 1 to 200%. When the crosslinkable compound is less than 0.1%, the flexibility of the coating film becomes insufficient, and when it exceeds 300%, the gas barrier property may be lowered. The silane coupling agent and the crosslinkable compound are stirred while being heated as necessary to obtain a coating composition.
By coating and drying the coating composition using the silane coupling agent and the crosslinkable compound as raw materials on the thin film layer, the hydrolysis / condensation reaction of the silane coupling agent and the crosslinking reaction by the crosslinkable compound proceed. As a result, a coating film of the planarized layer of polysiloxane having a crosslinked structure is obtained. For example, the planarizing layer is desirably a polysiloxane coating film having a crosslinked structure formed by hydrolysis, condensation, or crosslinking reaction using an aminoalkyl dialkoxysilane or aminoalkyltrialkoxysilane and a crosslinking compound. .
The above composition may further contain a silane compound having a hydrolyzable group and not having an organic functional group such as an amino group, specifically, tetramethoxysilane, tetraethoxysilane, tetraisosilane. Proposilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyl Dimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxy And silane, γ-glycidpropyltrimethoxysilane, γ-glycidpropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. 1 type (s) or 2 or more types can be used.
When containing a silane compound having the above hydrolyzable group and not having an organic functional group such as an amino group, co-hydrolysis of an organic functional group such as an amino group and a silane coupling agent having a hydrolyzable group -Condensation and crosslinking with a crosslinkable compound proceed to obtain a polysiloxane coating film having a crosslinked structure.
The coating composition for forming the planarizing layer further contains a silane coupling agent and / or a hydrolysis-condensation compound having at least one organic functional group such as an amino group and a hydrolysis group in the molecule. It may be.
In addition to these, various inorganic and organic additives such as silane compounds, solvents, curing catalysts, wettability improvers, plasticizers, anti-packaging agents, and thickeners are added to the coating composition as necessary. can do.
When this silane cut-ring agent is used, when a transparent inorganic compound layer formed by ion plating is provided as a gas barrier laminate substrate, the hydroxyl group of the flattening layer is hydrolyzed by combination with the flattening layer. By promoting the reaction, it becomes a glass-like highly oxidized film, and when a transparent inorganic compound layer formed by a sputtering method is provided as a gas barrier laminate base material, a transparent inorganic compound layer is combined with a flattening layer. Promoting the hole filling effect such as fine pinholes in the compound layer, and further providing a transparent inorganic compound layer formed by plasma enhanced chemical vapor deposition as a gas barrier laminate substrate, in combination with a planarizing layer, This is possible to promote the organic affinity of the two layers.
The method for forming the planarization layer in this case is not particularly limited, but the planarization layer is deposited by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method. Any of the methods may be used.
Additives such as antioxidants, ultraviolet absorbers, plasticizers, etc. as necessary in addition to adding conductive materials to make the thermosetting resins or photocurable resins mentioned above conductive. Can be added.
In any planarization layer, an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film.
Further, when the planarization layer is formed, the thin film is formed by dissolving or dispersing in an appropriate dilution solvent such as ethanol, chloroform, tetrahydrofuran, dioxane or the like, and any solvent may be used.
If the thickness of the flattening layer is too thin, it is not suitable for filling pinholes and protrusions in the transparent inorganic compound layer located in the lower layer, and if it is too thick, the amount of outgas generated during heat treatment increases. In the flattening layer formed by the above method, the range of 0.5 μm to 20 μm is preferable, and in the flattening layer formed by the dry coating method, the range of about 5 nm to 5 μm is preferable, and in the flattening layer formed by the wet coating method, 1 μm to 5 μm is particularly preferable. In the planarization layer formed by the dry coating method, 10 nm to 1 μm is desirable.

