JP2006330155A - Method for manufacturing color filter, color filter, liquid crystal element, and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter by which a pixel barrier wall with a smooth surface can be stably formed in a small number of steps and the surface resistance of a transparent electrode (ITO) formed on the color filter can be decreased, to provide a color filter having low surface roughness of a pixel barrier wall obtained by the above method, and to provide a liquid crystal display element having the color filter and a liquid crystal display apparatus having the above liquid crystal element. <P>SOLUTION: The method for manufacturing a color filter having two or more pixel groups in different colors from each other on a substrate, in which each pixel constituting the pixel groups is separated from each other by a deep-color barrier and each pixel is formed between pixel barriers by depositing drops of a color liquid composition between the pixel barriers, includes a photosensitive layer forming step of forming a layer comprising a deep-color photosensitive composition containing a photoacid generator, a crosslinking agent which crosslinks by an effect of the photoacid generator, and a colorant on a substrate; an exposure step of exposing the photosensitive layer to cure an exposed region; and a developing step of removing an unexposed photosensitive layer to form a pixel barrier. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a color filter, a color filter obtained by the method, a liquid crystal element using the color filter, and a liquid crystal display device, and more particularly, two or more image groups exhibiting different colors on a substrate. Each of the pixels constituting the pixel group is separated from each other by a dark color separation wall, and a method for producing a color filter formed by applying liquid droplets between the separation walls by inkjet or the like, a color The present invention relates to a filter, a liquid crystal display element including the color filter, and a liquid crystal display device including the liquid crystal display element.

  The color filter for a display device has a structure in which red, green, and blue dot-like images are arranged in a matrix on a substrate such as glass, and the boundary is divided by a dark color separation wall such as a black matrix. As a manufacturing method of 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), 4) A method of sequentially transferring images formed on a temporary support onto a final or temporary support, and 5) Preliminarily colored photosensitive resin liquid as a temporary support. A method of forming a colored layer by coating on the substrate, transferring the photosensitive colored layer directly onto the substrate, sequentially exposing, developing, and forming a multicolor image by repeating the number of colors ( Transfer method) is known. In addition, a method of forming each pixel using an ink jet method is also known.

  Among these methods, although the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive layer resin solution. On the other hand, although the method of forming each pixel using the ink jet method is advantageous in terms of cost with little loss of resin liquid, there is a problem that the positional accuracy of the pixel is poor.

  In order to overcome these problems, a color filter manufacturing method has also been proposed in which a black matrix is formed by a colored resist method to form a separation wall, and RGB pixels are manufactured by an inkjet method. However, according to this separation wall forming method, the surface of the separation wall becomes rough and fine irregularities are generated. For this reason, there is a problem that the surface resistance of the transparent electrode (ITO) formed on the color filter increases.

In order to prevent this, there is a method for providing a flatness by providing a protective layer on the color filter, but there is a problem that the cost increases because an extra layer is formed.
In addition, it is known that the surface roughness is adjusted by performing a dry etching process on the separation wall surface (see, for example, Patent Document 1). In this method, a complicated dry etching process is required, and the number of processing steps increases, so that not only the manufacturing cost is increased, but also there is a problem that it is difficult to adjust the surface roughness of the separation wall to a predetermined roughness.
JP 2001-343518 A

  Therefore, according to the present invention, a separation wall having a smooth surface can be stably formed with a small number of steps, and as a result, a color capable of reducing the surface resistance of the transparent electrode (ITO) formed on the color filter. An object of the present invention is to provide a method for producing a filter, a color filter obtained by this method and having a small surface roughness on a separation wall, a liquid crystal display element provided with this color filter, and a liquid crystal display device provided with this liquid crystal display element.

The invention of the present application solves the above-described problems and has the following configuration.
<1> A substrate having two or more image groups exhibiting different colors, each pixel constituting the pixel group being separated from each other by a dark color separation wall, A method for producing a color filter, which is applied between separation walls to form each pixel between separation walls,
A photosensitive layer forming step of forming on the substrate a layer made of a dark color photosensitive composition containing a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, and a colorant; and the photosensitive layer A method for producing a color filter, comprising: an exposure step of exposing an exposed region to cure an exposed region; and a developing step of forming a separation wall by removing a photosensitive layer in an unexposed portion.

