JP2002055222A - Optical device, method for manufacturing the same and liquid crystal device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent color mixing and void in the method for manufacturing an optical device by an ink jet method. SOLUTION: A positive resist pattern 3 is formed on a supporting substrate 1 and a resin composition layer 4 is formed thereon and fluorinated to increase the ink-repelling property of the surface of the resin composition layer 4. Then the resin composition layer 4 on the resist pattern 3 is removed together with the resist pattern 3 by a lift-off method to form barrier walls 5. Ink 8 is supplied to the openings 6 to form pixels 9.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter which is a component of a color liquid crystal element used in a color television, a personal computer, a pachinko game machine, and the like.
And, a manufacturing method for manufacturing an optical element such as a full-color display electroluminescent element having a plurality of light emitting layers using an inkjet method, furthermore, an optical element manufactured by the manufacturing method, and an optical element The present invention relates to a liquid crystal element using one color filter.

[0002]

2. Description of the Related Art In recent years, the development of personal computers,
In particular, with the development of portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, tends to increase. However, cost reduction is necessary for further popularization, and in particular, there is an increasing demand for cost reduction of color filters having a high specific gravity.

Conventionally, various methods have been tried to satisfy the above requirements while satisfying the required characteristics of the color filter, but no method has yet been established which satisfies all the required characteristics. The respective methods will be described below.

[0004] The first method is a dyeing method. In the dyeing method, first, a water-soluble polymer material layer, which is a material for dyeing, is formed on a transparent substrate, and this is patterned into a desired shape by a photolithography process, and the obtained pattern is immersed in a dye bath. To obtain a colored pattern. By repeating this process three times, R (red), G (green), B
A colored layer composed of three colored portions (blue) is formed.

[0005] The second method is a pigment dispersion method, which has been most frequently used in recent years. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a transparent substrate, and this is patterned to obtain a monochromatic pattern. This step is repeated three times to form a colored layer including three colored portions of R, G, and B.

A third method is an electrodeposition method. In this method, a transparent electrode is first patterned on a transparent substrate, and immersed in an electrodeposition coating solution containing a pigment, a resin, an electrolytic solution, and the like to electrodeposit a first color. This process is repeated three times, and R, G,
A colored layer composed of colored portions of three colors B is formed and finally baked.

As a fourth method, a pigment is dispersed in a thermosetting resin and printing is repeated three times to obtain R, G,
After separately applying B, the resin is thermally cured to form a colored layer. In either method,
Generally, a protective layer is formed on the coloring layer.

[0008] These methods have in common that R,
In order to color the three colors G and B, the same process needs to be repeated three times, which increases the cost. There is also a problem that the yield decreases as the number of steps increases. Further, in the electrodeposition method, the pattern shape that can be formed is limited.
T, that is, an active matrix driving method using a thin film transistor as a switching element) is difficult to be applied to the configuration of a liquid crystal element.

Further, the printing method has poor resolution, and is not suitable for forming a fine pitch pattern.

In order to compensate for the above-mentioned drawbacks, in recent years, a method of manufacturing a color filter using an ink jet system has been actively studied. The method using the inkjet method has an advantage that the manufacturing process is simple and the cost is low.

On the other hand, the ink jet method is not limited to the production of color filters, but can be applied to the production of electroluminescence elements.

The electroluminescent element has a structure in which a thin film containing a fluorescent inorganic and organic compound is sandwiched between a cathode and an anode, and electrons and holes are injected into the thin film to be recombined. Is an element that emits light using the emission of fluorescence when the exciton is deactivated. A fluorescent material used for such an electroluminescence element can be applied to a substrate on which an element such as a TFT is formed by an inkjet method to form a light emitting layer, thereby forming an element.

[0013]

As described above, the ink-jet method is applied to the manufacture of optical elements such as color filters and electroluminescent elements because the manufacturing process can be simplified and the cost can be reduced. However, in the manufacture of such an optical element, there are problems such as "color mixture" and "white spots" as problems specific to the ink jet system. Hereinafter, a case where a color filter is manufactured will be described as an example.

"Color mixture" is an obstacle that occurs when ink is mixed between adjacent pixels of different colors (colored portions). In a method of manufacturing a color filter in which a black matrix is used as a partition and a colored portion is formed by applying ink to the openings of the black matrix, the volume of the black matrix is several times to several tens times the volume of the openings of the black matrix. Need to be applied. When the solid content concentration of the colorant and curing component contained in the ink is high,
That is, when the volume of the ink to be applied is relatively small, the black matrix sufficiently functions as a partition and can hold the ink in the opening of the black matrix, so that the applied ink passes over the black matrix. Does not reach adjacent colored portions of different colors. However, when the solid content concentration in the ink is low, that is, when it is necessary to apply a large amount of ink, the ink overflows beyond the black matrix serving as the partition wall, and color mixing occurs between adjacent colored portions. Resulting in. In particular, there is a limit to the viscosity of ink that can be stably ejected from the nozzles of an ink jet head, and there is also a limit to the concentration of solids contained in the ink. Therefore, a technique for avoiding color mixing is required. .

Therefore, there has been proposed a method of preventing color mixing by utilizing a difference in ink wettability between the colored portion and the partition. For example, in JP-A-59-75205, in order to prevent the ink from spreading outside the target area,
A method of forming a diffusion prevention pattern with a substance having poor wettability has been proposed, but no specific technique has been disclosed.
On the other hand, Japanese Patent Application Laid-Open No. 4-123005 proposes, as a specific method, a method of patterning a silicone rubber layer having a large water-repellent and oil-repellent action to form a partition wall for preventing color mixing. Further, in Japanese Patent Application Laid-Open Nos. 5-241111 and 5-241012, a silicone rubber layer is formed on a black matrix serving as a light-shielding layer.
A technique used as a partition for preventing color mixing is disclosed.

According to these methods, even when an amount of ink far exceeding the height of the partition is applied, the ink is repelled because the surface layer of the partition exhibits ink repellency,
Color mixing can be effectively prevented without reaching the adjacent colored portion beyond the partition wall.