Furthermore, regarding the case where the gas barrier laminate substrate of the first example, the second example or the modification described above is used as a display substrate, each layer to be laminated will be briefly described below. <Transparent conductive layer>
When using the gas barrier laminate substrates of the first example, the second example, and the modified examples as display substrates, the following transparent conductive layers are usually provided on these gas barrier laminate substrates.
For the transparent conductive layer, indium tin oxide (hereinafter referred to as ITO) and / or indium zinc oxide (hereinafter referred to as IZO) can be suitably used.
Examples of the ITO or IZO film forming method include a physical vapor deposition method such as a vacuum deposition method, a sputtering method, and an ion plating method. The thickness of the transparent conductive layer is preferably in the range of about 50 nm to 500 nm.
Also, if the thickness of the transparent conductive layer is smaller than the above, a decrease in conductivity is observed. It is not preferable because conductivity is deteriorated due to the above.

<Stress relaxation layer>
The gas barrier laminate substrate of the present invention may further be provided with a transparent inorganic compound layer on the surface opposite to the side on which the planarization layer has already been formed.
By forming the transparent inorganic compound layer on the opposite side in this way, the stress generated when the film is formed on only one side can be offset or relaxed, and warpage can be prevented.
At the same time, since degassing generated from the opposite surface of the gas barrier substrate can be prevented, a high-quality gas barrier substrate can be stably formed.
When forming the layer of the transparent inorganic compound on the opposite side, it is desirable to consider the thickness of the layer to be formed, the inorganic material to be used, the layer configuration, etc., for stress cancellation or relaxation.
The layers formed on both sides of the transparent gas barrier substrate may have the same layer configuration so as to be plane-symmetric.
The material used for the transparent inorganic compound layer formed on the opposite side is not limited to silicon oxide, silicon nitride, and composites thereof, and may be any transparent inorganic compound such as aluminum oxide or indium oxide. Silicon oxide, silicon nitride and composites thereof are desirable.

<Organic EL formation layer>
Specific examples of the layer structure of the organic EL light emitting device include the following layer structures, but are not limited thereto.
(1) Anode / organic light emitting layer / cathode (2) Anode / hole injection layer / organic light emitting layer / cathode (3) Anode / organic light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / organic Light emitting layer / electron injection layer / cathode (5) Anode / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode A transparent conductive layer or a transparent electrode layer is formed in advance on the substrate, that is, a display substrate can be obtained.
The material of the transparent conductive layer (or transparent electrode layer) needs to efficiently transmit excitation light (that is, light in the near ultraviolet to visible range, preferably blue to blue green light) emitted from the organic EL light emitting element. As such a material, ITO (indium-tin oxide) or IZO (indium-zinc oxide) material can be used as described above.

  Next, examples will be described.

As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was used as the coating material 150 while the substrate was mounted on the holding rotating unit 120 and rotated at 500 rpm, and this was rotated with an average particle system of 20 μm. After spraying and applying by the chemical method, it was dried with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes to form a flattened layer (resin layer) with a thickness of 1.0 μm.
Furthermore, the average film thickness and the film thickness distribution were measured by deck tack.
The deck tack was a surface shape measuring device, DEKATAC3ST, manufactured by Nippon Vacuum Industry Co., Ltd., and measurement was performed at a needle distance of 20 mg and a measurement distance of 2 mm.

As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus.
Silicon nitride was used as a target, and a transparent inorganic compound layer was formed by performing film formation under the following film formation conditions until the film thickness of silicon oxynitride reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Nitrogen gas flow rate: 9sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The water contact angle of the silicon oxide film obtained at this time was 70 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was used as the coating material 150 while the substrate was mounted on the holding rotating unit 120 and rotated at 500 rpm, and this was rotated with an average particle system of 20 μm. After spraying and applying by the chemical method, it was dried with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes to form a flattened layer (resin layer) with a thickness of 1.0 μm.