<2> The method for producing a color filter according to <1>, wherein the dark color photosensitive composition further contains a copolymer containing at least one of methyl methacrylate or benzyl methacrylate.
<3> The photoacid generator is one or more compounds selected from the group consisting of an organic halogen compound, an onium salt, and a sulfonate ester. <1> or <2> Manufacturing method of color filter.
<4> The method for producing a color filter according to any one of <1> to <3>, wherein the crosslinking agent is a melamine resin or a urea resin.

<5> The method for producing a color filter according to any one of <1> to <4>, wherein a height of the separating wall is 1.8 μm or more and 10 μm or less.
<6> The method for producing a color filter according to any one of <1> to <5>, wherein an optical density of the separating wall is 2.5 or more and 10 or less.
<7> The method for producing a color filter according to any one of <1> to <6>, wherein the separation wall is black.

<8> A color filter produced by the production method according to any one of <1> to <7>, wherein the surface roughness (Ra value) of the separation wall is 5 nm or less.
<9> A liquid crystal display device comprising the color filter according to <8>.
<10> A liquid crystal display device comprising the liquid crystal display element according to <9>.

According to the method for producing a color filter of the present invention, a layer made of a dark photosensitive composition (hereinafter referred to as a photosensitive layer as appropriate) is formed on a substrate without requiring a dry etching step, and then separated. According to a simple process of exposing and developing the image according to the shape of the wall, a separation wall having finely improved surface irregularities can be obtained. Therefore, it is possible to obtain a color filter with a reduced surface resistance of ITO at a low cost with a small number of steps.
In addition, the color filter formed by the manufacturing method of the present invention has improved unevenness on the surface of the separation wall, and when forming each pixel by applying droplets by inkjet or the like, color mixing with adjacent pixels, etc. The occurrence of defects is suppressed and the surface resistance of ITO is low, which can be suitably used for a liquid crystal display element.

  The method for producing a color filter of the present invention has two or more image groups exhibiting different colors on a substrate, and each pixel constituting the pixel group is separated from each other by a dark separation wall, A method for producing a color filter in which each pixel is formed on a separation wall by a method in which droplets of a colored liquid composition are applied between separation walls, and a photoacid generator on a substrate and the action of the photoacid generator A photosensitive layer forming step of forming a layer composed of a dark color photosensitive composition containing a crosslinking agent and a colorant that are crosslinked by the step, an exposure step of exposing the photosensitive layer to cure an exposed region, and unexposed And a developing step of forming a separation wall by removing the photosensitive layer.

Hereinafter, this manufacturing method will be described in the order of steps.
In the production method of the present invention, first, a photosensitive layer is formed on a substrate. A dark color photosensitive composition that can be used to form a photosensitive layer contains a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, and a colorant, and the photoacid generator upon exposure to light. Is a negative photosensitive composition that decomposes and generates acid, and the crosslinking agent forms a crosslinked structure by the acid generated from the photoacid generator and cures, and the dark color separation wall on the substrate has this composition It is formed by curing the product.

[Dark color photosensitive composition]
The dark color photosensitive composition (hereinafter, appropriately referred to as a photosensitive composition) contains a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, and a colorant.
Here, the dark color 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 to 6.0. Is more preferable, and 3.0 to 5.0 is particularly preferable. Moreover, since this photosensitive 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 2.0 to 10.0, preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the shape of the separation wall may not be as desired, and if it exceeds 10.0, polymerization cannot be started and it is difficult to produce the separation wall itself.