FIG. 3 shows a conceptual diagram thereof. In the figure, 31 is a transparent substrate, 33 is a black matrix also serving as a partition, 36
Is ink. When the upper surface of the black matrix 33 has ink repellency, as shown in FIG. 3B, the applied ink 36 is held in the opening of the black matrix 33 and reaches the adjacent colored portion. There is no. However, when the ink repellency of the upper surface of the black matrix 33 is low, as shown in FIG. 3A, the applied ink 36 spreads over the black matrix 33 and is applied to the adjacent opening. It mixes with ink.

In general, a fluorine compound can provide better ink repellency than a silicon compound. For example, JP-A-2000-355
No. 11 discloses a method of forming a positive resist pattern on a light-shielding portion and further applying an ink-repellent treatment agent on the pattern, and using a fluorine compound as the ink-repellent treatment agent. Is disclosed. However, in the case of this method, it is necessary to remove the positive resist pattern provided on the light-shielding portion after forming the colored portion. However, when the resist pattern is removed, problems such as dissolution, peeling, and swelling of pixels may occur. is there.

As a method for fluorinating the surface of the resin layer, Japanese Patent Application Laid-Open No. 6-65408 proposes a method in which a reactive gas of a fluorine compound is turned into plasma to be treated.
Further, as an example of applying this technology to a color filter, Japanese Patent Application Laid-Open No. 11-271753 discloses a multilayer structure in which a partition has a lower layer having affinity for ink and an upper layer having non-affinity, and the upper layer has ink. As a method of making the material incompatible with the above, a method of performing a plasma treatment with a gas containing a fluorine compound is disclosed.

However, all of the above-mentioned methods involve multi-layering of the barrier ribs, and require the photolithography step to be carried out a plurality of times. Therefore, there is a problem that the process becomes complicated, the cost is increased, and the yield is reduced. is there.

On the other hand, "white spots" are obstacles that occur mainly because the applied ink cannot be sufficiently and uniformly diffused into the area surrounded by the partition walls, and cause color unevenness and contrast. This causes display defects such as a decrease in image quality.

FIG. 4 is a conceptual diagram of a white spot. In the drawing, the same members as those in FIG. 3 are denoted by the same reference numerals. Reference numeral 38 denotes a blank portion.

In recent years, in a color filter for a TFT type liquid crystal element, the opening shape of the black matrix 33 is complicated in order to protect the TFT from external light or to obtain a bright display by increasing the aperture ratio. It has become
Since one having a plurality of corners is generally used, there arises a problem that the ink 36 does not sufficiently diffuse into the corners as shown in FIG. When forming the black matrix 33,
Generally, a photolithography process using a resist is used, and contaminants adhere to the surface of the transparent substrate 31 due to various components contained in the resist, which may hinder the diffusion of the ink 36. Further, when the ink repellency of the side surface of the black matrix 33 is extremely high compared to the surface of the transparent substrate 31, the ink 36 is repelled on the side surface of the black matrix 33 as shown in FIG. In some cases, a problem may occur that the color becomes light at the portion where the ink 36 and the black matrix 33 are in contact with each other.

As a method for solving such a problem of color mixing and white spots, Japanese Patent Application Laid-Open No. 9-203803 discloses a method in which a region (concave portion) surrounded by a black matrix (convex portion) is formed.
It has been proposed to use a substrate which has been subjected to an ink-philic treatment so as to have a contact angle of 20 ° or less with water. Examples of a method for imparting ink affinity include a water-soluble leveling agent and a water-soluble surfactant. Further, in order to simultaneously solve the above-described problem of color mixing, a method of treating the surface of the convex portion with an ink repellent treatment agent in advance to impart ink repellency is disclosed. A method of coating with a fluorine-based solvent using a silane coupling agent is exemplified. In this case, as a method for selectively making only the surface layer of the convex portion ink-repellent and not repelling the side surface of the convex portion, two kinds of materials are laminated so that the convex portion itself has such a property. After covering the portions other than the convex portions with a resist, only the upper surface of the convex portions is treated to be ink-repellent. After forming a resist layer on a transparent substrate, the entire surface is treated to be ink-repellent, the resist layer is formed by a photolithography process. A method of forming a convex portion by patterning is exemplified.

Japanese Patent Application Laid-Open No. 9-230129 also discloses a method of irradiating an energy ray as a method for making a concave portion ink-philic. Also in this case, as a method of performing ink-repellent treatment only on the surface layer of the convex portion, a photosensitive material for forming the convex portion is applied on a glass substrate,
A method of patterning a photosensitive material by a photolithography process after treating the entire surface with an ink repellent treatment agent is exemplified. After that, the projections and the depressions are simultaneously subjected to the irradiation of energy rays, or the ink-affinity-selective treatment is selectively performed on either of them.

However, in any of these methods, the surface of the convex portion is subjected to the ink-repellent treatment, and then the concave portion is subjected to the ink-repellent treatment. There is a problem that the ink repellency of the surface of the portion is reduced. Therefore, it is difficult to obtain sufficient ink affinity on the surface of the transparent substrate and the side surface of the black matrix, and to obtain sufficient ink repellency on the upper surface of the black matrix.

The above problem also occurs when an electroluminescent element is manufactured by an ink jet method. That is, in the electroluminescence element, for example, when an organic semiconductor material that emits R, G, and B light is used as ink, and the ink is applied to a region surrounded by partition walls to form a pixel (light emitting layer). When ink is mixed between adjacent light emitting layers, there arises a problem that light emission of a desired color and luminance cannot be obtained in the light emitting layer. Further, even in the case of a single color light emitting layer, since the amount of ink filled in the partition walls is made uniform, when ink flows into adjacent pixels, the amount of ink becomes non-uniform and is recognized as uneven brightness. Becomes In addition, when the ink is not sufficiently diffused in the region surrounded by the partition, there is a problem that sufficient light emission luminance cannot be obtained at the boundary between the light emitting layer and the partition. In the following description, for the sake of convenience, even in the case of manufacturing an electroluminescence element, the mixing of ink between adjacent light emitting layers is referred to as “mixing”, and the light emission luminance due to the repulsion of ink at the boundary between the light emitting layer and the partition. The occurrence of unevenness is referred to as “white spots”.