As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was used as the coating material 150 while the substrate was mounted on the holding rotating unit 120 and rotated at 500 rpm, and this was rotated with an average particle system of 20 μm. After spraying and applying by the chemical method, it was dried with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes to form a flattened layer (resin layer) with a thickness of 1.0 μm.
The laminate obtained in the above process was placed in a chamber of an ion plating apparatus.
Indium tin oxide (ITO) was used as the sublimation material, and the transparent conductive layer was formed by performing film formation under the following film formation conditions until the film thickness of indium tin oxide (ITO) reached 150 nm. .
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A

As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus.
A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was used as the coating material 150 while the substrate was mounted on the holding rotating unit 120 and rotated at 500 rpm, and this was rotated with an average particle system of 20 μm. After spraying and applying by the chemical method, it was dried with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes to form a flattened layer (resin layer) with a thickness of 1.0 μm.
The laminate obtained in the above process was placed in a chamber of an ion plating apparatus.
Indium tin oxide (ITO) was used as the sublimation material, and the transparent conductive layer was formed by performing film formation under the following film formation conditions until the film thickness of indium tin oxide (ITO) reached 150 nm. .
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A
Manufacturing Process of Display Substrate The gas barrier base material obtained in the above process was placed in the chamber of an ion plating apparatus. Indium tin oxide (ITO) is used for the sublimable material, and the following film formation conditions:
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A
The display substrate on which the transparent conductive layer was formed was obtained by performing film formation until the film thickness of indium tin oxide reached 150 nm.
Manufacturing process of color organic EL display Organic having a six-layer structure of transparent electrode layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode on the display substrate manufactured as described above. An EL light emitting device was formed as follows.
That is, after applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the transparent conductive layer of indium zinc oxide obtained in the above process, patterning is performed by a photolithographic method. A transparent electrode layer formed by forming a stripe pattern having a thickness of 0.094 mm, a gap of 0.016 mm, and a film thickness of 100 nm was obtained.
Next, the display substrate having the transparent electrode layer was mounted in a resistance heating vapor deposition apparatus, and a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron injection layer were sequentially formed on the entire surface without breaking the vacuum. . During film formation, the internal pressure of the vacuum chamber was reduced to 1 × 10 −4 Pa.
As the hole injection layer, copper phthalocyanine (CuPc) was laminated so as to have a film thickness of 100 nm.
As the hole transport layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was stacked so as to have a film thickness of 20 nm.
As the organic light emitting layer, 4,4′-bis (2,2′-diphenylvinyl) biphenyl (DPVBi) was laminated so as to have a film thickness of 30 nm.
As the electron injection layer, aluminum chelate (tris (8-hydroxyquinoline) aluminum complex, Alq) was laminated so as to have a film thickness of 20 nm.
Next, using a mask that can obtain a pattern with a width of 0.30 mm and an interval of 0.03 mm orthogonal to the stripe pattern of the anode (transparent electrode layer) without breaking the vacuum, a 200 nm thick Mg / Ag (mass) A cathode composed of 10/1 ratio layers was formed.
The organic EL light-emitting device thus obtained was sealed using a gas barrier substrate prepared in Example 7 and a UV curable adhesive in a dry nitrogen atmosphere in the glove box (both oxygen and moisture concentrations were 10 ppm or less). A color organic EL display was obtained.
The obtained color organic EL display was continuously driven for 100 hours, and then the number of dark spots per unit area in the panel was measured.

Next, a comparative example is given.
[Comparative Example 1]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was applied as the coating material 150 while being mounted on the holding rotating unit 120 and rotated. A flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air for 2 minutes at 160 ° C. for 2 minutes.
Furthermore, the average film thickness and the film thickness distribution were measured by deck tack.

[Comparative Example 2]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The above substrate is mounted on the holding rotating part 120, and without rotating, the coating resin V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) is used as the coating material 150. After spraying and coating by the method, a flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes.
Furthermore, the average film thickness and the film thickness distribution were measured by deck tack.

