JP2006301038A - Optical element, manufacturing method of optical element and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical element free from void display and color mixing between adjacent pixels, to provide a manufacturing method of the optical element and to provide a liquid crystal display using the optical element. <P>SOLUTION: The optical element having at least a plurality of pixels and a dark color pixel separating wall separating the pixels on a substrate and the manufacturing method of the optical element satisfy at least: (a) a corner projecting to the dark color pixel separating wall side when a boundary line between the pixel and the dark color pixel separating wall is viewed in a substrate thickness direction from a pixel formation side has a curve shape having ≥0.5 μm radius of curvature; (b) formation of the pixels is performed by a method of applying liquid drops of a colored liquid composition between the dark color pixel separating walls after the dark color pixel separating wall is formed; and (c) the formation of the dark color pixel separating wall is performed by exposing a layer formed on the substrate and composed of a photosensitive resin composition under an oxygen poor atmosphere. The liquid crystal display using the optical element is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical element such as a color filter, which is a constituent member of a liquid crystal display device used in color televisions, personal computer monitors, and the like, and a full-color display electroluminescent element including a plurality of light emitting layers, and a method for manufacturing the same.

A color filter for a display device has a structure in which rectangular images such as red, green, and blue are arranged in a matrix on a substrate such as glass, and the boundaries are divided by dark color separation walls such as a black matrix. As a method for producing such a color filter, conventionally, a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development. Colored photosensitive resin liquid method (colored resist method) (see, for example, Patent Document 1), 4) Method of sequentially transferring images formed on a temporary support onto a final or temporary support (for example, Patent Document) 2), 5) A colored layer is formed by applying a pre-colored photosensitive resin solution on a temporary support, and the photosensitive colored layer is transferred directly onto the substrate, exposed, and developed. A method (transfer system) for forming a multicolor image by a method of repeating this for the number of colors is known (for example, see Patent Document 3).
What is common to these methods is that when three-color pixels of red, green, and blue are formed, it is necessary to repeat the same process three times, resulting in high costs. In addition, since the number of processes is large, there is a problem that the yield is likely to decrease.

In order to overcome these problems, a color filter manufacturing method in which a black matrix is formed by a colored resist method and an RGB pixel is manufactured by an ink jet method has been studied in recent years. This method using the ink jet method has an advantage that the manufacturing process is simple and the cost is low.
In addition, the inkjet method is not limited to the manufacture of color filters, but can also be applied to the manufacture of electroluminescent elements.

  An electroluminescence 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 excitons are obtained by injecting electrons and holes into the thin film and recombining them. Is generated by utilizing the emission of fluorescence or phosphorescence 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 ink jet method to form a light emitting layer, whereby the element can be configured.

  As described above, the ink jet method or the like method for applying droplets can be applied to the manufacture of optical elements such as a color filter and an electroluminescence element 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 of “white spots” and “color mixing” as problems specific to the method of applying droplets.

As a technique for solving the white spot problem, for example, the parent ink treatment is performed so that the contact angle between the dark color separation walls (the region surrounded by the dark color separation walls) is 20 ° or less with respect to water. It has been proposed to use a thick substrate (see, for example, Patent Document 4). Examples of methods for imparting ink affinity include water-soluble leveling agents and water-soluble surfactants. Further, it has been proposed to perform a plasma treatment as a method for cleaning a substrate by dry etching and performing an ink repellent treatment on the substrate (see, for example, Patent Document 5). Furthermore, a method using a surfactant (see, for example, Patent Document 6) is disclosed as a method for performing an ink repellent treatment. However, such a method requires a step of imparting ink affinity, and costs are increased. Disadvantageous. Further, these means have not yet been sufficient to prevent color mixing and further to suppress white spots.
JP-A-63-298304 JP-A-61-99103 JP-A-61-99102 JP-A-9-203803 JP 2001-343518 A JP 2001-235618 A

  Accordingly, an object of the present invention is to provide an optical element free from white spots and color mixture between adjacent pixels, a method for producing an optical element that can stably obtain the optical element, and a liquid crystal display using the optical element To provide an apparatus.

The above conventional problems are achieved by the present invention described below. That is, the optical element of the present invention is
<1> An optical element having at least a plurality of pixels and a dark color separation wall separating the pixels on the substrate, and satisfying at least the following (a), (b) and (c): It is an optical element characterized by these.

(A) When the boundary line between the pixel and the dark color separation wall is observed from the pixel forming side in the thickness direction of the substrate, the convex corner on the dark color separation wall side has a radius of curvature of 0.5 μm or more. It must be a curved shape.
(B) The pixel is formed by a method of applying droplets of a colored liquid composition between the dark color separation walls after the dark color separation wall is formed.
(C) The dark color separation wall is formed by exposing a layer made of the photosensitive resin composition formed on the substrate in a poor oxygen atmosphere.

  <2> The optical element according to <1>, wherein the method for applying the droplet according to (b) is an inkjet method.

  <3> The optical element according to <1> or <2>, wherein the dark color separation wall has a height of 1.8 μm or more and 10 μm or less.

  <4> The optical element according to any one of <1> to <3>, wherein the dark color separation wall is black.

  <5> The optical element according to <4>, wherein the dark color separation wall has an optical density of 2.5 or more and 10 or less.

In addition, the method for producing the optical element of the present invention includes:
<6> a step of forming a layer made of a photosensitive resin composition on a substrate, a step of exposing the layer made of the photosensitive resin composition in a poor oxygen atmosphere to form a dark color separation wall, Any one of the above <1> to <5>, through at least a step of forming a pixel by applying droplets of a colored liquid composition between the dark color separation walls after the dark color separation wall is formed A method for producing an optical element, comprising obtaining the optical element described in 1.

  <7> The method for producing an optical element according to <6>, further comprising: a plasma water repellency treatment step between the step of forming the dark color separation wall and the step of forming the pixel. It is.