An object of the present invention is to solve the above problems when manufacturing optical elements such as a color filter and an electroluminescent element at a low cost by a simple process using an ink jet method, and to produce a highly reliable optical element. To provide well. Specifically, when applying ink to the area surrounded by the partition walls, color mixing between adjacent pixels is prevented, and the ink is sufficiently diffused in the area to remove pixels without white spots. Is to form. Another object of the present invention is to provide a liquid crystal element having excellent color display characteristics at a lower cost by using the optical element obtained by the manufacturing method.

[0029]

A first aspect of the present invention is a method for producing an optical element having at least a plurality of pixels and a partition wall made of a resin composition located between adjacent pixels on a supporting substrate, A step of forming a positive resist pattern in a region surrounded by a partition on the support substrate, a step of forming a resin composition layer over the entire support substrate covering the resist pattern, and a fluorination treatment on the surface of the resin composition layer Forming a partition by removing the resin composition layer on the resist pattern together with the resist pattern, and applying ink to a region surrounded by the partition by an inkjet method to form a pixel. And a method for producing an optical element.

In the present invention, the fluorination treatment is a plasma treatment in which a gas containing at least a fluorine atom is introduced to perform plasma irradiation, and the partition is formed of a resin composition containing a light-shielding agent. That the light-shielding agent is carbon black, that the surface of the support substrate is subjected to an ink-philic treatment before the positive resist pattern forming step, that the ink-philic treatment is a cleaning treatment with an alkaline aqueous solution, A cleaning treatment, an excimer cleaning treatment, a corona discharge treatment, or an oxygen plasma treatment; the ink contains at least a curing component, water and an organic solvent; the ink contains a colorant; Manufacturing a color filter, and manufacturing an electroluminescent element in which the pixel is a light emitting layer. It is intended to include.

A second aspect of the present invention is characterized in that the optical element has at least a plurality of pixels and a partition wall located between adjacent pixels on a supporting substrate, and is manufactured by the method of manufacturing an optical element of the present invention. Optical element.

In the second aspect of the present invention, the partition is a light-shielding layer, the support substrate is a transparent substrate, and the pixels are colored portions formed of ink containing a colorant. Being a color filter having a colored portion, having a protective layer on the colored portion, having a transparent conductive film on the surface, the pixel is a light emitting layer, and having electrodes above and below the light emitting layer. It is a preferred embodiment that the present invention is an electroluminescent element.

A third aspect of the present invention is characterized in that a liquid crystal is sandwiched between a pair of substrates, and one of the substrates is formed using a color filter which is one embodiment of the optical element of the present invention. Liquid crystal element.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION
In the step of forming a partition on the support substrate, a positive resist pattern is formed on the support substrate, a resin composition layer for forming the partition is formed thereon, and a fluorination treatment is applied to the surface of the resin composition layer. After increasing the ink repellency of the above, the resin composition layer on the resist pattern is removed together with the resist pattern by lift-off to form a partition, and ink is applied by an inkjet method to form a pixel. Have. Therefore, in the present invention, when the ink is applied, the ink repellency of the upper surface of the partition wall sufficiently holds a large amount of ink to prevent color mixing, while the side wall of the partition wall and the surface of the support substrate have high ink affinity, and The ink spreads and spreads, and white spots are prevented.

In the present invention, the above-mentioned “ink” is
After drying and curing, for example, liquids having optical and electrical functionality are collectively referred to, and are not limited to conventionally used coloring materials.

The optical element of the present invention manufactured by the manufacturing method of the present invention includes a color filter and an electroluminescent element. First, the optical element of the present invention will be described with reference to embodiments.

FIG. 8 schematically shows a cross section of an example of a color filter which is an embodiment of the optical element of the present invention. In the figure, 101 is a transparent substrate as a support substrate, 102 is a black matrix also serving as a partition, 103 is a colored portion which is a pixel, and 104 is a protective layer formed as needed. When a liquid crystal element is formed using the color filter of the present invention, ITO (indium tin) for driving liquid crystal is provided on the colored portion 103 or on the protective layer 104 formed on the colored portion 103. In some cases, a transparent conductive film made of a transparent conductive material such as (oxide) is formed and provided.

FIG. 9 is a schematic cross-sectional view of one embodiment of the liquid crystal device of the present invention constituted by using the color filter of FIG. In the figure, 107 is a common electrode (transparent conductive film), 10
8 is an alignment film, 109 is a liquid crystal, 111 is a counter substrate, 112
Is a pixel electrode, and 113 is an alignment film. The same members as those in FIG.

The color liquid crystal element is generally formed by aligning the substrate 101 on the color filter side with the counter substrate 111 and sealing the liquid crystal 109. TFTs (not shown) and pixel electrodes 112 are formed in a matrix inside one substrate 111 of the liquid crystal element. The pixel electrode 112 is provided inside the substrate 101 on the color filter side.
The colored portion 103 of the color filter is formed so that R, G, and B are arranged at a position facing the color filter, and a transparent common electrode 107 is formed thereon. Further, alignment films 108 and 113 are formed in the plane of both substrates, and the liquid crystal molecules are arranged in a certain direction. These substrates are arranged to face each other via a spacer (not shown), are adhered by a sealing material (not shown), and the gap is filled with the liquid crystal 109.

In the case of the transmissive liquid crystal element, the substrate 111 and the pixel electrode 112 are formed of a transparent material, a polarizing plate is bonded to the outside of each substrate, and a fluorescent lamp and a scattering plate are generally combined. The display is performed by using the backlight and using the liquid crystal compound as an optical shutter for changing the transmittance of the backlight. In the case of a reflective type, the substrate 111 or the pixel electrode 112 is formed of a material having a reflective function, or a reflective layer is provided on the substrate 111, a polarizing plate is provided outside the transparent substrate 101, and a color plate is provided. Display is performed by reflecting light incident from the filter side.