[Comparative Example 3]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. Silicon nitride was used as a target, and a transparent inorganic compound layer was formed by performing film formation under the following film formation conditions until the film thickness of silicon oxynitride reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Nitrogen gas flow rate: 9sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The water contact angle of the silicon oxide film obtained at this time was 70 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was applied as the coating material 150 while being mounted on the holding rotating unit 120 and rotated. A flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air for 2 minutes at 160 ° C. for 2 minutes.

[Comparative Example 4]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The above substrate is mounted on the holding rotating part 120, and without rotating, the coating resin V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) is used as the coating material 150. After spraying and coating by the method, a flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes.
Furthermore, the average film thickness and the film thickness distribution were measured by deck tack.

[Comparative Example 5]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was applied as the coating material 150 while being mounted on the holding rotating unit 120 and rotated. A flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air for 2 minutes at 160 ° C. for 2 minutes.
The laminate obtained in the above process was placed in a chamber of an ion plating apparatus. Indium tin oxide (ITO) was used as the sublimation material, and the transparent conductive layer was formed by performing film formation under the following film formation conditions until the film thickness of indium tin oxide (ITO) reached 150 nm. .
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A

[Comparative Example 6]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The above substrate is mounted on the holding rotating part 120, and without rotating, the coating resin V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) is used as the coating material 150. After spraying and coating by the method, a flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes.
Furthermore, the average film thickness and the film thickness distribution were measured by deck tack.
The laminate obtained in the above process was placed in a chamber of an ion plating apparatus. Indium tin oxide (ITO) was used as the sublimation material, and the transparent conductive layer was formed by performing film formation under the following film formation conditions until the film thickness of indium tin oxide (ITO) reached 150 nm. .
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A

[Comparative Example 7]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. The coating substrate V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) was applied as the coating material 150 while being mounted on the holding rotating unit 120 and rotated. A flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air for 2 minutes at 160 ° C. for 2 minutes.
The laminate obtained in the above process was placed in a chamber of an ion plating apparatus. Indium tin oxide (ITO) was used as the sublimation material, and the transparent conductive layer was formed by performing film formation under the following film formation conditions until the film thickness of indium tin oxide (ITO) reached 150 nm. .
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A
-Manufacturing process of display substrate The gas barrier base material obtained in the above process was placed in a chamber of an ion plating apparatus. Indium tin oxide (ITO) is used for the sublimable material, and the following film formation conditions:
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A
The display substrate on which the transparent conductive layer was formed was obtained by performing film formation until the film thickness of indium tin oxide reached 150 nm.
Manufacturing process of color organic EL display On the display substrate manufactured as described above, a 6-layer structure of transparent electrode layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode is formed. An organic EL light emitting device was formed as follows.
That is, after applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the transparent conductive layer of indium zinc oxide obtained in the above process, patterning is performed by a photolithographic method. A transparent electrode layer formed by forming a stripe pattern having a thickness of 0.094 mm, a gap of 0.016 mm, and a film thickness of 100 nm was obtained.
Next, the display substrate having the transparent electrode layer was mounted in a resistance heating vapor deposition apparatus, and a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron injection layer were sequentially formed on the entire surface without breaking the vacuum. . During film formation, the internal pressure of the vacuum chamber was reduced to 1 × 10 −4 Pa.
As the hole injection layer, copper phthalocyanine (CuPc) was laminated so as to have a film thickness of 100 nm.
As the hole transport layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was stacked so as to have a film thickness of 20 nm. As the organic light emitting layer, 4,4′-bis (2,2′-diphenylvinyl) biphenyl (DPVBi) was laminated so as to have a film thickness of 30 nm.
As the electron injection layer, aluminum chelate (tris (8-hydroxyquinoline) aluminum complex, Alq) was laminated so as to have a film thickness of 20 nm.
Next, using a mask that can obtain a pattern with a width of 0.30 mm and an interval of 0.03 mm orthogonal to the stripe pattern of the anode (transparent electrode layer) without breaking the vacuum, a 200 nm thick Mg / Ag (mass) A cathode composed of 10/1 ratio layers was formed.
The organic EL light-emitting device thus obtained was sealed using a gas barrier substrate prepared in Example 7 and a UV curable adhesive in a dry nitrogen atmosphere in the glove box (both oxygen and moisture concentrations were 10 ppm or less). A color organic EL display was obtained.
The obtained color organic EL display was continuously driven for 100 hours, and then the number of dark spots per unit area in the panel was measured.

