JP2007178916A - Manufacturing method of color filter, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a color filter free of voids. <P>SOLUTION: The manufacturing method of the color filter comprises forming colored layers by forming deep color separating picture walls having light shieldability on a substrate, and spraying and depositing inks of R, G and B by an ink jet system to recessed parts compartmentalized by the deep color separating picture walls, and satisfying the following (a), (b) and (c): (a) The ink is a polymerizable ink containing a colorant, a polymerizable compound, and a polymerization initiator and having a solvent amount in the ink of ≤50mass%; (b): The corner convex to the deep color separating picture wall side when the boundary line between the colored layer and the deep color separating picture wall is observed from the thickness direction colored layer forming side of the substrate is a curve shape of ≥0.5 μm in the radius of curvature, and (c): The colored layers are formed by spraying and depositing the inks of R, G and B, then curing the same by active energy rays. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystal display device used for a color television, a personal computer monitor, and the like, a color filter which is a constituent member of the liquid crystal display device, and a manufacturing method thereof.

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.

  Recently, there has been described a method for producing a color filter that uses an ink containing a pigment, a monofunctional monomer, and a polyfunctional monomer to form R, G, and B pixels and then cures them with UV light or an electron beam (for example, However, a liquid crystal display device manufactured by a known method using a color filter manufactured by this method has many problems such as display unevenness. This is due to the problem of “white spots” peculiar to the method of applying droplets in the production of such an optical element.

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 different substrate (see, for example, Patent Document 6). Examples of methods for imparting ink affinity include water-soluble leveling agents and water-soluble surfactants.
However, such a method requires a step of imparting ink affinity, which is disadvantageous in terms of cost. Further, these means have not yet been sufficient to suppress white spots.
JP-A-63-298304 JP-A-61-99103 JP-A-61-99102 JP 2002-371216 A JP 2002-372615 A JP-A-9-203803

  Accordingly, an object of the present invention is to provide a method for producing a color filter without white spots, and to provide a color filter obtained by the production method and a liquid crystal display device using the color filter.

The above conventional problems are achieved by the present invention described below. That is, the method for producing the color filter of the present invention includes:
<1> A dark color separation wall having light-shielding properties is formed on a substrate, and R, G, and B inks are sprayed and deposited on the concave portions delimited by the dark color separation wall to form a colored layer. And a color filter manufacturing method characterized by satisfying the following (a), (b) and (c).
(A) The ink contains a colorant, a polymerizable compound, and a polymerization initiator, and the amount of solvent in the ink is 50% by mass or less.
(B) When the boundary line between the colored layer and the dark color separation wall is observed from the colored layer forming side in the thickness direction of the substrate, a corner convex toward the dark color separation wall side has a radius of curvature of 0.5 μm. It must be the above curve shape.
(C) The R, G, and B inks are sprayed and deposited, and then cured by active energy rays to form the colored layer.

<2> The method for producing a color filter according to <1>, wherein the colored layer is formed by further curing with heat after curing with the active energy ray.
<3> The method for producing a color filter according to <1> or <2>, wherein the polymerizable ink is a radical polymerizable composition.
<4> The method for producing a color filter according to <1> or <2>, wherein the polymerizable ink is a cationic polymerizable composition.
<5> The <1> to <1>, wherein the formation of the dark color separation wall on the substrate is performed using a photosensitive composition containing a colorant, a polymerizable compound, and a photopolymerization initiation system. <4> A method for producing a color filter according to any one of the above.
<6> The method for producing a color filter according to any one of <1> to <5>, wherein the dark color separation wall has a height of 1 to 10 μm.
<7> The formation of a dark color separation wall on the substrate is performed by transferring onto the substrate a photosensitive transfer material having a light-shielding layer on a temporary support. It is a manufacturing method of the color filter as described in any one of 1>-<6>.

The color filter of the present invention is
<8> A color filter produced by the production method according to any one of <1> to <7>.