FIG. 7 is a schematic cross-sectional view of an example of an organic electroluminescence element (hereinafter, referred to as an “EL element”) which is another embodiment of the optical element of the present invention.
In the drawing, reference numeral 91 denotes a driving substrate which is a supporting substrate, 92 denotes a partition wall, 9
3 is a light emitting layer which is a pixel, 94 is a transparent electrode, and 96 is a metal layer. In this figure, only one pixel region is shown for simplification.

On the drive substrate 91, a TFT (not shown), a wiring film, an insulating film and the like are laminated in multiple layers.
In addition, a voltage can be applied between the transparent electrodes 94 arranged for each light emitting layer 93 in units of light emitting layers. The drive substrate 91 is manufactured by a known thin film process.

Regarding the structure of the organic EL device of the present invention,
There is no particular limitation as long as at least one of the transparent and translucent electrodes is composed of a pair of anodes and cathodes and at least a light-emitting material is filled in a partition made of a resin composition, and the structure is known. And various modifications can be made without departing from the gist of the present invention.

The laminated structure includes, for example, (1) electrode (cathode) / light-emitting layer / hole injection layer / electrode (anode) (2) electrode (anode) / light-emitting layer / electron injection layer / electrode (cathode) ( 3) Electrode (anode) / hole injection layer / light-emitting layer / electron injection layer / electrode (cathode) (4) Electrode (anode or cathode) / light-emitting layer / electrode (cathode or anode) The present invention can be applied to an EL element having a laminated structure provided with an organic compound layer having any of the above structures.

The above (1) has a two-layer structure, (3) has a three-layer structure, and (4) has a single-layer structure. Although the organic EL element of the present invention is based on these laminated structures, it may have a combined structure of (1) to (4) and a plurality of layers other than these. Further, full color display may be realized by combining with a color filter. The shape, size, material, manufacturing method, and the like of the organic EL device of the present invention having such a laminated structure are appropriately selected according to the use of the organic EL device and the like, and are not particularly limited.

The light emitting material used for the light emitting layer of the organic EL device of the present invention is not particularly limited, and various materials can be applied. Specifically, a low molecular weight fluorescent substance and a high molecular weight fluorescent substance are preferable, and a high molecular weight fluorescent substance is more preferable.

Examples of the low molecular weight organic compound include, but are not limited to, naphthalene and its derivatives, anthracene and its derivatives, perylene and its derivatives, polymethine, xanthene, coumarin, and cyanine dyes; -Metal complexes of hydroxyquinoline and its derivatives, aromatic amines, tetraphenylcyclopentadiene and its derivatives, tetraphenylbutadiene and its derivatives, and the like can be used. Specifically, for example, known materials such as those described in JP-A-57-51781 and JP-A-59-194393 can be used.

The polymer organic compound which can be used as the light emitting material is not particularly limited, and examples thereof include polyphenylenevinylene, polyarylene, polyalkylthiophene, polyalkylfluorene and the like.

The polymer fluorescent substance used in the organic EL device of the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure between them, such as a block-like polymer. Or a random copolymer. From the viewpoint of obtaining a polymeric fluorescent substance having a high quantum yield of fluorescence, a random copolymer having block properties or a block or graft copolymer is preferable to a complete random copolymer. In addition, since the organic EL device of the present invention utilizes light emission from a thin film, a polymer fluorescent material having fluorescence in a solid state is used.

As a good solvent for the polymer fluorescent substance,
Examples include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene and the like.
Although it depends on the structure and molecular weight of the polymeric fluorescent substance, it can be usually dissolved in these solvents in an amount of 0.1% by weight or more.

In the organic EL device of the present invention, it is used in the electron transport layer when an electron transport layer is further provided between the layer containing the light emitting material and the cathode, or used in combination with the hole transport material and the light emitting material. The electron transporting material has a function of transmitting electrons injected from the cathode to the light emitting material. There is no particular limitation on such an electron transporting material, and any one of conventionally known compounds can be selected and used.

Preferred examples of the electron transporting material include:
Examples include nitro-substituted fluorenone derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides, and carbodiimides.

Further, a fluorenylidenemethane derivative,
Anthraquinodimethane derivatives, anthrone derivatives, oxadiazole derivatives and the like can be mentioned. Also,
Although disclosed as a material for forming the light emitting layer, a metal complex of 8-hydroxyquinoline and its derivative and the like can also be used as the electron transporting material.

Next, a typical method for manufacturing an organic EL device having a laminated structure, which is an example of the present invention, will be described. As a transparent or translucent electrode comprising a pair of electrodes consisting of an anode and a cathode, for example, a transparent or translucent electrode formed on a transparent substrate such as transparent glass or transparent plastic is used.

In the EL device of the present invention, the light emitting layer generally forms a thin film in combination with an appropriate binder resin.
The binder can be selected from a wide range of binder resins,
For example, polyvinyl carbazole resin, polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin, phenolic resin, epoxy resin, silicone resin, polysulfone resin, urea resin, etc. But are not limited to these. These may be used alone or as a copolymer in one kind or as a mixture of two or more kinds. The anode material preferably has a work function as large as possible. For example, nickel, gold, platinum, palladium, selenium, rhenium, iridium and alloys thereof, or tin oxide, indium tin oxide (ITO), and copper iodide are preferable. Further, conductive polymers such as poly (3-methylthiophene), polyphenylene sulfide, and polypyrrole can also be used.

On the other hand, as a cathode material, silver, lead, tin, magnesium, aluminum, calcium, manganese, indium, chromium or an alloy thereof having a small work function is used.

Hereinafter, a method for manufacturing an optical element of the present invention will be described with reference to the drawings.