Furthermore, the liquid crystal display device of the present invention is
<8> A liquid crystal display device comprising the optical element according to any one of <1> to <5>.

  According to the present invention, an optical element free from white spots and color mixture between adjacent pixels is provided, and a method for manufacturing an optical element capable of stably obtaining the optical element and a liquid crystal display device using the optical element are provided. Can be provided.

The optical element of the present invention is an optical element having at least a plurality of pixels and a dark color separation wall separating the pixels on a substrate, and at least the following (a), (b) and (c) ) Is satisfied.
(A) When the boundary line between the pixel and the dark color separation wall is observed from the pixel forming side in the thickness direction of the substrate, the convex corner on the dark color separation wall side has a radius of curvature of 0.5 μm or more. It must be a curved shape.
(B) The pixel is formed by a method of applying droplets of a colored liquid composition between the dark color separation walls after the dark color separation wall is formed.
(C) The dark color separation wall is formed by exposing a layer made of the photosensitive resin composition formed on the substrate in a poor oxygen atmosphere.

  By setting the radius of curvature of the boundary line between the pixel of the optical element and the dark color separation wall to 0.5 μm or more, white spots can be effectively prevented, and a photosensitive material for forming the dark color separation wall is formed. The color mixing can be very effectively prevented by forming the photosensitive resin composition by exposure in an oxygen-poor atmosphere and forming a dark color separation wall.

Here, the phenomenon of “white spots” and “mixed colors” will be described.
“White void” is a liquid droplet (hereinafter sometimes simply referred to as “ink”) mainly formed from a colored liquid composition that diffuses sufficiently and uniformly into a pixel portion surrounded by a dark color separation wall. This is a failure that occurs due to the inability to do so, and causes display defects such as color unevenness and a decrease in contrast. Here, FIG. 1 shows a conceptual diagram of white spots.
Hereinafter, the cause of white spots will be described. When the dark color separation wall 33 is formed, a photolithography process using a resist is generally used, and contaminants adhere to the surface of the substrate 31 due to various components contained in the resist, so that the ink This may hinder the diffusion of 36.
In recent years, in color filters for TFT-type liquid crystal elements, the shape of the opening of the dark color separation wall 33 is complicated in order to protect the TFT from external light and to obtain a bright display by increasing the aperture ratio. In general, those having a plurality of corners are used.
Therefore, as shown in FIG. 1, there is a problem that the ink 36 does not diffuse sufficiently with respect to the corner.

Further, “mixed color” is a failure that occurs when ink is mixed between adjacent pixels (colored portions) of different colors. In the method of manufacturing a color filter that forms a colored portion by applying ink between dark color separation walls (region surrounded by the dark color separation wall), the volume of the opening of the dark color separation wall is It is necessary to apply an ink having a volume several times to several tens of times.
When the solid content concentration of the colorant or the curing component contained in the ink is high, that is, when the volume of the applied ink is relatively small, the dark color separation wall sufficiently functions as a dark color separation wall, Since the ink can be held between the dark color separation walls, the applied ink does not get over the dark color separation wall and reach the 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 color separation wall, so color mixing occurs between adjacent colored portions. Resulting in. In particular, when ink is applied by an ink jet method, 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. Techniques to avoid it are necessary.

The above problem also occurs when manufacturing an electroluminescence element. That is, in an electroluminescence element, for example, 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 a dark color separation wall to form a pixel (light emitting layer). When forming, when ink mixes between adjacent light emitting layers, the light emitting layer cannot emit light of a desired color and luminance. Even in the case of a single color light emitting layer, the amount of ink that is normally filled in the dark color separation wall is made uniform, so when ink flows into the adjacent light emitting layer, the amount of ink becomes non-uniform and the luminance is increased. It is recognized as unevenness and becomes a problem. In addition, if the ink is not sufficiently diffused in the area surrounded by the dark color separation wall, there is a problem that sufficient light emission luminance cannot be obtained at the boundary portion between the light emitting layer and the dark color separation wall. Arise.
According to the present invention, it is possible to obtain an optical element that effectively suppresses the white spots and color mixture between adjacent pixels.

Hereinafter, in describing the present invention in detail, the dark color separation wall in the present invention will be described in detail, and then the optical element of the present invention, its manufacturing method, and a liquid crystal display device will be described.
In the following description, for the sake of convenience, even when an electroluminescence element is manufactured, the mixing of ink between adjacent light emitting layers is referred to as “mixed color”, and the ink at the boundary between the light emitting layer and the dark color separation wall is used. Occurrence of light emission luminance unevenness due to repulsion is referred to as “outline”.

<Dark color separation wall>
In the present invention, the boundary line between the dark color separation wall and the adjacent pixel is a corner that protrudes toward the dark color separation wall side when viewed from the pixel forming side in the thickness direction of the substrate (hereinafter simply referred to as “dark color”). The corner having a convexity on the side of the separation wall is sometimes referred to as a curved shape having a curvature radius of 0.5 μm or more, and the dark-colored separation wall is formed to have the curved shape.
Here, FIGS. 2 to 4 show examples of corners protruding toward the dark color separation wall in various embodiments of the present invention. As shown in FIGS. 2 to 4, the “convex angle toward the dark color separation wall” is an angle on the pixel side (an angle in the case where it is assumed that the straight line portion intersects as it is, not a curved shape). The portion is less than 180 °, and the shape is not particularly limited except that the radius of curvature is 0.5 μm or more.
The observation from the “pixel forming side in the thickness direction of the substrate” means not only the observation of the boundary line between the formed dark color separation wall and the pixel but also the dark color separation wall and the pixel. It includes a case where the substrate is cut so as to be orthogonal to the film thickness direction and the cross section is observed from the pixel forming side in the thickness direction of the substrate.