[Comparative Example 8]
As a transparent resin film of a supporting substrate, a sheet-like (30 cm × 21 cm) (meth) acrylic resin [94 parts by weight of an alicyclic skeleton bis (meth) acrylate and 6 parts by weight of an alicyclic skeleton mono (meth) acrylate The resin composition consisting of parts] film, linear expansion coefficient 60 ppm, total light transmittance 86%) was placed in the chamber of the magnetron sputtering apparatus. A transparent inorganic compound layer was formed on the transparent resin base film by using silicon as a target and performing film formation under the following film formation conditions until the film thickness of silicon oxide reached 50 nm.
Deposition pressure: 2.5 × 10 −1 Pa
Argon gas flow rate: 20 sccm
Oxygen gas flow rate: 10sccm
Frequency: 13.56MHz
Electric power: 1.2kW
The contact angle of water of the silicon oxide film obtained at this time was 35 ° at 25 ° C.
Subsequently, the substrate is set in a processing chamber (hereinafter also referred to as a chamber) of the coating apparatus shown in FIG. 1, and DC-40 KV is applied between the atomizing unit 110 </ b> A and the holding rotating unit 120 by the voltage supply source 130. The above substrate is mounted on the holding rotating part 120, and without rotating, the coating resin V-259-EH (manufactured by Nippon Steel Chemical Co., Ltd.) is used as the coating material 150. After spraying and coating by the method, a flattened layer (resin layer) was formed to a thickness of 1.0 μm by drying with hot air at 120 ° C. for 2 minutes and subsequently at 160 ° C. for 60 minutes.
Furthermore, the average film thickness and the film thickness distribution were measured by deck tack.
The laminate obtained in the above process was placed in a chamber of an ion plating apparatus. Indium tin oxide (ITO) was used as the sublimation material, and the transparent conductive layer was formed by performing film formation under the following film formation conditions until the film thickness of indium tin oxide (ITO) reached 150 nm. .
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A
-Manufacturing process of display substrate The gas barrier base material obtained in the above process was placed in a chamber of an ion plating apparatus. Indium tin oxide (ITO) is used for the sublimable material, and the following film formation conditions:
Deposition pressure: 1.5 × 10 −1 Pa
Argon gas flow rate: 18sccm
Oxygen gas flow rate: 28sccm
Deposition current value: 60A
The display substrate on which the transparent conductive layer was formed was obtained by performing film formation until the film thickness of indium tin oxide reached 150 nm.
Manufacturing process of color organic EL display On the display substrate manufactured as described above, a 6-layer structure of transparent electrode layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode is formed. An organic EL light emitting device was formed as follows.
That is, after applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the transparent conductive layer of indium zinc oxide obtained in the above process, patterning is performed by a photolithographic method. A transparent electrode layer formed by forming a stripe pattern having a thickness of 0.094 mm, a gap of 0.016 mm, and a film thickness of 100 nm was obtained.
Next, the display substrate having the transparent electrode layer was mounted in a resistance heating vapor deposition apparatus, and a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron injection layer were sequentially formed on the entire surface without breaking the vacuum. . During film formation, the internal pressure of the vacuum chamber was reduced to 1 × 10 −4 Pa. As the hole injection layer, copper phthalocyanine (CuPc) was laminated so as to have a film thickness of 100 nm.
As the hole transport layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was stacked so as to have a film thickness of 20 nm.
As the organic light emitting layer, 4,4′-bis (2,2′-diphenylvinyl) biphenyl (DPVBi) was laminated so as to have a film thickness of 30 nm.
As the electron injection layer, aluminum chelate (tris (8-hydroxyquinoline) aluminum complex, Alq) was laminated so as to have a film thickness of 20 nm.
Next, using a mask that can obtain a pattern with a width of 0.30 mm and an interval of 0.03 mm orthogonal to the stripe pattern of the anode (transparent electrode layer) without breaking the vacuum, a 200 nm thick Mg / Ag (mass) A cathode composed of 10/1 ratio layers was formed.
The organic EL light-emitting device thus obtained was sealed using a gas barrier substrate prepared in Example 7 and a UV curable adhesive in a dry nitrogen atmosphere in the glove box (both oxygen and moisture concentrations were 10 ppm or less). A color organic EL display was obtained.
The obtained color organic EL display was continuously driven for 100 hours, and then the number of dark spots per unit area in the panel was measured.