FIGS. 1 and 2 are process diagrams schematically showing a method for manufacturing an optical element according to the present invention. Hereinafter, each step will be described. The following steps (a) to (h) correspond to (a) to (h) in FIGS. 1 and 2, (a-1) to (h-1) on the left side of the drawing are schematic plan views of the substrate, and (a-2) to (h-2) on the right side of the drawing are (a-).
It is AB sectional schematic diagram of 1)-(h-1). In the figure, 1
Is a support substrate, 2 is a positive resist layer, 3 is a resist pattern, 4 is a resin composition layer, 5 is a partition, 6 is a region (opening) surrounded by the partition 5, 7 is an inkjet head, 8 is ink, 9 is a pixel.

Step (a) A support substrate 1 is prepared. The support substrate 1 is a transparent substrate 101 when the color filter illustrated in FIG. 8 is manufactured. In general, a glass substrate is used. However, for the purpose of forming a liquid crystal element, desired transparency and mechanical strength are required. A plastic substrate or the like can also be used as long as it has the necessary characteristics such as described above.

In the case of manufacturing the EL device shown in FIG. 7, the support substrate 1 is a drive substrate 91 on which the transparent electrode 94 is formed. When light emission is observed from the substrate side as shown in FIG. A transparent substrate such as a glass substrate is used as the driving substrate 91.

It is desirable that the support substrate 1 is previously subjected to an ink-philic treatment so that the ink easily spreads in the step (g) described later. As the ink-philic treatment, for example, a method such as a cleaning treatment with an alkaline aqueous solution, a UV cleaning treatment, an excimer cleaning treatment, a corona discharge treatment, and an oxygen plasma treatment is suitably used.

Step (b) On the supporting substrate 1, a positive resist layer 2 is formed.

Step (c) The positive resist layer 2 is patterned to form a resist pattern 3. The resist pattern 3 is finally removed. At this time, the resin composition layer 4 formed on the upper layer is lifted off to leave a predetermined pattern of the resin composition layer, and the partition walls 5 are removed.
To form Further, it is a member for protecting a region serving as a side surface of the partition wall 5 and a surface of the support substrate 1 in a fluorination treatment described later. Therefore, the pattern of the resist pattern 3 is formed so as to be a pattern opposite to that of the partition 5.
Note that it is necessary to use a material that can be removed after the fluorination treatment as the resist. In particular, when an alkali-soluble positive resist is used, the surface of the support substrate 1 can be made to be ink-philic by alkali washing at the time of removing the resist. Higher and preferred.

Step (d) A resin composition layer 4, which is a material for the partition walls 5, is formed on the entire surface of the support substrate 1 so as to cover the resist pattern 4. In the present invention, as the resin composition used to form the partition walls 5, photosensitive resins such as an epoxy resin, an acrylic resin, a polyimide resin containing polyamideimide, a urethane resin, a polyester resin, and a polyvinyl resin are used. Alternatively, a non-photosensitive resin material can be used.
It is preferable to have the above heat resistance, and from that point, an epoxy resin, an acrylic resin, and a polyimide resin are preferably used.

When the partition wall 5 is used as a light shielding layer, a black resin composition in which a light shielding agent is dispersed in the above resin composition is used. As the light-shielding agent, it is desirable to use carbon black because high light-shielding properties can be obtained, and as the carbon black, channel black, roller black, those manufactured by a contact method called disk black, Gas furnace black, those manufactured by the furnace method called oil furnace black, thermal black, those manufactured by the thermal method called acetylene black, and the like can be used. Channel black, gas furnace black and oil furnace black are preferred. Further, if necessary, R, G,
A mixture of the B pigment may be added. A commercially available black resist can also be used. If necessary, a light-shielding layer having a high resistance may be used.

The resin composition layer 4 can be formed by a method such as spin coating, roll coating, bar coating, spray coating, dip coating, or a printing method.

Step (e) The surface of the resin composition layer 4 is fluorinated to increase the ink repellency of the surface. As the fluorination treatment, as a method in which the process is simple and the surface of the resin composition layer 4 can be satisfactorily fluorinated to increase the ink repellency, plasma irradiation by introducing at least a gas containing a fluorine atom is performed. Performed plasma treatment is preferably used.

The gas containing at least a fluorine atom used in this step includes CF ₄ , CHF ₃ ,
It is preferable to use at least one halogen gas selected from C ₂ F ₆ , SF ₆ , C ₃ F ₈ and C ₅ F ₈ . In particular, C ₅ F ₈
(Octafluorocyclopentene) has an ozone depletion potential of 0 and an air life longer than that of a conventional gas by (C).
F _4: 5 million years, C ₄ F _8:. 3200 years) 0 98 years and very short. Therefore, the global warming potential is 90 (100-year integrated value with CO ₂ = 2), which is (C
(F ₄ : 6500, C ₄ F ₈ : 8700) Very small, extremely effective in protecting the ozone layer and the global environment, and is desirable for use in the present invention.

Further, as the introduced gas, a gas such as oxygen, argon, helium or the like may be used in combination, if necessary.
In this step, the above CF ₄ , CHF ₃ , C ₂ F ₆ , SF
_When a mixed gas of at least one halogen gas selected from ₆ , C ₃ F ₈ and C ₅ F ₈ and O ₂ is used, the ink repellency of the surface of the resin composition layer 4 to be fluorinated in the present step is obtained. Can be controlled. However, in the mixed gas, the oxidation reaction mixture ratio by O ₂ exceeds 30% of O ₂ is dominant, because the ink repellency enhancing effect is prevented, also, O ₂ mixing ratio is more than 30% When the mixed gas is used, it is necessary to use a mixture ratio of O ₂ within a range of 30% or less.

As a method for generating plasma, a method such as low-frequency discharge, high-frequency discharge, and microwave discharge can be used. Conditions such as pressure, gas flow rate, discharge frequency, and processing time during plasma processing are as follows. It can be set arbitrarily.

FIGS. 5 and 6 are schematic views of a plasma generator that can be used in the above-described plasma processing step. In the figure, 51 is an upper electrode, 52 is a lower electrode, 53 is a substrate to be processed, and 54 is a high-frequency electrode. The device is a parallel plate 2
A high frequency voltage is applied to the pole electrode to generate plasma. FIG. 5 shows an apparatus of a cathode coupling system, and FIG. 6 shows an apparatus of an anode coupling system. In both systems, the ink repellency of the surface of the resin composition layer 4 depends on conditions such as pressure, gas flow rate, discharge frequency, and processing time. Properties to a desired degree.