(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.
In the dark color photopolymerizable resin composition of the present invention, organic pigments, inorganic pigments, dyes and the like can be suitably used. When the photopolymerizable resin layer is required to have light shielding properties, carbon black, titanium oxide In addition to light-shielding agents such as metal oxide powder such as iron tetroxide, metal sulfide powder, and metal powder, a mixture of pigments such as red, blue, and green can be used. Known colorants (dyes and pigments) can be used. Among the known colorants, when a pigment is used, it is preferably dispersed uniformly in the dark color composition.
From the viewpoint of sufficiently shortening the development time, the ratio of the colorant in the solid content of the dark color composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and 50 More preferably, it is -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. Pigment green 7, C.I. I. Pigment Green 36
C. I. Pigment brown 23, C.I. I. Pigment Brown 25
C. I. Pigment black 1, C.I. I. Pigment black 7 and the like.

In the present invention, among the colorants, a black colorant is preferable. Illustrative examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.
The pigment is desirably used as a dispersion. 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 [mu] m, more preferably 0.01 to 0.08 [mu] m, from the viewpoint of dispersion stability. On the other hand, if the number average particle diameter of the pigment exceeds 0.1 μm, the polarization is canceled by the pigment, 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.

[Photoacid generator]
Examples of the photoacid generator that generates an acid by light irradiation include organic halogen compounds, onium salts, and sulfonic acid esters. Among these, organic halogen compounds are preferable, and halomethylated triazine and halomethylated oxadiazole compounds are particularly preferable. Specifically, the halomethylated triazine compound is represented by the general formula (1).

(In general formula (1), R ¹ and R ² are halomethyl groups, and Y is an organic group having 5 or more carbon atoms.)
Examples of the halomethyl group include a trichloromethyl group, a tribromomethyl group, a dichloromethyl group, and a dibromomethyl group. Examples of the organic group having 5 or more carbon atoms include a phenyl group that may have a substituent, Examples include naphthyl group, styryl group, styrylphenyl group, furylvinyl group, quaternized aminoethylamino group. Specific examples of the halomethylated triazine compound include the compounds described in paragraphs [0015] to [0025] of JP-A-2002-351075.
Specific examples of the halomethyloxadiazole compound include those described in paragraph numbers [0026] to [0033] of the same publication.

  A photo-acid generator is 0.05-15 mass% with respect to solid content in a photosensitive composition, Preferably it is 5-15 mass%. When the content of the photoacid generator is within this range, the swelling of the composition is suppressed, a sufficient amount of acid is generated by exposure, the crosslinkability of the crosslinker is sufficiently expressed, and a high-strength cured film is formed. It is formed.

[Crosslinking agent]
The cross-linking agent has a function of forming a cross-linked structure by the action of an acid generated from the photoacid generator and curing a film made of the photosensitive composition. Examples of the crosslinking agent include compounds having at least one or more substituents capable of forming a crosslinked structure such as an unsaturated double bond (hereinafter appropriately referred to as crosslinkable substituents).

Specific examples of such a crosslinkable substituent include, for example, (i) a hydroxyalkyl group such as a hydroxyalkyl group, an alkoxyalkyl group, an acetoxyalkyl group, or a derivative thereof;
(Ii) a carbonyl group such as a formyl group, a carboxyalkyl group or a derivative thereof;
(Iii) nitrogen-containing group-containing substituents such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group;
(Iv) Glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group;
(V) Aromatic derivatives such as allyloxyalkyl groups such as benzyloxymethyl group and benzoyloxymethyl group, and aralkyloxyalkyl groups;
(Vi) Substituents containing polymerizable multiple bonds such as vinyl groups and isopropenyl groups. As the crosslinkable substituent of the crosslinking agent of the present invention, a hydroxyalkyl group, an alkoxyalkyl group or the like is preferable, and an alkoxymethyl group is particularly preferable.

Examples of the crosslinking agent having a crosslinkable substituent include (i) methylol groups such as (i) methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing glycoluril compounds, and methylol group-containing phenol compounds. Containing compounds;
(Ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds;
(Iii) Carboxymethyl group-containing compounds such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycoluril compounds, carboxymethyl group-containing phenol compounds;
(Iv) Examples include bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, and epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds. it can.

  The cross-linking agent of the present invention is preferably an alkoxymethylated urea compound or a resin thereof, or an alkoxymethylated glycoluril compound or a resin thereof. Preferred examples of the crosslinking agent that can be used in the present invention are described in paragraphs [0038] to [0047] of JP-A-2002-351075, and these descriptions can also be referred to in the present invention.