Furthermore, the liquid crystal display device of the present invention is
<9> A liquid crystal display device comprising the color filter according to <8>.

  According to the present invention, it is possible to provide a method for producing a color filter without white spots, and to provide a color filter obtained by the production method and a liquid crystal display device using the color filter.

In the method for producing a color filter of the present invention, after forming a dark color separation wall having light shielding properties on a substrate, inks of R, G, and B are applied by ink jet method to the recesses defined by the dark color separation wall. A production method for forming a colored layer by spraying and depositing, wherein the following (a), (b) and (c) are further satisfied.
(A) The ink contains a colorant, a polymerizable compound, and a polymerization initiator, and the amount of solvent in the ink is 50% by mass or less.
(B) When the boundary line between the colored layer and the dark color separation wall is observed from the colored layer forming side in the thickness direction of the substrate, a corner convex toward the dark color separation wall side has a radius of curvature of 0.5 μm. It must be the above curve shape.
(C) The R, G, and B inks are sprayed and deposited, and then cured by active energy rays to form the colored layer.

  When a polymerizable ink (solvent-free ink) having a solvent amount of 50% by mass or less is dropped on a concave portion partitioned by a previously formed dark color separation wall, the ink does not enter the corners of the dark color separation wall and white spots are generated. A malfunction occurred. This is more conspicuous as the amount of solvent decreases and the concentration increases. However, according to the present invention, the above-mentioned white can be obtained by setting the radius of curvature of the convex corner on the dark color separation wall side to 0.5 μm or more. Omission can be effectively prevented.

Here, the phenomenon of the “white spot” is described.
The “white spot” is a failure that occurs mainly because the applied ink cannot sufficiently and uniformly diffuse into the colored layer portion surrounded by the dark color separation wall, This causes display defects such as 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.
For this reason, as shown in FIG. 1, there is a problem that the ink 36 is not sufficiently diffused with respect to the corners and white spots 38 are generated.

  Hereinafter, in describing the present invention in detail, each element constituting the color filter of the present invention will be described in detail, and then the liquid crystal display device of the present invention will be described.

<Dark color separation wall>
In the present invention, the boundary line between the dark color separation wall and the adjacent colored layer, when viewed from the colored layer formation side in the thickness direction of the substrate, a convex angle to the dark color separation wall side (hereinafter simply referred to as “ The corner is sometimes referred to as a “convex corner on the dark color separation wall side”.) Has a curved shape with a radius of curvature of 0.5 μm or more, and the dark color 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 “corner that protrudes toward the dark color separation wall” is an angle on the colored layer side (an angle when it is assumed that straight portions intersect as they are, not curved shapes). Means a portion whose angle is less than 180 °, and the shape thereof is not particularly limited except that the radius of curvature is 0.5 μm or more.
Further, the observation from the “colored layer forming side of the substrate in the thickness direction” means, of course, the case of observing the boundary line between the formed deep color separation wall and the colored layer and the dark color separation wall and The case where the colored layer is cut so as to be orthogonal to the film thickness direction and the cross section is observed from the colored layer forming side of the substrate in the thickness direction is also included.

Note that the radius of curvature of the corner convex toward the dark color separation wall is 0.5 μm or more at the portion corresponding to the corner convex toward the dark color separation wall of the mask used for exposure. By doing so, it is possible to control within the above range.
By setting the radius of curvature to 0.5 μm or more, ink droplets are sufficiently wet 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. When the radius of curvature is smaller 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 / colored layer pattern cannot be formed.

(Photosensitive composition)
The dark color separation wall in the present invention is formed from a dark photosensitive composition containing a colorant (hereinafter also referred to as “photosensitive resin composition”). 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 is measured by the same method (OD ₀ ), and the value obtained by subtracting OD ₀ from OD is the optical density of the dark color separation wall.

-Colorant-
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 a light-shielding agent 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%.