In the plasma generating apparatus shown in FIGS. 5 and 6, the cathode coupling method shown in FIG. 5 can shorten the processing time and is advantageous for the processing step.
Further, the anode coupling method shown in FIG. 6 is advantageous in that the support substrate 1 is not unnecessarily damaged. Therefore, the plasma generator used in this step may be selected according to the materials of the support substrate 1 and the resin composition layer 4.

Step (f) In the lift-off step, the resin composition layer 4 on the resist pattern 3 is removed together with the resist pattern 3, and the remaining resin composition layer 4 is heat-cured if necessary to form a partition wall 5. To form

As a method for removing the resist pattern 3,
Although it depends on the material of the resist used, it is necessary to use a method that does not adversely affect the adhesion of the partition walls 5 and the ink repellency of the upper surface of the fluorinated partition walls 5. For example, there is a method of dissolving with an aqueous alkali solution or an organic solvent, and a method of additionally using ultraviolet energy irradiation.

By these series of steps, only the upper surface of the partition 5 has ink repellency, and the surface of the support substrate 1 exposed in the region surrounded by the partition 5 and the side surface of the partition 5 have ink affinity. Is obtained.

Step (g) Using an ink jet recording apparatus, the ink 8 is applied from the ink jet head 7 to a region (opening 6) surrounded by the partition wall 5. As the ink jet, a bubble jet (registered trademark) type using an electrothermal converter as an energy generating element, a piezo jet type using a piezoelectric element, or the like can be used. In the case of a color filter, the ink 8 contains a colorant of each color so as to form R, G, and B colored portions after curing, and EL
In the case of an element, a material that forms a light-emitting layer that emits light by voltage application after curing is used. In any case, the ink 8 preferably contains at least a curing component, water, and a solvent. Hereinafter, the composition of the ink used when a color filter is manufactured by the manufacturing method of the present invention will be described in more detail.

[1] Colorant As the colorant to be contained in the ink in the present invention, both dyes and pigments can be used. When a pigment is used, it is necessary to disperse it uniformly in the ink. A dye-based coloring agent is preferably used because it is necessary to separately add a dispersing agent and the ratio of the coloring agent in the total solid content becomes low. Further, the amount of the coloring agent to be added is preferably equal to or less than the amount of the curing component described later.

[2] Curing component In consideration of process resistance, reliability, and the like in the post-process, a component that cures by heat treatment or light irradiation and fixes the colorant, ie, a crosslinkable monomer or polymer, etc. It is preferable to contain components. In particular, it is preferable to use a curable resin composition in consideration of heat resistance in a later step. Specifically, for example, as a base resin, an acrylic resin having a functional group such as a hydroxyl group, a carboxyl group, an alkoxy group, or an amide group, a silicone resin; or a cellulose derivative such as hydroxypropylcellulose, hydroxyethylcellulose, methylcellulose, or carboxymethylcellulose; Modified products thereof; and vinyl polymers such as polyvinylpyrrolidone, polyvinyl alcohol, and polyvinyl acetal. Further, a crosslinking agent and a photoinitiator for curing these base resins by light irradiation or heat treatment can be used. Specifically, melamine derivatives such as methylolated melamine are used as crosslinking agents, and dichromates, bisazide compounds, radical initiators, cationic initiators, anionic initiators, etc. are used as photoinitiators. It is possible. Further, these photoinitiators can be used as a mixture of plural kinds thereof or in combination with other sensitizers.

[3] Solvent As the medium of the ink used in the present invention, a mixed solvent of water and an organic solvent is preferably used. As the water, it is preferable to use ion-exchanged water (deionized water) instead of general water containing various ions.

Examples of the organic solvent include those having 1 carbon atom such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol.
To 4 alkyl alcohols; dimethylformamide,
Amides such as dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol;
Ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol and diethylene glycol having 2 to 4 Glycerins; lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene glycol methyl ether, and triethylene glycol monomethyl ether; N-methyl-2-pyrrolidone, 2-pyrrolidone, etc. It is preferable to select from the following.

In addition to the above-mentioned components, two or more kinds of organic solvents having different boiling points may be used in combination to form an ink having desired physical properties, if necessary. Preservatives and the like may be added.

Step (h) The pixel 9 is formed by performing necessary processing such as heat treatment and light irradiation, and removing and curing the solvent component in the ink 8.

Further, in the case of a color filter, as described above, a protective layer and a transparent conductive film are formed as necessary. As the protective layer in this case, a resin material of a photo-curing type, a thermo-setting type, or a photo- and heat-curable type, or an inorganic film formed by vapor deposition, sputtering, or the like can be used. Any material can be used as long as it has transparency and can withstand the subsequent transparent conductive film formation process, alignment film formation process, and the like. Further, the transparent conductive film may be formed directly on the colored portion without using the protective layer. In the case of an EL element, a necessary member such as a metal layer is formed on the pixel.

[0084]

EXAMPLES (Example 1) [Formation of resist pattern] A glass substrate (“1737” manufactured by Corning) was subjected to UV cleaning treatment, and a positive type photoresist (“OFPR resist” manufactured by Tokyo Ohka) having a film thickness of 1.5 was obtained.
The resist was applied so as to have a thickness of μm and subjected to predetermined exposure, development, and baking to obtain a resist pattern in which a plurality of rectangular resists of 75 μm × 225 μm were arranged vertically and horizontally.

[Formation of Resin Composition Layer] Next, a graphite paint for black matrix (manufactured by Hitachi Powdered Metals) having a thickness of 2 μm was formed on the glass substrate on which the resist pattern was formed.
It applied so that it might become. [Fluorination Treatment] The glass substrate on which the graphite coating layer was formed as the resin composition layer was subjected to plasma treatment under the following conditions using a parallel plate type plasma treatment apparatus.