  The content of the crosslinking agent is preferably 5 to 40% by mass and more preferably 10 to 30% by mass with respect to the total solid content of the photosensitive composition, and is selected according to the purpose.

The dark color photosensitive composition used in the present invention preferably contains a binder polymer from the viewpoint of improving the film-forming property, in addition to the above essential components, and particularly contains at least one of methyl methacrylate or benzyl methacrylate. It is preferable to contain a copolymer.
[Copolymer containing at least one of methyl methacrylate or benzyl methacrylate]
In the present invention, the copolymer containing at least one of methyl methacrylate or benzyl methacrylate includes a copolymer containing methyl methacrylate, a copolymer containing benzyl methacrylate, and a copolymer containing methyl methacrylate and benzyl methacrylate. Etc.
The copolymer containing methyl methacrylate includes a methacrylic acid / methyl methacrylate copolymer (copolymerization ratio: 14 to 17.6 mol% / 82.4 to 86 mol%, weight average molecular weight 20,000 to 140, 000), methacrylic acid / methyl methacrylate / ethyl acrylate copolymer (copolymerization ratio: 5-10 mol% / 70-60 mol% / 25-30 mol%, weight average molecular weight 20,000-140,000), etc. Is mentioned.
Copolymers containing benzyl methacrylate include methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio: 25 to 37 mol% / 75 to 63 mol%, weight average molecular weight 20,000 to 150,000), methacrylic acid / And benzyl methacrylate / styrene copolymer (copolymerization ratio: 20 mol% / 17.8 mol% / 62.2 mol%, weight average molecular weight 20,000 to 140,000).
Further, the copolymer containing methyl methacrylate and benzyl methacrylate includes a methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer (copolymerization ratio: 14.6 to 27.2 mol% / 79.1 to 32.7). Mol% / 16.3 to 40 mol%, weight average molecular weight 20,000 to 150,000), methacrylic acid / methyl methacrylate / benzyl methacrylate / 2-ethylhexyl acrylate copolymer (copolymerization ratio: 10 to 15 mol%) / 70 to 65 mol% / 10 mol% / 10 mol%, weight average molecular weight 20,000 to 150,000).

  Cresol novolak resins and polyhydroxystyrenes and derivatives thereof, which are often used with commercially available negative resist compositions, are colored after exposure and baking, but methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / benzyl A methacrylate copolymer or the like is particularly preferable since it is less colored during the baking process after exposure and the light transmittance does not decrease.

  The content of the copolymer used in combination as desired is preferably 20 to 70 mass%, more preferably 30 to 60 mass%, based on the total solid content of the photosensitive composition.

[Other ingredients]
Various additives can be contained in the photosensitive composition for various purposes. Examples of additives include surfactants, adhesion promoters, plasticizers, and the like.
The surfactant can be used to improve the coating property and smoothness of the resulting coating film. Specific examples thereof include BM-1000 (manufactured by BM Chemie), Megafax F142D, F172, and the like. F173, F183, F176PF, F177PF (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC-135, FC-170C, Florard FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.) ), Surflon S-112, S-113, S-131, S-141, S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, Fluorine-based or silica commercially available under the trade names SZ-6032, SF-8428, DC-57, DC-190 (above, manufactured by Toray Silicone Co., Ltd.) It may be mentioned as being preferred and over emissions based surfactant.

  The content of the surfactant is 0.05 to 10% by mass of the total solid content of the photosensitive composition, preferably 0.08% to 5% by mass, and particularly preferably 0.1 to 3% by mass. . If the content is too small, the effect of addition cannot be sufficiently obtained, but if the content is too large, the adhesion between the photosensitive layer and the substrate tends to decrease.

(UV absorber)
The photosensitive composition according to the present invention may 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.
Specific examples include compounds described in paragraph No. [0028] of JP-A No. 2001-142228.
In addition, as for content of the ultraviolet absorber with respect to the total solid of a photosensitive composition, 0.5-15 mass% is common, 1-12% mass is preferable, and 1.2-10 mass% is especially preferable. .