上記の表１から明らかなように、作製例１、２のガスバリア性積層基材は、比較例１〜４と比較して、水蒸気バリア性、表面平滑性が優れていることが分かる。
また、作製例１の膜厚分布は、比較例１、２の膜厚分布より優れていることが分かる。 更に、表２より作製例３のガスバリア性積層基材は、比較例５、６と比較して表面平滑性及びシート抵抗値が優れていることが分かる。
表３によれば、作製例４の本発明のガスバリア性基材を用いて形成したカラー有機ＥＬディスプレイは、比較例７、８に比べてダークスポットの発生が抑制されていることが分かる。
尚、ダークスポットは、直径０．１〜２ｍｍのものを測定し、２ｍｍ以上のものは不良品として測定の対象から除外した。
[Evaluation methods]
About the gas-barrier laminated base material or each display substrate produced in the above Production Examples 1 to 4 and Comparative Examples 1 to 8, tests were performed on the evaluation items shown below, and the data were measured.
(1) Measurement of water vapor transmission rate (WVTR) Using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-W 3/31: trade name) under the conditions of a measurement temperature of 37.8 ° C. and a humidity of 100% Rh. Measured (with individual zero).
(2) Measurement of surface roughness (Ra) and maximum height difference (P-V) Measurement was performed using Nanopics (trade name, manufactured by Seiko Instruments Inc.) under the conditions of a scanning range of 20 μm and a scanning speed of 90 sec / frame.
(3) Measurement of infrared absorption spectrum The IR measurement was performed by using a Fourier transform infrared spectrophotometer (manufactured by JASCO, Herschel) equipped with an ATR (multiple reflection) measuring device (manufactured by JASCO, ATR-300 / H: trade name). FT / IR-610). The infrared absorption spectrum was measured using a germanium crystal as a prism at an incident angle of 45 degrees.
(4) Measurement of resistance value It measured using the 4-probe method of the surface electrical resistivity measuring apparatus (Loresta AP: brand name, Mitsubishi Yuka Co., Ltd. product).
(5) Measurement of linear expansion coefficient The linear expansion coefficient at 25-200 degreeC was measured using TMA8310 (brand name) by Rigaku Corporation.
(6) Measurement of total light transmittance Total light transmittance was measured using a total light transmittance apparatus (COLOR S & M COMPUTER MODEL SM-C: model number) manufactured by Suga Test Co., Ltd.
(7) Measurement of film thickness Using DEKTAC3S (surface shape measuring device manufactured by Nippon Vacuum Industry Co., Ltd.), the needle pressure was 20 mg and the measurement distance was 2 mm.
The evaluation results (measurement results) are shown in the following table.