  Specific examples of the known dyes or pigments include the color materials described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. The pigment described in JP-A-2005-17521 and the colorants described in [0080] to [0088] can be suitably used.

  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 is preferably a photosensitive composition containing a polymerizable compound (monomer) and a photopolymerization initiation system in addition to the colorant. Furthermore, it preferably comprises at least a binder, a resin and a polymer. 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.

-Photopolymerization initiation system-
As a method for curing the photosensitive resin composition, a thermal initiation system using a thermal initiator and a photopolymerization initiation system using a photoinitiator are common, but in the present invention, it is preferable to use a photopolymerization initiation 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 in particular, 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, and 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-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 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.

-Polymerizable compound-
The polymerizable compound (monomer) used in the photosensitive resin composition is preferably a polyfunctional monomer, and 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.

Reaction of compounds having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate with diisocyanates 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 substrate or a temporary support in 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 to 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% by mass, preferably 0.01 to 0.5% by mass, and 0.03 to 0%. .3% by mass 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.
The content of the ultraviolet absorber relative to the total solid content of the photosensitive resin composition is generally 0.5 to 15% by mass, preferably 1 to 12% by mass, and particularly preferably 1.2 to 10% by mass. preferable.

-Others-
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% by mass, preferably 0.02 to 0.7% by mass, and 0.05 to 0.5% by mass 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 color filter, a metallic support, a metal bonded support, glass, ceramic, a 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. (1) The dark color separation wall is formed by applying and drying a photosensitive resin composition containing a colorant on a substrate and then exposing and developing the photosensitive resin composition.
The dark color separation wall can also be obtained by other methods. (2) A dark color photosensitive transfer layer (dark color photosensitive resin layer) formed on a temporary support by the photosensitive resin composition. ) Is transferred onto the substrate, and then exposed and developed to form a dark color separation wall.

The dark color separation wall is generally black in many cases, but is not limited to black.
Here, the black color in the present invention refers to a color whose chromaticity deviation from an 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 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.

-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, pre-baking is performed to obtain a dark color photosensitive resin layer. The dark color photosensitive resin layer may be obtained by removing an unnecessary coating solution around the substrate with an EBR (edge bead remover) or the like and then pre-baking.
The coating is not particularly limited, and can be performed using a known coater for glass substrate having a slit-like nozzle (for example, product name: MH-1600, manufactured by FS Asia Co., Ltd.).
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, in a state where the substrate and a mask having an image pattern (for example, quartz exposure mask) are set up vertically, the distance between the exposure mask surface and the photosensitive resin layer 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 High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ). it can.

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 (transfer method)-
A photosensitive transfer material in which a photosensitive resin layer and a protective film are provided on the photosensitive resin layer is prepared on a temporary support. If necessary, a thermoplastic resin layer or an oxygen barrier 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 heated and pressurized through a laminator or the like to laminate (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, between the temporary support and the photosensitive resin layer (when a thermoplastic resin layer or an oxygen blocking layer is provided, between the temporary support and the thermoplastic resin layer or between the thermoplastic resin layer and the oxygen blocking layer) And the temporary support may be removed. Subsequently, a desired photomask is placed above the removal surface after removal of the temporary support, exposed from a light source, and developed using a predetermined processing solution after exposure to obtain a patterning image. In response to this, washing with water is performed 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 later 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, 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 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 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 during exposure may be insufficient, and 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 pH of the developer is preferably 8-13. A roller conveyor or the like is installed in the developing tank, and the substrate moves horizontally. In order to prevent scratches on the roller conveyor, the photosensitive resin is preferably formed on the upper surface of the substrate. When the substrate size exceeds 1 meter, when the substrate is transported horizontally, the developer stays in the vicinity of the center of the substrate, and a difference in development between the center of the substrate and the peripheral portion becomes a problem. In order to avoid this, it is desirable to incline the substrate diagonally. The inclination angle is preferably 5 ° to 30 °.