The radius of curvature of the corner convex toward the dark color separation wall is 0.5 μm or more at the radius of curvature of the portion of the mask used for exposure corresponding to the corner of the dark color separation wall. By doing so, it is possible to control within the above range.
By setting the radius of curvature to 0.5 μm or more, droplets of the colored liquid composition are sufficiently wetted and spread at the corners, and white spots can be effectively prevented. The curvature radius is further preferably 1.0 μm or more, more preferably 2.0 μm or more, and particularly preferably 3.0 μm or more. If the radius of curvature is less than 0.5 μm, the droplets do not wet and spread at the corners, and white spots occur. The radius of curvature is not particularly limited from the viewpoint that droplets are likely to spread and spread, but if it is too large, the radius of curvature is preferably 10,000 μm or less from the viewpoint that a dark color separation wall / pixel pattern cannot be formed.

(Photosensitive resin composition)
The dark color separation wall in the present invention is formed from a dark photosensitive resin composition containing a colorant. Here, the dark photosensitive resin composition is a composition having a high optical density, and the value is preferably 2.5 or more, more preferably 2.5 to 10.0, and 2.5 -6.0 is still more preferable, and 3.0-5.0 is especially preferable.
Moreover, since this photosensitive resin composition is preferably cured by a photoinitiating system as described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is preferably 2.0 to 10.0, more preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the dark color separation wall shape may not be as desired, and if it exceeds 10.0, polymerization may not be started and formation of the dark color separation wall itself may be difficult. .

The measurement of the optical density is the same except that the photosensitive resin composition is used, a layer having the same thickness as the dark color separation wall formation of the present invention is formed on the transparent substrate, and the pattern is not exposed. Through the steps, a measurement sample (film-like) is obtained. This transmission optical density was measured at 555 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100) (OD). Separately, the transmission optical density of the transparent substrate was measured by the same method (OD ₀ ), and the value obtained by subtracting OD ₀ from OD was defined as the optical density of the dark color separation wall.

(Coloring agent)
Specific examples of the colorant used in the present invention include those given the color index (CI) numbers described in the following dyes and pigments.
For the photosensitive resin composition in the present invention, organic pigments, inorganic pigments, dyes, and the like can be suitably used. When the photosensitive resin layer is required to have light shielding properties, carbon black, titanium oxide, tetraoxide In addition to light-shielding agents such as metal oxide powder such as iron, metal sulfide powder, and metal powder, a mixture of pigments such as red, blue, and green can be used.
When using a pigment among colorants, it is preferable that the pigment is uniformly dispersed in the photosensitive resin composition. The ratio of the colorant in the solid content of the photosensitive resin composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, from the viewpoint of sufficiently shortening the development time. More preferably, it is 50-55 mass%.

  Examples of the known dyes or pigments include Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 5, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185;

  C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73; C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97, C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265;

  C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60; C.I. I. Pigment green 7, C.I. I. Pigment green 36; C.I. I. Pigment brown 23, C.I. I. Pigment brown 25; C.I. I. Pigment black 1, C.I. I. Pigment black 7 and the like.

  In the present invention, it is preferable to use a black colorant among the colorants. Illustrative examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.

  Moreover, when using a pigment, it is desirable to use it as a dispersion liquid. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state. The portion is a liquid that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

  The colorant (for example, pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. When the number average particle diameter exceeds 0.1 μm, the polarization is canceled by the colorant, and the contrast is lowered. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, This 100 average value is said.

  The photosensitive resin composition in the present invention preferably comprises at least a binder / resin / polymer, a polymerization initiator, and a monomer in addition to the colorant. Further, if necessary, a known additive such as a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter, and the like can be further contained. Further, the photosensitive resin composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

(Binder / Resin / Polymer)
As a binder used for the photosensitive resin composition, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 A coalescence etc. can be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. These binder polymers having a polar group may be used alone or in a composition used in combination with a normal film-forming polymer.

(Initiator)
As a method for curing the photosensitive resin composition, a thermal initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are common, but in the present invention, it is preferable to use a photoinitiation system. The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray (also referred to as exposure). It is a compound to be obtained and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.

For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds A compound etc. can be mentioned.
Specifically, a trihalomethyloxazole derivative or s-triazine derivative substituted with a trihalomethyl group described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, Trihalomethyl group-containing compounds such as the trihalomethyloxadiazole compounds described in US Pat. No. 4,221,976;

  9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane 1,9-bis (9-acridinyl) nonane, 1,1,0-bis (9-acridinyl) decane, 1,1,1-bis (9-acridinyl) undecane, 1,1,2-bis (9 Acridine compounds such as bis (9-acridinyl) alkanes such as -acridinyl) dodecane;

6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazine compounds such as trichloromethyl) -s-triazine;
In addition, 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2'-bis (2,4-dichlorophenyl) -4,4 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and particularly selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.

  Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. As a total amount in the photosensitive resin composition of the said photoinitiator, 0.1-20 mass% of the total solid (mass) of the photosensitive resin composition is preferable, and 0.5-10 mass% is especially preferable. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. The “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.
The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor). The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2. , 5-dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.
Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.

  The hydrogen donor can be used alone or in admixture of two or more, and the formed image is less likely to fall off from the permanent support during development, and can be improved in strength and sensitivity. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzobenzone. Thiazole / 4,4′-bis (diethylamino) benzophenone.

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. As a total amount in the photosensitive resin composition of the said hydrogen donor, 0.1-20 mass% of the total solid (mass) of the photosensitive resin composition is preferable, and 0.5-10 mass% is especially preferable.

(monomer)
As the polyfunctional monomer used in the photosensitive resin composition, the following compounds are preferably used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide.

Moreover, reaction of a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate with a diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate, and xylene diisocyanate. Things can also be used.
Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  As content in the photosensitive resin composition of a polyfunctional monomer, 5-80 mass% is preferable with respect to the total solid (mass) of the photosensitive resin composition, and 10-70 mass% is especially preferable. When the content is less than 5% by mass, the resistance to an alkaline developer at the exposed portion of the composition may be inferior, and when it exceeds 80% by mass, the tackiness when a photosensitive resin composition is obtained. It may increase and may be inferior in handleability.