Gas used: CF ₄ gas flow rate: 80 sccm Pressure: 8 Pa RF power: 150 W Processing time: 60 sec

[Lift-off of Resin Composition Layer] After exposing the entire surface of the glass substrate subjected to the plasma treatment from the back surface,
After dipping in an alkaline aqueous solution (“NMD developer” manufactured by Tokyo Ohka), the graphite paint on the resist pattern is removed together with the resist pattern by spraying pure water with a high-pressure spray, and heat treatment is performed at 200 ° C. for 30 minutes. Thus, a black matrix pattern having a rectangular opening with a thickness of 2 μm and a size of 75 μm × 225 μm was formed.

[Evaluation of Ink Repellency] The contact angle of the substrate on which the black matrix was formed (black matrix substrate) with respect to pure water was measured. As a result, the upper surface of the black matrix was 130 ° and the surface of the glass substrate was 20 °.

[Adjustment of Ink] R, G, and B inks were prepared with the following compositions using an acrylic copolymer having the following composition as a thermosetting component.

Curing component Methyl methacrylate 50 parts by weight Hydroxyethyl methacrylate 30 parts by weight N-methylolacrylamide 20 parts by weight

R ink C.I. I. Acid Orange 148 3.5 parts by weight C.I. I. Acid Red 289 0.5 parts by weight Diethylene glycol 30 parts by weight Ethylene glycol 20 parts by weight Deionized water 40 parts by weight 6 parts by weight of the above curing component

G ink C.I. I. Acid Yellow 23 2 parts by weight Zinc phthalocyanine sulfonamide 2 parts by weight Diethylene glycol 30 parts by weight Ethylene glycol 20 parts by weight Deionized water 40 parts by weight 6 parts by weight of the above curing component

B ink C.I. I. Direct Blue 199 4 parts by weight Diethylene glycol 30 parts by weight Ethylene glycol 20 parts by weight Deionized water 40 parts by weight 6 parts by weight of the above curing component

[Preparation of Colored Section] Using an ink jet recording apparatus equipped with an ink jet head having a discharge amount of 20 pl, the above R, R
The G and B inks were applied in the range of 200 to 800 pl per opening, with the amount being changed every 100 pl. Next, heat treatment was performed at 90 ° C. for 10 minutes and then at 230 ° C. for 30 minutes to cure the ink to form colored portions (pixels), thereby producing seven types of color filters having different amounts of applied ink.

[Evaluation of color mixture and white spots] When the obtained color filters were observed with an optical microscope, no color mixture or white spots were observed in all the color filters.

Example 2 Example 1 was repeated except that a glass substrate was subjected to oxygen plasma treatment, a positive photoresist was applied, and the gas used in the fluorination treatment was changed from CF ₄ gas to C ₂ F _6. A color filter was produced in the same manner as described above.

[Evaluation of Ink Repellency] When the contact angle of the black matrix substrate with pure water was measured, the upper surface of the black matrix was 130 ° and the surface of the glass substrate was 10 °.

[Evaluation of color mixture and white spots] When the obtained color filters were observed with an optical microscope, no color mixture or white spots were observed in all the color filters.

Comparative Example 1 A color filter was manufactured in the same manner as in Example 1 except that the fluorination treatment was not performed.

[Evaluation of Ink Repellency] When the contact angle of the black matrix substrate with pure water was measured, the upper surface of the black matrix was 70 ° and the surface of the glass substrate was 20 °.

[Evaluation of color mixture and white spots] The obtained color filter was observed with an optical microscope. As a result, color mixture was observed in the color filter having an applied amount of 400 pl or more. No white spots were observed.

Comparative Example 2 A color filter was manufactured in the same manner as in Example 1 except that the glass substrate was not subjected to UV cleaning and fluorination was not performed.

[Evaluation of Ink Repellency] When the contact angle of the black matrix substrate with pure water was measured, the upper surface of the black matrix was 70 ° and the surface of the glass substrate was 60 °.

[Evaluation of color mixture and white spots] When the obtained color filters were observed with an optical microscope, white spots were observed in all the color filters. In addition, color mixing was observed in a color filter having an applied amount of 400 pl or more.

(Embodiment 3) A TF formed by laminating multiple layers of wiring films, insulating films, etc., formed by a thin film process
ITO was formed to a thickness of 40 nm as a transparent electrode by sputtering on a T drive substrate for each pixel (light emitting layer), and patterning was performed according to the pixel shape by a photolithography method.

Next, a partition for filling the light emitting layer was formed. After the above-mentioned TFT substrate was subjected to UV cleaning in the same manner as in Example 1, a positive type photoresist was applied to a thickness of 1.0 μm, and predetermined exposure, development, and baking were performed.
A resist pattern of 5 μm × 225 μm was formed. Next, a transparent photosensitive resin ("CT" manufactured by Fuji Film Ohlin Co., Ltd.)
-2000 L ") to a thickness of 0.5 μm and pre-baked, and then subjected to the same fluorination treatment, lift-off treatment, and heat treatment at 200 ° C. for 30 minutes as in Example 1 to form a film on the ITO transparent electrode. 0.5μm, 75μ
A transparent matrix pattern having a rectangular opening of m × 225 μm was created. The contact angles of pure water on the ITO transparent electrode and on the transparent matrix pattern were 17 ° on the ITO transparent electrode and 105 ° on the transparent matrix pattern.

Next, a light emitting layer was filled in the partition wall of the substrate. As the light emitting layer, an electron transporting 2,5-bis (5-t
ert-butyl-2-benzoxazolyl) -thiophene [an electron-transporting blue light-emitting dye having a fluorescence peak of 450 nm, and is one of the compounds forming an emission center. Less than,
30% by weight of poly (N-vinylcarbazole) (molecular weight: 150,000, manufactured by Kanto Chemical Co., Ltd.)
Hereinafter, both are dissolved in a dichloroethane solution so that the molecules can be dispersed in a hole-transporting host compound consisting of “PVK”. In the dichloroethane solution of PVK-BBOT, Nile Red which is another luminescent center forming compound is further dissolved so as to have a concentration of 0.015 mol%, and the solution is used as an ink, and an opening surrounded by a transparent resin by an inkjet method. The inside was filled and dried to form a light emitting layer having a thickness of 200 nm. At this time, each pixel (light-emitting layer) was independent, and the solution containing the light-emitting material was not mixed in the adjacent pixels between the partition walls. Further on this,
Mg: Ag (10: 1) is vacuum deposited to a thickness of 200n
m of Mg: Ag cathode was formed. When a voltage of 18 V was applied to each pixel of the EL element thus manufactured,
Uniform white light emission of 480 cd / m ² was obtained.