  Further, it is preferable to spray pure water before development and moisten the photosensitive resin layer, since a uniform development result is obtained. After development, if air is blown lightly on the substrate to remove excess liquid substantially and then washed with shower water, a more uniform development result is obtained. Further, when the residue is removed by spraying ultrapure water with a pressure of 3 to 10 MPa with an ultrahigh pressure washing nozzle before washing with water, a high-quality image without residue can be obtained. If the substrate is transported to a subsequent process with water droplets attached thereto, the process is soiled or stains remain on the substrate. Therefore, it is preferable to remove excess water and water droplets by draining with an air knife.

(Post exposure)
Post-exposure is preferably performed between development and heat treatment from the viewpoints of controlling the cross-sectional shape of the image, controlling the hardness of the image, controlling the surface unevenness of the image, and controlling the film thickness reduction of the image. Examples of the light source used for the post-exposure include an ultra-high pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp described in paragraph No. 0074 of JP-A-2005-3861. In the post-exposure, it is preferable from the viewpoint of simplification of equipment and power saving that the substrate is directly irradiated with light from a light source such as an ultra-high pressure mercury lamp or a metal halide without using an exposure mask. Implement from both sides as needed. The exposure amount is also adjusted as appropriate according to the control purpose in the range of the upper surface: 100 to 2000 mJ / square centimeter and the lower surface: 100 to 2000 mJ / square centimeter.

(Heat treatment)
The hardness of the image can be ensured by reacting the monomer and the crosslinking agent contained in the photosensitive resin layer of the present invention by heat treatment. The temperature of the heat treatment is preferably in the range of 150 ° C to 250 ° C. If it is less than 150 ° C., the hardness is insufficient, and if it exceeds 250 ° C., the resin is colored and the color purity is deteriorated. The heat treatment time is preferably 10 minutes to 150 minutes. If it is less than 10 minutes, the hardness is insufficient, and if it exceeds 150 minutes, the resin is colored and the color purity is deteriorated. The heat treatment may be changed depending on the color. In addition, after all colors are formed, the final heat treatment may be performed to stabilize the hardness. In that case, it is preferable in terms of hardness to be carried out at a higher temperature (for example, 240 ° C.).

  The height of the dark color separation wall obtained from the above is preferably 1.0 μm or more and 10 μm or less, more preferably 1.9 μm or more and 10 μm or less, and further preferably 2.0 μm or more and 7 μm or less. Especially preferably, it is 2.2 μm or more and 5 μm or less. Setting the height to 1.0 μm or more is preferable in that it can prevent the ink from overcoming adjacent pixels. On the other hand, if it exceeds 10 μm, there is a concern that it is difficult to form a dark color separation wall.

(Method for producing photosensitive transfer material for forming dark color separation image wall)
Here, the production of the photosensitive transfer material will be described.

-Temporary support-
The temporary support in the 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.

-Photosensitive resin layer-
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.

-Oxygen barrier layer-
In addition, the photosensitive transfer material may have an oxygen blocking layer as necessary.
As the oxygen blocking layer in the present invention, it is preferable to use a film having an oxygen blocking ability, and its oxygen transmission rate is preferably 500 cm ³ / (m ² · day · atm) or less, more preferably 100 cm ³ / ( m ² · day · atm) or less, more preferably 50 cm ³ / (m ² · day · atm) or less.