(solvent)
In the photosensitive resin composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

(Surfactant)
In forming the dark color separation wall in the present invention, the photosensitive resin composition can be applied to a temporary support in a substrate or a photosensitive transfer material by using a slit-like nozzle described later, By containing an appropriate surfactant in the photosensitive resin composition, it is possible to control the film thickness to be uniform and effectively prevent coating unevenness.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
The surfactant content relative to the total solid content of the photosensitive resin composition is generally 0.001 to 1%, preferably 0.01 to 0.5%, and preferably 0.03 to 0.3. % Is particularly preferred.

(UV absorber)
The photosensitive resin composition of the present invention can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate series, benzophenone series, benzotriazole series, cyanoacrylate series, nickel chelate series, hindered amine series and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone , Nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebake 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4- Piperidenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine -2-yl] amino} -3-phenylcoumarin and the like.
In addition, as for content of the ultraviolet absorber with respect to the total solid of the photosensitive resin composition, 0.5 to 15% is common, 1 to 12% is preferable, and 1.2 to 10% is especially preferable.

(Other)
-Thermal polymerization inhibitor-
Moreover, it is preferable that the photosensitive resin composition of this invention contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.
The content of the thermal polymerization inhibitor relative to the total solid content of the photosensitive resin composition is generally 0.01 to 1%, preferably 0.02 to 0.7%, and preferably 0.05 to 0.00. 5% is particularly preferred.
Moreover, in the photosensitive resin composition of this invention, the "adhesion adjuvant" described in Unexamined-Japanese-Patent No. 11-133600, other additives, etc. other than the said additive can be contained.

(substrate)
As the substrate (permanent support) constituting the optical element, a metallic support, a metal bonded support, glass, ceramic, synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

(Formation of dark color separation wall)
The dark color separation wall in the present invention is formed using the photosensitive resin composition. That is, (1) the dark color separation wall is formed by applying a photosensitive resin composition containing a colorant to a substrate and drying it, and then subjecting the dark color photosensitive resin layer formed on the substrate to a poor oxygen atmosphere. To be exposed and developed.
The dark color separation wall can also be obtained by other methods. Other methods include (2) transferring a photosensitive transfer material having a dark photosensitive transfer layer (dark photosensitive resin layer) formed on a temporary support by the photosensitive resin composition onto the substrate. After that, exposure and development are performed in an oxygen-poor atmosphere in the same manner as described above to form a dark color separation image wall.

The dark color separation wall is generally black in many cases, but is not limited to black.
Here, black in the present invention refers to a color in which the chromaticity deviation from the achromatic color point (x = 0.333, y = 0.333) is ΔE within 30, and the actual measurement is Using the material for forming the dark color separation wall of the present invention, a layer having the same thickness as that of the dark color separation wall formation of the present invention is formed on the transparent substrate, and the pattern of the present invention is not exposed. A sample for measurement is obtained through the same process as the dark-colored separation wall, and this is measured.
Chromaticity is measured with a C light source, and x, y, and Y of this sample are calculated. When calculating the chromaticity shift from the achromatic color point, the calculation is performed assuming that the Y of the achromatic color point is equal to the Y value of the sample. More preferably, it is within 15 and most preferably within 10. When the color difference ΔE exceeds 30, when the dark color separation wall functions as a black matrix, light leakage occurs, which is not preferable. In addition, the color difference ΔE has no lower limit and is preferably as small as possible, and is preferably within a range in which a liquid crystal display device can be manufactured.

-Anoxic atmosphere-
The above-mentioned poor oxygen atmosphere when exposing and curing the photosensitive resin composition in the present invention means that the partial pressure of oxygen is 0.15 atm or less, and these are as follows in detail. .
Normally, the partial pressure of oxygen is 0.21 atm under the atmosphere (1 atm). Therefore, in order to reduce the partial pressure of oxygen to 0.15 atm or less, (a) the atmosphere at the time of exposure is reduced to 0 0.7 b or less, or (b) a gas other than air and oxygen (for example, an inert gas such as nitrogen or argon) is mixed by 40 vol% or more with respect to air.
The poor oxygen atmosphere in the present invention is not particularly limited, and any of the above methods can be used.
When using the method in which the oxygen partial pressure is 0.15 atm or less, it is preferably 0.10 atm or less, more preferably 0.08 atm or less, and particularly preferably 0.05 atm or less. There is no particular limitation on the lower limit of the oxygen partial pressure. By substituting the vacuum or atmosphere with a gas other than air (eg, nitrogen), the oxygen partial pressure can be effectively reduced to zero, which is also a preferred method. The oxygen partial pressure can be measured using an oximeter.

The inert gas refers to a general gas such as N ₂ , H ₂ , or CO ₂ or a rare gas such as He, Ne, or Ar. Among these, N ₂ is preferably used because of safety, availability, and cost.
The reduced pressure in the method (a) is preferably 500 hPa or less, more preferably 100 hPa or less.

  The photosensitive resin layer is exposed in an oxygen-poor atmosphere to form a dark color separation wall, whereby droplets are ejected between the dark color separation walls (area surrounded by the dark color separation wall). Drops are difficult to get over the dark color separation wall. Therefore, it is possible to obtain a good optical element while preventing color mixing with adjacent pixels. In addition, there is an advantage that exposure sensitivity is increased, exposure time load is reduced, and productivity is improved.