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

The photosensitive layer forming step is a step of forming a photosensitive layer by dissolving or dispersing the dark color photosensitive composition as described above in an appropriate solvent (dispersing agent), coating the substrate, and drying. .
First, after cleaning the substrate, the substrate is heat-treated to stabilize the surface state. After the temperature of the substrate is adjusted, the photosensitive composition is applied.
As the coating solvent for the photosensitive composition, organic solvents such as ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone, various ethers, and esters are generally used.
The coating method is not particularly limited, and can be performed using a known glass substrate coater having a slit-like nozzle (for example, product name: MH-1600, manufactured by F.S. Japan).

After the photosensitive composition is applied, one part of the solvent is dried to eliminate the fluidity of the coating layer, and then the unnecessary coating solution around the substrate is removed with an EBR (edge bead remover) or the like and prebaked. Thus, a photosensitive layer is obtained.
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.

The thickness of the photosensitive layer is selected according to the desired height of the separation wall to be formed.
In the present invention, the height h of the dark color separation wall (the distance between the highest point of the dark color separation wall H and the foot G of the perpendicular line from the H to the substrate) is 1. It is preferably 8 μm or more, more preferably 1.9 μm to 10 μm, still more preferably 2.0 μm to 7.0 μm, and particularly preferably 2.2 μm to 5.0 μm. By setting the height of the dark color separation wall in the range of 1.8 μm to 10 μm, color mixing can be prevented more effectively, and thus the coating film thickness of the photosensitive composition is also selected in this range. If the film thickness is less than 1.8 μm, color mixing tends to occur in the resulting color filter, and if it exceeds 10 μm, it is difficult to form a dark color separation wall.

Next, the exposure process which exposes the photosensitive layer formed at the said process and hardens an exposure area | region is implemented. The exposure light source may be selected according to the absorption wavelength of the photoacid generator contained in the photosensitive composition, and a light source in the ultraviolet region is preferably selected.
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.
The exposure is pattern exposure according to the shape of the image separation wall, and may be a method of exposing the entire surface through a mask or scanning exposure.

Hereinafter, as an example of pattern exposure performed through a mask, the distance between the exposure mask surface and the photosensitive layer is appropriately set in a state where a substrate and a mask having an image pattern (for example, a quartz exposure mask) are set up vertically. (For example, 200 μm) and the entire surface of the substrate is exposed.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount can be appropriately selected (for example, 300 mJ / cm ² ).
By this exposure, a crosslinked structure is formed by the acid generated only in the exposed area in the photosensitive layer, and the exposed area is cured.

  After the pattern exposure, baking is performed. The baking conditions vary depending on the photosensitive resin, photoacid generator, cross-linking agent, etc., but are generally 80 to 140 ° C., preferably 100 to 120 ° C., preferably 15 seconds to 3 minutes, preferably Performs a baking process for 15 seconds to 1 minute. The cross-linking reaction proceeds in the presence of acid generated during pattern exposure, and further baking is performed to diffuse the acid generated on the surface (exposed surface side) of the photosensitive resin layer to the deep part of the photosensitive resin layer. The crosslinking reaction can proceed to the deep part of the film.

Next, a developing step for forming a separation wall by removing the photosensitive layer in the unexposed area is performed.
Prior to the development step, it is preferable that pure water is sprayed on the surface of the photosensitive layer with a shower nozzle or the like in advance to uniformly wet the surface of the photosensitive layer.
Thereafter, development is performed with a developing solution to remove the unexposed portion, and a pattern of the image separation wall is formed. Examples of the developer used in the development step include a dilute aqueous solution of an alkaline substance, and a known alkaline developer can be appropriately used. A small amount of an organic solvent miscible with water may be added to the alkaline aqueous solution.

[Developer]
Examples of the alkaline substance used for preparing the developer include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates ( For example, sodium hydrogen carbonate, potassium hydrogen carbonate), alkali metal silicates (for example, sodium silicate, potassium silicate), alkali metal metasilicates (for example, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine Monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like.
The concentration of the alkaline substance in the developer is preferably from 0.01 to 30% by mass, and the pH is preferably from 8 to 14.