As apparent from Table 1 above, it can be seen that the gas barrier laminate substrates of Production Examples 1 and 2 are superior in water vapor barrier properties and surface smoothness as compared with Comparative Examples 1 to 4.
Moreover, it turns out that the film thickness distribution of the manufacture example 1 is superior to the film thickness distribution of the comparative examples 1 and 2. Furthermore, it can be seen from Table 2 that the gas barrier laminate substrate of Production Example 3 is superior in surface smoothness and sheet resistance compared to Comparative Examples 5 and 6.
According to Table 3, it can be seen that the color organic EL display formed using the gas barrier base material of the present invention of Production Example 4 has suppressed generation of dark spots as compared with Comparative Examples 7 and 8.
The dark spot having a diameter of 0.1 to 2 mm was measured, and the dark spot having a diameter of 2 mm or more was excluded from the object of measurement as a defective product.

It is a schematic block diagram of an example of embodiment of the coating device of this invention. It is the figure which showed one example of the application part of FIG. 3 (a) and 3 (b) are diagrams showing the layer structure of a coated substrate (also referred to as a gas barrier laminate substrate). FIGS. 3 (c) and 3 (d) are gas barriers using them. It is the figure which showed the layer structure of the property laminated base material.

Explanation of symbols

110 Application part 110A Atomization part 111 Rotation part (motor)
112 Shaving nozzle 112a Air flow direction 113 Rotating shaft 114 Atomizing head 115 Enclosure (housing)
116 Air curtain nozzle 116 a Air curtain 120 Holding and rotating unit 125 Rotating shaft 130 Voltage supply source 135 Ground 140 Processing chamber 150 (Dropped) coating material 180 Substrate to be coated (or coating substrate)
310 Film resin base material (hereinafter also referred to as transparent resin film or plastic substrate)
320 Resin layer (also called planarization layer)
330, 340 Transparent inorganic compound layer

Claims (13)

  A coating apparatus for applying a coating material made of a conductive resin in a mist to a substrate to be coated, a holding rotating unit that holds and rotates the substrate to be coated, and a mist of the conductive coating material A voltage supply source for applying a voltage necessary to form an electric field between the application unit and the holding rotation unit, and further grounding. A characteristic coating apparatus.   A coating method for applying a coating material made of a conductive resin in the form of a mist to apply to a substrate to be coated. The substrate to be coated is mounted on a rotating rotating part that holds and rotates the substrate to be coated and rotates. In this state, the conductive coating material is supplied in the form of a mist from the coating unit while being evacuated, and is applied, and the coating is performed by applying a voltage between the coating unit and the holding rotating unit. A coating method characterized by the above.   3. The coating method according to claim 2, wherein the voltage applied between the coating unit and the holding rotating unit is a DC voltage or an AC voltage.   4. The coating method according to claim 2, wherein either one of the coating unit and the holding rotating unit is grounded. 5. The coating method according to claim 2, wherein the coating material has a resistance value of 1 × 10 ⁶ Ω · cm or less.   6. A coated substrate, wherein a coating material is coated on the substrate to be coated by the coating method according to claim 2.   The coated substrate according to claim 6, wherein the coated substrate is a film, a glass substrate, a wafer substrate, or any one of these workpieces.   The coated substrate according to any one of claims 6 to 7, wherein the coated substrate is a gas barrier having water vapor barrier properties and oxygen barrier properties by application of a coating material.   The coated substrate according to any one of claims 6 to 8, wherein the surface portion has a center line average roughness Ra (JISB0061) of 2 nm or less and a mountain-valley is 20 nm or less. An application substrate.   The coated substrate according to any one of claims 7 to 9, wherein the coated substrate is for display.   A display substrate, wherein a transparent conductive layer is provided on the coating material of the coating substrate according to claim 9.   A transparent electrode layer, an organic EL light-emitting element forming layer, and a counter electrode arranged in order on the coating material of the coating substrate according to claim 9 are used for an organic EL display element. A display substrate characterized by the above. It is for the liquid crystal display element which arrange | positioned the transparent electrode layer patterned in order on the coating material of the coating base material of Claim 9, the liquid crystal display element formation layer, and the counter electrode. A display substrate.

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