-Formation of dark color separation walls using photosensitive resin composition (coating method)-
First, after cleaning the substrate, the substrate is heat-treated to stabilize the surface state. After temperature-controlling this board | substrate, the said photosensitive resin composition is apply | coated and the photosensitive resin composition coating film is formed. Subsequently, after part of the solvent is dried to eliminate the fluidity of the coating film, unnecessary coating liquid around the substrate is removed by EBR (edge bead remover), etc., and pre-baked to dark-color photosensitive resin. Get a layer.
The application is not particularly limited, and can be performed using a known coater for glass substrates having a slit-like nozzle (for example, product name: MH-1600, manufactured by F.S. Japan).
The drying can be performed using a known drying apparatus (for example, VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)).
Although it does not specifically limit as prebaking, For example, it can achieve by making 120 degreeC 3 minutes.

Subsequently, a distance between the exposure mask surface and the photosensitive resin layer in a state where the photosensitive resin layer is placed in a poor oxygen atmosphere and a mask having an image pattern (for example, a quartz exposure mask) stands vertically. Is appropriately set (for example, 200 μm) and exposed.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, and the exposure amount can be appropriately selected (for example, 300 mJ / cm ² ). .

Next, it develops with a developing solution, a patterning image is obtained, and if necessary, it wash-processes and obtains a deep color separation wall.
Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin layer. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water.
Examples of the light source used for the light irradiation include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

-Formation of dark color separation walls using photosensitive transfer material-
A photosensitive transfer material provided with a photosensitive resin layer on a temporary support and a protective film on the layer is prepared. If necessary, a thermoplastic resin layer may be provided between the temporary support and the photosensitive resin layer.
First, after removing and removing the protective film, the exposed surface of the photosensitive resin layer is bonded onto a permanent support (substrate), and laminated by heating and pressurizing through a laminator or the like (laminate). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to further increase the productivity.

Next, peeling is performed between the temporary support and the photosensitive resin layer (in the case where a thermoplastic resin layer is provided, it may be between the temporary support and the thermoplastic resin layer), and the temporary support is removed. . Subsequently, a desired photomask is disposed above the removal surface after removal of the temporary support, exposed from a light source in an oxygen-poor atmosphere, and developed using a predetermined processing solution after exposure to form a patterning image. Then, if necessary, it is washed with water to obtain a dark color separation wall.
As the developer used for the development process and the light source used for the exposure, the developer and the light source in the formation using the coating method are similarly used.

  Examples of the alkaline substance in the coating method using the photosensitive resin composition and the method using the photosensitive transfer material described below include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, Sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, metasilicate) Acid sodium, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin layer, methods such as rubbing with a rotating brush or a wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance at the time of exposure may be insufficient. If it is too long, the exposed area may be etched. In either case, it is difficult to make the dark color separation wall shape suitable. In this development step, the dark color separation wall shape is formed as described above.

  The height of the dark color separation wall obtained from the above is preferably 1.8 μm or more and 10 μm or less, more preferably 1.9 μm or more and 10 μm or less, and further preferably 20 μm or more and 7 μm or less. Particularly preferably, it is 2.2 μm or more and 5 μm or less. By setting the height to 1.8 μm or more, color mixing can be more effectively prevented. If it exceeds 10 μm, it may be difficult to form a dark color separation wall.

-Manufacture of photosensitive transfer materials-
Here, the production of the photosensitive transfer material will be described.
The temporary support in the above photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  The dark color photosensitive resin layer in the photosensitive transfer material is formed from the photosensitive resin composition, and the characteristics such as the shape, the formation method, and the like are the same as the layer formed by the coating method, The preferred embodiment is also the same.

Further, the photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is alkali-soluble and includes at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, it is possible to exhibit good adhesion to the permanent support in the above-described dark color separation wall forming method.
Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.
For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.
In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.
Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate.
In addition, the preferable film thickness of a thermoplastic resin layer is 2-30 micrometers.

  It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material. The thickness of the protective film is generally 4 to 40 μm, preferably 5 to 30 μm, and particularly preferably 10 to 25 μm.

In the photosensitive transfer material of the present invention, a thermoplastic resin layer is provided by applying a coating solution (a coating solution for a thermoplastic resin layer) in which the additive for the thermoplastic resin layer is dissolved on the temporary support, and drying. Then, the coating solution for the dark color photosensitive resin layer can be prepared on the thermoplastic resin layer by a method such as coating with a solvent that does not dissolve the thermoplastic resin layer and drying.
In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer on a protective film are prepared so that the thermoplastic resin layer and the dark photosensitive resin layer are in contact with each other. It can also be produced by sticking together.
In addition, although application | coating in the said preparation method can be performed with a well-known coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using a slit-shaped nozzle.

(Plasma water repellent treatment)
The substrate on which the dark color separation wall is formed by the above-described method is preferably subjected to water repellency treatment using plasma as a means for preventing “color mixing”. The gas introduced in the plasma treatment water repellent treatment step is a gas containing at least fluorine atoms, preferably selected from CF ₄ , SF ₆ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , and C ₅ F _8. A mixture of at least one halogen gas selected from CF ₄ , SF ₆ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ and C ₅ F ₈ and O ₂ gas A gas having a O ₂ mixing ratio of 30% or less is used.

<Formation of each pixel>
The pixel in the optical element of the present invention is characterized in that droplets made of a colored liquid composition are formed between the dark color separation walls on the substrate on which the dark color separation walls are formed as described above. To do.
That is, a colored liquid composition for forming pixels (for example, RGB pixels) between dark color separation walls (regions surrounded by dark color separation walls) formed on the substrate in the development step. A plurality of pixels are formed by allowing an object to enter the gap.
As a method for allowing the colored liquid composition to enter between the deep color separation walls, a known method such as an ink jet method or a stripe Geyser coating method can be used, and the ink jet method is preferable in terms of cost. In addition, before forming each pixel in this way, the shape of the dark color separation wall may be fixed, and the means is not particularly limited, but includes the following. That is, 1) re-exposure after development (sometimes referred to as post-exposure), and 2) heat treatment at a relatively low temperature after development. The heat treatment here refers to heating a substrate having a dark color separation wall in an electric furnace, a dryer or the like, or irradiating an infrared lamp.