Examples of the “water-miscible organic solvent” added to the developer as desired 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-methyl Pyrrolidone and the like are preferred.
The concentration of the water-miscible organic solvent in the developer is preferably from 0.1 to 30% by mass.
A known surfactant can also be added to the developer, 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 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 varies depending on the composition of the dark color photosensitive layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added, but is usually about 10 seconds to 2 minutes. is there. If it is too short, the development of the unexposed area may be insufficient and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. It becomes difficult to make it suitable. In this developing process, a separating wall shape is formed.
After the alkali development treatment, the remaining developer may be removed by washing with water.

  In the present invention, the separation wall is formed by pattern exposure without etching, so that the surface roughness of the dark separation wall can be reduced by controlling the coating surface property of the photosensitive layer. it can. According to the production method of the present invention, the surface roughness Ra value of the dark color separation wall can be 5 nm or less, preferably 4.0 nm or less, more preferably 3.6 nm or less. When the surface roughness Ra value of the dark color separation wall is 5 nm or less, it is possible to prevent the movement of the colored liquid composition on the surface of the dark color separation wall along the surface of the dark color separation wall, As a result, color mixing due to movement of the colored liquid composition between adjacent pixels can be prevented in advance.

In the above method, a photosensitive layer was formed on a support by a coating method, and then a separation wall was formed by exposure and development. However, the formation method is not limited to this, and a photosensitive layer is provided. It can also be formed using a transfer method using a transfer material. Hereinafter, a forming method using a transfer method will be described.
-Formation of separation walls using photosensitive transfer materials-
A photosensitive transfer material having at least a photosensitive layer provided on a temporary support is prepared.

(Photosensitive transfer material)
By providing a protective film on the photosensitive layer, it is possible to prevent the photosensitive layer from being damaged. The photosensitive transfer material peels off the protective film, transfers the photosensitive layer onto the substrate, forms the photosensitive layer on the substrate, exposes it to a separating wall, and bakes and develops as necessary. Thus, a separation wall pattern can be formed.

(Temporary support)
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 or a laminate thereof such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, or polypropylene 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.

(Thermoplastic resin layer)
The photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is preferably alkali-soluble and comprises 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 a permanent support in the dark color separation wall forming method described later.
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.

(Protective film)
A thin protective film is preferably provided on the photosensitive 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 must be easily separated from the photosensitive layer.
As the protective film material, for example, a silicone paper, a polyolefin resin sheet or a polytetrafluoroethylene sheet is suitable, and a polypropylene sheet is particularly preferable. The thickness of the protective film is generally 4 to 40 μm, preferably 5 to 30 μm, and particularly preferably 10 to 25 μm.

(Method for producing photosensitive transfer material)
The photosensitive transfer material used in the production method of the present invention is obtained by applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support and drying it. It can be produced by providing a plastic resin layer and then applying a dark color photosensitive composition coating solution and drying it. Here, the thermoplastic resin layer is not necessarily provided.
In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive layer on a protective film are prepared, and the thermoplastic resin layer and the dark photosensitive layer are in contact with each other. It can also be produced by bonding.
The photosensitive layer can be applied to the temporary support or the protective film in the above production method by a known application device or the like, similar to the application to the substrate surface. It is preferable to use a coating apparatus (slit coater) using

(Production of separation walls using photosensitive transfer material)
First, after peeling off and removing the protective film of the photosensitive transfer material, the surface of the photosensitive layer is bonded onto a permanent support (substrate in the present invention) and laminated by heating and pressing through a laminator or the like (laminate). .
As the laminator used for the bonding, 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 increase productivity.

Next, the temporary support is removed. In this way, a photosensitive layer is formed on the substrate. The exposure process, the baking process, the development process, and the water washing process that is performed if desired after the removal of the temporary support may be performed in the same manner as in the coating method described above. A painting wall can be obtained.
As described above, the dark color photosensitive layer can be formed on the substrate by either a coating method or a transfer method.
As described above, in any of the methods, it is possible to easily form a dark color separation wall having a smooth surface according to the exposure pattern.