[0108]

As described above, according to the present invention,
A highly reliable optical element having pixels without color mixing or white spots can be manufactured with a high yield by a simple process using an ink-jet method. Not E
L elements can be provided with high yield. Therefore,
By using the color filter, a liquid crystal element having excellent color display characteristics can be provided at lower cost.

[Brief description of the drawings]

FIG. 1 is a process chart of one embodiment of a method for manufacturing an optical element of the present invention.

FIG. 2 is a process chart of one embodiment of a method for manufacturing an optical element of the present invention.

FIG. 3 is a conceptual diagram of color mixing that occurs in a method of manufacturing an optical element by an inkjet method.

FIG. 4 is a conceptual diagram of white spots generated in a method of manufacturing an optical element by an inkjet method.

FIG. 5 is a schematic diagram showing an example of a configuration of a plasma generator that can be used in the manufacturing method of the present invention.

FIG. 6 is a schematic diagram showing another configuration of a plasma generator that can be used in the manufacturing method of the present invention.

FIG. 7 is a schematic cross-sectional view of an example of an electroluminescence element which is an embodiment of the optical element of the present invention.

FIG. 8 is a schematic cross-sectional view of an example of a color filter as another embodiment of the optical element of the present invention.

FIG. 9 is a schematic cross-sectional view of one embodiment of the liquid crystal element of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support substrate 2 positive resist layer 3 resist pattern 4 resin composition layer 5 partition 6 opening 7 inkjet head 8 ink 9 pixel 31 transparent substrate 33 black matrix 36 ink 38 white spot 51 upper electrode 52 lower electrode 53 substrate to be processed 54 High frequency electrode 91 Drive substrate 92 Partition wall 93 Light emitting layer 94 Transparent electrode 96 Metal layer 101 Transparent substrate 102 Black matrix 103 Coloring section 104 Protective layer 107 Common electrode 108 Alignment film 109 Liquid crystal 111 Opposite substrate 112 Pixel electrode 113 Alignment film

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ken Okada 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hiroshi Yani 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Taketo Nishida 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Junichi Sakamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. ( 72) Inventor Kenwichi Iwata 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yoshikatsu Okada 3-30-2 Shimomaruko 3-chome, Ota-ku, Tokyo F-term ( Reference) 2C056 EA24 FA03 FA04 FB01 2H048 BA02 BA11 BA28 BA29 BA64 BB02 BB14 BB22 BB37 BB44 2H091 FA03Y FA35Y FB02 FC10 FC23 GA13 LA15 LA30 MA10 2H096 AA00 AA27 AA28 BA09 EA00 GA00 HA30 JA04 LA02

Claims (16)

[Claims] 1. A method of manufacturing an optical element having at least a plurality of pixels and a partition made of a resin composition located between adjacent pixels on a support substrate, wherein a positive electrode is formed in a region surrounded by the partition on the support substrate. Forming a mold resist pattern, forming a resin composition layer on the entire surface of the support substrate covering the resist pattern, performing a fluorination treatment on the surface of the resin composition layer, and forming a resin on the resist pattern. Removing the composition layer together with the resist pattern to form a partition, and applying an ink to a region surrounded by the partition by an inkjet method to form a pixel,
A method for producing an optical element, comprising: 2. The method of manufacturing an optical element according to claim 1, wherein the fluorination treatment is a plasma treatment in which a gas containing at least a fluorine atom is introduced to perform plasma irradiation. 3. The method for manufacturing an optical element according to claim 1, wherein the partition is formed of a resin composition containing a light-shielding agent. 4. The method for producing an optical element according to claim 3, wherein the light shielding agent is carbon black. 5. The method for manufacturing an optical element according to claim 1, wherein before the positive resist pattern forming step, the surface of the support substrate is subjected to an ink-philic treatment. 6. The method for manufacturing an optical element according to claim 5, wherein the treatment for making the ink lyophilic is one of a cleaning treatment with an alkaline aqueous solution, a UV cleaning treatment, an excimer cleaning treatment, a corona discharge treatment, and an oxygen plasma treatment. 7. The ink according to claim 1, wherein the ink comprises at least a curing component, water,
The method for producing an optical element according to claim 1, further comprising an organic solvent. 8. The method for manufacturing an optical element according to claim 1, wherein the ink contains a colorant, and a color filter in which pixels are colored portions is manufactured. 9. The method for manufacturing an optical element according to claim 1, wherein said pixel is a light emitting layer for manufacturing an electroluminescent element. 10. The display device according to claim 1, further comprising at least a plurality of pixels and a partition located between adjacent pixels on the supporting substrate.
An optical element manufactured by the method for manufacturing an optical element according to any one of the above. 11. The optical element according to claim 10, wherein the partition is a light shielding layer. 12. The color filter according to claim 10, wherein the support substrate is a transparent substrate, the pixels are colored portions formed of ink containing a colorant, and the color filters are provided with colored portions of a plurality of colors. The optical element as described in the above. 13. The optical element according to claim 12, further comprising a protective layer on the colored portion. 14. A transparent conductive film on the surface.
Or the optical element according to 13. 15. The optical element according to claim 10, wherein the pixel is a light emitting layer, and the pixel is an electroluminescent element having electrodes above and below the light emitting layer. 16. A liquid crystal sandwiched between a pair of substrates,
A liquid crystal element, wherein one of the substrates is configured using the optical element according to claim 12.