Here, the exposure amount in the case of performing 1) above, if the atmosphere 500~3000mJ / cm ^2, preferably 1000~2000mJ / cm ^2. Similarly, the heating temperature in the case of 2) is 50 to 120 ° C., preferably about 70 to 100 ° C., and the heating time is about 10 to 40 minutes. When the temperature is lower than 50 ° C., there is a concern that the dark color separation wall will not be cured, and when it is higher than 120 ° C., there is a concern that the dark color separation wall shape may be broken.

  Regarding the ink jet method used for forming each pixel, a known method such as a method of thermally curing ink, a method of photocuring, or a method of performing droplet ejection after forming a transparent image receiving layer on a substrate in advance is used. be able to.

  Preferably, after each pixel is formed, a heating step of performing a heat treatment (so-called baking treatment) is provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The heating temperature and time depend on the composition of the photosensitive resin composition and the thickness of the formed layer, but generally from about 120 ° C. to about 120 ° C. from the viewpoint of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at 250 ° C. for about 10 minutes to about 120 minutes is preferred.

  The pattern shape of the pixel thus formed is not particularly limited, and even if it is a general stripe shape or lattice shape (specifically, a shape as shown in FIG. 6B), Further, it may be in a delta arrangement (specifically, a shape as shown in FIG. 6A). The pattern forming mask used at the time of exposure may be a general stripe shape, a lattice shape, or a delta arrangement.

(Inkjet method)
The ink jet system used in the present invention includes a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and an ink is intermittently heated by using its foam. Various methods such as a method of injecting the ink can be employed.
The ink used can be either oily or water-based. Further, the colorant contained in the ink can be used for both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability. In addition, a coating-type colored ink (colored resin composition, for example, described in JP-A No. 2005-3861 [0034] to [0063]) or JP-A No. 10-195358 [0009] is used for producing a known color filter. ]-[0026] The inkjet composition as described above can also be used.
In consideration of the process after coloring, a component that is cured by heating or that is cured by energy rays such as ultraviolet rays can be added to the ink in the present invention. Various thermosetting resins are widely used as components that are cured by heating, and examples of components that are cured by energy rays include those obtained by adding a photoinitiator to an acrylate derivative or a methacrylate derivative. In particular, in view of heat resistance, those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and even those that are sparingly soluble in water can be used after being emulsified.
In this case, the photosensitive resin composition containing a colorant such as a pigment as mentioned in the above section <Photosensitive resin composition> can be suitably used.

  Further, as the ink that can be used in the present invention, a thermosetting ink for a color filter containing at least a binder and a bifunctional to trifunctional epoxy group-containing monomer can also be used as a suitable ink.

The optical element in the present invention is preferably one in which pixels are formed by an inkjet method.
This optical element is an element that controls light transmission and light emission, and is used as a color filter, an electroluminescence element, or the like.

<Liquid crystal display device>
There are no particular limitations on the liquid crystal display device to which the present invention can be applied. For example, various types of liquid crystal display devices described in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)” Applicable. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The optical element of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the examples, “parts”, “%” and “molecular weight” mean “parts by mass”, “mass%” and “weight average molecular weight” unless otherwise specified.

Example 1
-Formation of dark color separation walls-
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 1 below is applied on a glass substrate coater (manufactured by FS Japan, trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K1 was applied. Subsequently, after part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the substrate periphery was unnecessary with EBR (edge bead remover). The coating solution was removed and prebaked at 120 ° C. for 3 minutes to obtain a photosensitive resin layer K1 having a thickness of 2.4 μm.

With a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and the photosensitive resin The distance between the layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen gas atmosphere. The mask shape is a lattice shape, and the radius of curvature of the curved portion is 0.6 μm.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then a KOH-based developer (KOH, containing a nonionic surfactant, product name: CDK-1) , Manufactured by Fuji Film Electronics Materials Co., Ltd.) and subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, thereby obtaining a separation wall. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

Here, preparation of the colored photosensitive resin composition K1 described in Table 1 will be described.
The colored photosensitive resin composition K1 is first weighed in K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then The amounts of cyclohexanone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) -3'- Bromophenyl] -s-triazine and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes.

Of the compositions listed in Table 1,
* The composition of K pigment dispersion 1 is
Carbon black (trade name Special Black 250, manufactured by Degussa) 13.1 parts 5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] Phenylazo]-
0.65 parts of butyroylaminobenzimidazolone ・ Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000) 6.72 parts ・ 79.53 parts of propylene glycol monomethyl ether acetate

* The composition of binder 1 is
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer, molecular weight 40,000) 27 parts, propylene glycol monomethyl ether acetate 73 parts

* The composition of DPHA solution is
・ Dipentaerythritol hexaacrylate (polymerization inhibitor MEHQ
Containing 500 ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts, 24 parts of propylene glycol monomethyl ether acetate

* The composition of surfactant 1 (Megafac F-780-F (manufactured by Dainippon Ink & Chemicals, Inc.))
C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ : 40 parts and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ : 55 parts and H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ : 5 And a copolymer of
(Molecular weight 30,000) 30 parts / Methyl ethyl ketone 70 parts

-Plasma water repellency treatment-
Thereafter, plasma water repellency treatment was performed by the following method.
A plasma water repellency treatment was performed on the substrate on which the dark color separation wall was formed using a cathode coupling parallel plate type plasma treatment apparatus under the following conditions.
Gas used: CF ₄ gas flow rate: 80 sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

-Preparation of colored ink for pixels-
Among the following components, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.
<Composition of colored ink for red pixels>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 3 parts ・ First epoxy resin (novolak type epoxy resin) ,
Epicoat 154 manufactured by Yuka Shell Co., Ltd.) 2 parts, second epoxy resin (neopentyl glycol diglycidyl ether) 5 parts, curing agent (trimellitic acid) 4 parts, solvent: ethyl 3-ethoxypropionate 80 parts For the solvent, ethyl 3-ethoxypropionate, the standard solution shown in the wetting test specified in JIS-K6768 was used, and the contact angle (θ) after 30 seconds was measured after contacting the droplet. The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined from the graph of the plot was 18 °, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m was 0 °. .