(Formation of each pixel)
In the method for producing a color filter of the present invention, a pixel group comprising a dark color separation wall produced by the method for producing a dark color separation wall on the substrate and a plurality of pixels having two or more colors. And the plurality of pixels are formed by forming a dark color separation wall and then applying a colored liquid composition between the dark color separation walls.
That is, a colored liquid composition for forming pixels of two or more colors (for example, RGB pixels) is applied to the gap between the dark color separation walls formed on the substrate in the development process. Thus, a plurality of pixels having two or more colors are formed.
As a method for causing the colored liquid composition to enter the separation wall gap, 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, also, the heating temperature when also 2) perform 50 It is about -120 degreeC, Preferably it is about 70-100 degreeC, 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 temperature and time of heating depend on the composition of the dark color photopolymerizable composition and the thickness of the formed layer, but generally from about 120 ° C. to about 100% from the viewpoint of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.

  The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

(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 to be used can be both oily and water-based, and water-based inks based on water are more preferred from the viewpoint of surface tension. The coloring material 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. Further, a coating-type colored ink (colored resin composition, for example, described in JP-A-2005-3861 [0034] to [0063] or JP-A-10-195358 [0009], which is used for producing a known color filter. The composition for inkjet described in [0026] 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 photoacid-crosslinking photosensitive composition containing a colorant such as a pigment described in the section <Photosensitive composition> can be preferably 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 color filter in the present invention is preferably a color filter in which pixels are formed by an inkjet method, and it is preferable to form three color filters by spraying RGB three color inks.
This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.

[Display device]
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. Definitions of display devices and explanations of each display device are, for example, “Electronic display devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display devices (written by Junaki Ibuki, Sangyo Tosho Co., Ltd.) Issue)).
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. 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 by Toray Research Center Research Division 2001)".

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 compensation film. The black matrix 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 (issued by Kentaro Shimadzu Corp., 1994)”, “2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Part 2)” (Omoyoshikichi Co., Ltd.) Fuji Chimera Research Institute published in 2003) ”.

[Target use]
The color filter of the present invention can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile terminals such as mobile phones, digital cameras, car navigation systems, and the like without any particular limitation.

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these. Unless otherwise specified, “%” and “part” represent “% by mass” and “part by mass”, and “molecular weight” means “mass average molecular weight”.

(Example 1)
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., a photosensitive substrate having a composition described below on a glass substrate coater (manufactured by FS Japan Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Composition K1 was applied. Subsequently, after a part of the solvent was dried by VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the EBR (edge bead remover) was unnecessary around the substrate. The coating solution was removed and prebaked at 120 ° C. for 3 minutes to obtain a photosensitive layer K1 having a thickness of 2 μm.

<Photosensitive composition K1>
Carbon black dispersion (composition below) 25.0 parts Propylene glycol monomethyl ether acetate 37.4 parts Methyl ethyl ketone 24.9 parts Binder 1 9.1 parts 2,2-bis (trichloromethyl) -6- [ -4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine 1.2 parts, crosslinking agent (MW-30M manufactured by Sanwa Chemical Co., Ltd.) 2.4 parts, surfactant 1 0.044 parts

<Carbon black dispersion>
・ Carbon black (Nexex 35 manufactured by Degussa) 13.1%
・ Dispersant (the following structure) 0.65%
・ Polymer (benzyl methacrylate / methacrylic acid =
72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

(Exposure process)
In a proximity-type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the photosensitive layer K1 The distance between them was set to 200 μm, and pattern exposure was performed at an exposure amount of 400 mJ / cm ² under a nitrogen atmosphere.
(Bake process)
A heat treatment (110 ° C., 60 seconds) was performed 1 minute after the exposure was completed.

(Development process)
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark photosensitive layer K1, and then a KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, (Fuji Film Electronics Materials Co., Ltd.) was 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 ultra-high pressure cleaning nozzle to remove the residue, and post exposure was performed at an exposure amount of 2000 mJ / cm ^{2 in the} atmosphere to obtain an optical density of 3.9. Got a separation wall. When the surface roughness of the separation wall thus obtained was measured with a contact film thickness meter (tencor stylus type surface roughness meter P10), Ra was 3.2 nm and the separation wall height was 2. It was 0 μm.