  Further, neopentyl glycol diglycidyl ether as the second epoxy resin has a contact angle of 37 ° with respect to the surface of the test piece having a critical surface tension of 30 mN / m and a critical surface tension of 70 mN / m in the same test. The contact angle with respect to the surface of the test piece was 0 ° C.

Further, C.I. I. Pigment Red 254 instead of C.I. I. A colored ink composition for green (G) pixels was prepared in the same manner as in the red pixel portion colored ink composition except that the same amount of pigment green 36 was used.
Further, C.I. I. Pigment Red 254 instead of C.I. I. A blue (B) pixel colored ink composition was prepared in the same manner as the red pixel colored ink composition except that the same amount of CI Pigment Blue 15: 6 was used.

-Pixel formation-
Next, the ink composition of each color of RGB obtained as described above is recorded in the ink jet system between the dark color separation walls of the pixel forming substrate obtained above (in the region divided by the dark color separation wall). The ink composition was discharged using the apparatus until a desired density was obtained, thereby forming pixels composed of red, green, and blue patterns. The substrate after discharging the ink composition was baked in an oven at 230 ° C. for 30 minutes, whereby each pixel was completely cured to produce a color filter.

-Overcoat layer-
After that, the substrate on which the pixels are formed is cleaned with a clean-tech low-pressure mercury lamp (effective wavelength 254 nm) UV cleaning device to remove residues and foreign matters, and then the transparent overcoat agent is added to a film thickness of 1.5 μm. After coating the entire surface, baking was performed at 230 ° C. for 40 minutes. At this time, in order to form a transparent overcoat layer, a polyamic acid represented by the following chemical formula 6 and an epoxy compound represented by the chemical formula 7 were mixed at a mass ratio of 3: 1.

  In Formula 6, R is a methylene group, and m is an integer of 50.

-Formation of ITO pattern (PVA mode)-
The glass substrate on which the overcoat layer is formed is put in a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. Then, an ITO pattern was formed by a photo process, and unnecessary ITO was etched with aqua regia to complete pattern formation.

-Spacer formation-
Similar to the substrate after the ITO formation except that the prescription of the colored photosensitive resin composition K1 in the dark color separation wall produced above was changed to the following coating solution prescription S1 for the photosensitive resin layer. A spacer was prepared using this method.
However, the following methods were used for exposure, development, and baking.
Proximity exposure was performed at 300 mJ / cm ² with an ultrahigh pressure mercury lamp through a predetermined photomask. After the exposure, the unexposed portion of the photosensitive resin layer was dissolved and removed using a KOH developer [CDK-1 (trade name) 100-fold diluted solution (pH = 11.8), manufactured by Fuji Photo Film Co., Ltd.]. .
Subsequently, baking was performed at 230 ° C. for 30 minutes to form a transparent columnar spacer pattern having a diameter of 16 μm and an average height of 3.7 μm on the ITO film on the glass substrate.

* Prescription of coating solution for photosensitive resin layer: S1
-Methacrylic acid / allyl methacrylate copolymer: 108 parts (molar ratio = 20/80, molecular weight 40000)
Dipentaerythritol hexaacrylate (polymerizable monomer) 64.7 parts 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) -3'-bromophenyl]- s-triazine: 6.24 parts, hydroquinone monomethyl ether: 0.0336 parts, Victoria Pure Blue BOHM (manufactured by Hodogaya Chemical Co., Ltd.): 0.874 parts, MegaFuck F780F: 0.856 parts (Dainippon Ink Chemical Co., Ltd.) ) Made; Surfactant)
・ Methyl ethyl ketone: 328 parts ・ 1-methoxy-2-propyl acetate: 475 parts ・ Methanol: 16.6 parts

-Production of liquid crystal display device-
Using the liquid crystal display device substrate obtained above, the liquid crystal display device of Example 1 was produced using the method described in the first example [0079] to [0082] of JP-A-11-242243. did.

(Example 2)
A dark color separation wall was produced in the same manner as in Example 1 except that the mask shape was a lattice and the radius of curvature was 2.1 μm. Next, a color filter composed of red, green, and blue patterns was formed using an ink jet recording apparatus, and a transparent electrode film was formed on the color filter by sputtering of ITO without providing an overcoat layer. A liquid crystal display device was produced in the same manner as in Example 1 except that spacers were formed on the ITO-formed substrate in the same manner as in Example 1 and liquid crystal alignment control protrusions were formed in the following manner. .

-Formation of liquid crystal alignment control protrusions-
For the dark color separation wall produced in Example 1, for the liquid crystal alignment control using the same method except that the formulation of the colored photosensitive resin composition K1 was changed to the following coating solution formulation T1 for photosensitive resin layer Protrusions were made.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the proxy is passed through the photomask by an ultrahigh pressure mercury lamp at an irradiation energy of 150 mJ / cm ² in a nitrogen gas atmosphere. Mitty exposed. Thereafter, the 2.38% tetramethylammonium hydroxide aqueous solution was developed while sprayed on a substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions (exposed portions) of the photosensitive resin layer were developed and removed. On the color filter side substrate, a liquid crystal alignment control protrusion made of a photosensitive resin layer patterned in a desired shape was formed.
Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form liquid crystal alignment control protrusions on the liquid crystal display device substrate.

* Composition of photosensitive resin layer coating solution T1; positive resist solution (Fuji Film Electronics Materials Co., Ltd.,
FH-2413F) 53.3 parts ・ Methyl ethyl ketone 46.7 parts ・ Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.04 parts

(Example 3)
A liquid crystal display device was produced in the same manner as in Example 1 except that the colored photosensitive resin composition K1 was changed to the colored photosensitive resin composition K2, the mask shape was latticed and the curvature radius was 1.1 μm. did.

Example 4
A liquid crystal display device was produced in the same manner as in Example 1 except that the colored photosensitive resin composition K1 was changed to the colored photosensitive resin composition K2, the mask shape was latticed and the radius of curvature was 3.2 μm. did.

(Example 5)
In Example 3, the step of exposing in a nitrogen gas atmosphere was changed to the step of exposing in an environment where the pressure was reduced to 0.7 atm (oxygen partial pressure was 0.15 atm). A liquid crystal display device was produced by this method.

(Comparative Example 1)
In Example 1, except that the step of exposing in a nitrogen gas atmosphere was changed to a step of exposing at 3000 mJ / cm ² under atmospheric pressure (1 atm (oxygen partial pressure is 0.21 atm)). A liquid crystal display device was produced in the same manner as in Example 1.

(Comparative Example 2)
A liquid crystal display device was produced in the same manner as in Example 1 except that the mask shape was a lattice and the radius of curvature was 0.3 μm.

[Evaluation methods]
<Curvature radius>
As shown in FIG. 5, for each corner that is observed with the optical microscope from the substrate and the pixel forming side in the thickness direction and is convex toward the dark color separation wall side, 1 μm on both sides centering on the vertex of the corner, 2 μm in total The radius of curvature of the boundary line of the length was obtained.

<Height of dark separation wall>
Using a contact type surface roughness meter P-10 (manufactured by TENCOR), the height of the dark color separation wall after baking was measured.

<Optical density>
For the optical density, each of the examples and comparative examples is the same as the examples and comparative examples, except that the material having the dark color separation wall formed in the examples and comparative examples is used, a layer having the same thickness is formed on the transparent substrate, and the pattern is not exposed. A sample for measurement (film-like) was obtained through the same steps. This transmission optical density was measured at 555 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100) (OD). Separately, the transmission optical density of the glass substrate was measured by the same method (OD0). The value obtained by subtracting OD0 from OD was defined as the transmission optical density of the dark color separation wall.

<Measurement of chromaticity of dark color separation wall>
The photosensitive resin composition used for the dark color separation wall preparation in the above-mentioned examples and comparative examples was formed on a transparent substrate by forming a layer having the same thickness as the examples and comparative examples, and a sample for measurement was prepared by exposure. . The chromaticity of this sample was measured with a C light source, and x, y, and Y of this sample were calculated. The chromaticity deviation ΔE from the achromatic color point (x, y = 0.33, 0.33) was calculated. The achromatic color point Y value was calculated to be similar to the sample Y value.

<Mixed colors and white spots>
It observed with the optical microscope from the board | substrate and the thickness direction pixel formation side, and mixed food and white-out were evaluated. For mixed colors, observe if there is a color mixture in the pixel, and for white spots, observe whether there is any ink in the pixel, and ink remains on the upper surface of the dark color separation wall. Observed.
The observation of the color mixture was performed on an arbitrary 100 pixels in the optical element.
The observation of white spots was performed at arbitrary 100 points in the pixel that had a convex corner toward the dark color separation wall.
The evaluation results are shown in Table 2 below.

  Here, in Table 2, (* 1) indicates that no color mixture was observed, but there was one ink adhesion on the image separation wall. The ink adhesion is not a problem in practical use.

(A) is a conceptual diagram at the time of observing the pixel and dark color separation wall from which the white spot has generate | occur | produced from the thickness direction with respect to a board | substrate, (b) is AB line of (a). It is a conceptual diagram when the cross section in is observed from the side. It is a conceptual diagram which shows one Embodiment of the shape of the deep color separation wall in this invention. It is a conceptual diagram which shows one Embodiment of the shape of the deep color separation wall in this invention. It is a conceptual diagram which shows one Embodiment of the shape of the deep color separation wall in this invention. It is a conceptual diagram which shows the measurement part at the time of calculating | requiring the curvature radius of a corner convex on the dark color separation wall side. (A) is a conceptual diagram showing pixels formed in a delta arrangement, and (B) is a conceptual diagram showing pixels formed in a stripe shape or a lattice shape.

Explanation of symbols

31 Substrate 33 Dark color separation wall 36 Ink 38 White spot

Claims (8)

An optical element having at least a plurality of pixels and a dark color separation wall separating the pixels on a substrate, wherein the optical element satisfies at least the following (a), (b), and (c): Optical element.
(A) When the boundary line between the pixel and the dark color separation wall is observed from the pixel forming side in the thickness direction of the substrate, the convex corner on the dark color separation wall side has a radius of curvature of 0.5 μm or more. It must be a curved shape.
(B) The pixel is formed by a method of applying droplets of a colored liquid composition between the dark color separation walls after the dark color separation wall is formed.
(C) The dark color separation wall is formed by exposing a layer made of the photosensitive resin composition formed on the substrate in a poor oxygen atmosphere.   2. The optical element according to claim 1, wherein the method for applying droplets according to (b) is an ink jet method. 3.   The optical element according to claim 1, wherein a height of the dark color separation wall is 1.8 μm or more and 10 μm or less.   The optical element according to any one of claims 1 to 3, wherein the dark color separation wall is black.   5. The optical element according to claim 4, wherein an optical density of the dark color separation wall is 2.5 or more and 10 or less.   Forming a layer made of a photosensitive resin composition on a substrate; exposing the layer made of the photosensitive resin composition in an oxygen-poor atmosphere to form a dark color separation wall; and 6. The optical device according to claim 1, through at least a step of forming a pixel by applying droplets of a colored liquid composition between dark-colored separation walls after the image wall is formed. A method for producing an optical element, comprising obtaining an element.   The method of manufacturing an optical element according to claim 6, further comprising a plasma water repellency treatment step between the step of forming the dark color separation wall and the step of forming the pixel.   A liquid crystal display device comprising the optical element according to claim 1.

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