[Plasma water repellency treatment]
The substrate on which the separation wall was formed was subjected to plasma water repellency treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.
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: 80 parts ethyl 3-ethoxypropionate

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.

  Next, using the above-described colored inks for R, G, and B pixels, an ink jet method is used in the region (the concave portion surrounded by the convex portion) divided by the separation wall of the image forming substrate obtained above. Was used to discharge the ink composition until the desired concentration was obtained, and a color filter composed of R, G, and B patterns was produced. The color filter after image coloring was baked in an oven at 230 ° C. for 30 minutes to completely cure the black matrix and each pixel.

  The ink constituting each pixel of the color filter thus obtained fits exactly in the gap between the image separation walls, and no defect such as a color mixture with adjacent pixels was found. This is presumably because the ink did not reach the adjacent pixel area because the wettability with respect to the ink on the surface of the upper part of the image separation wall was unexpectedly lowered by using the present invention.

(Overcoat layer)
Thereafter, the glass on which the colored layer has been formed is washed with a low-pressure mercury lamp (effective wavelength 254 nm) UV cleaning device to remove residues and foreign matters, and then a transparent overcoat agent is applied and baked. After coating the front surface so that the thickness of the film was 1.5 μm, it was baked 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 (A) and an epoxy compound represented by the chemical formula (B) were mixed at a weight ratio of 3: 1.

(Formation of ITO)
ITO (indium tin oxide) was formed on the color filter on which the overcoat layer was formed by sputtering to obtain an ITO transparent electrode substrate. The ITO resistance of the color filter was measured (Mitsubishi Yuka "Loresta"; the sheet resistance was measured by the four-probe method) and found to be 13 Ω / □.

(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.

(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / cm with an ultrahigh pressure mercury lamp through the photomask. Proximity exposure at ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.

<Positive photosensitive resin layer coating solution formulation>
-Positive resist solution 53.3 parts (FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.)
・ Methyl ethyl ketone 46.7 parts ・ Surfactant 0.04 parts (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc.)

(Creation of liquid crystal display device)
Using the liquid crystal display device substrate obtained above, a liquid crystal display device was produced using the method described in the first examples [0079] to [0082] of JP-A No. 11-242243.

(Evaluation)
The screen of the liquid crystal display device was a good screen with no color mixing. Moreover, the quality of black display was also good.

Claims (10)

The substrate has two or more image groups exhibiting different colors, and each pixel constituting the pixel group is separated from each other by a dark color separation wall. A color filter manufacturing method for forming each pixel between image separation walls by applying between
A photosensitive layer forming step of forming on the substrate a layer made of a dark color photosensitive composition containing a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, and a colorant; and the photosensitive layer A method for producing a color filter, comprising: an exposure step of exposing an exposed region to cure an exposed region; and a developing step of forming a separation wall by removing a photosensitive layer in an unexposed portion.   The method for producing a color filter according to claim 1, wherein the dark color photosensitive composition further contains a copolymer containing at least one of methyl methacrylate or benzyl methacrylate.   3. The color filter according to claim 1, wherein the photoacid generator is one or more compounds selected from the group consisting of organic halogen compounds, onium salts, and sulfonate esters. Manufacturing method.   The method for producing a color filter according to claim 1, wherein the crosslinking agent is a melamine resin or a urea resin.   5. The method for producing a color filter according to claim 1, wherein a height of the separating wall is 1.8 μm or more and 10 μm or less.   6. The method for producing a color filter according to claim 1, wherein an optical density of the image separation wall is 2.5 or more and 10 or less.   The color filter manufacturing method according to claim 1, wherein the separation wall is black.   A color filter produced by the production method according to claim 1, wherein the separation wall has a surface roughness (Ra value) of 5 nm or less.   A liquid crystal display device comprising the color filter according to claim 8.   A liquid crystal display device comprising the liquid crystal display element according to claim 9.