Specifically, the oxygen blocking layer is preferably a layer mainly composed of polyethylene, polyvinylidene chloride, polyvinyl alcohol or the like, and among them, a layer mainly composed of polyvinyl alcohol is more preferable.
The polyvinyl alcohol preferably has a saponification degree of 80% or more. As content of the said polyvinyl alcohol in the said oxygen interruption | blocking layer, 25 mass%-99 mass% are preferable, 50 mass%-90 mass% are more preferable, 50 mass%-80 mass% are especially preferable. Further, polymers such as polyvinyl pyrrolidone and polyacrylamide may be added as necessary, and among them, polyvinyl pyrrolidone is preferable. The addition amount of these polymers is 1-40 mass% of the whole layer, More preferably, it is 10-35 mass%. If the amount of polyvinylpyrrolidone added is too large, oxygen barrier properties may be insufficient.
As the oxygen barrier layer that can be used in the present invention, “separation layer” described in JP-A-5-72724, [0014] to [0015] is also preferred.
In addition, as a film thickness of an oxygen interruption | blocking layer, what is necessary is just a film thickness which can exhibit oxygen interruption | blocking ability, Preferably it is 0.2-10 micrometers, More preferably, it is 0.5-3.0 micrometers.

-Thermoplastic resin layer-
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, and biphenyl diphenyl phosphate.
The preferred film thickness of the thermoplastic resin layer in the photosensitive transfer material is 2 to 30 μm.

-Protective film-
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 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, apply a solution of oxygen barrier layer material consisting of a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, dry it, and then apply the dark color photosensitive resin layer coating solution with a solvent that does not dissolve the oxygen barrier layer. It can be produced by a method such as coating and drying.
Further, a sheet provided with a thermoplastic resin layer and an oxygen blocking layer on the temporary support and a sheet provided with a photosensitive resin layer on a protective film are prepared, and the oxygen blocking layer and the dark photosensitive resin layer are prepared. Further, by sticking together so as to be in contact with each other, a sheet provided with a thermoplastic resin layer on the temporary support, and a sheet provided with a dark color photosensitive resin layer and an oxygen blocking layer on a protective film are further provided. It can also be produced by preparing and bonding them together so that the thermoplastic resin layer and the oxygen blocking layer are in contact with each other.
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.

(Ink repellent treatment)
In the present invention, after ink repellent treatment is performed on the dark color separation wall, that is, in a state where at least a part of the dark color separation wall has ink repellency, ink is applied between the separation wall. It is preferable. This is preferable in order to eliminate inconveniences such as the ink getting over the image separation wall and mixing with the adjacent color when applying droplets by a method such as inkjet.
The ink repellent process is a process of repelling the ink to be applied, and there is no particular limitation on the means. For example, there is a method of applying a fluorine compound, a silicon compound, or the like to at least a part of the dark color separation wall by the method described below.

  Examples of the ink repellent treatment include a method of applying an ink repellent material on the upper surface of the dark color separation wall, a method of newly providing an ink repellent layer, a method of imparting ink repellency by plasma treatment, Examples thereof include a method of kneading into an image wall and a method of imparting ink repellency with a photocatalyst. Note that the present invention is not limited to this.

The ink repellent process will be described in detail below.
(1) <Method of kneading an ink repellent substance on a dark color separation wall>
As a means for preventing “color mixing”, there is a method of preparing a dark color separation wall by adding a fluorine-containing resin (A) to a photoresist obtained from the photosensitive resin composition for forming the dark color separation wall.
The fluororesin (A) in the present invention has an Rf group (a) having a polyfluoroether structure represented by the following formula 1 and an acidic group (b), and an acid value of 1 to 300 mgKOH / g. It is preferable that

-(X-O) _n- Y ... Formula 1
In Formula 1, X is a C1-C10 divalent saturated hydrocarbon group or a C1-C10 fluorinated divalent saturated hydrocarbon group, and is the same for each unit surrounded by n Y represents a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or A fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is shown, and n is an integer of 2 to 50. However, the total number of fluorine atoms in Formula 1 is 2 or more.

As an aspect of X and Y in Formula 1, X is preferably an alkylene group that is fluorinated except for one hydrogen atom having 1 to 10 carbon atoms or a perfluorinated alkylene group that has 1 to 10 carbon atoms. Each of the units enclosed by n represents the same group or a different group, and Y represents a fluorinated alkyl group or a par group having 1 to 20 carbon atoms except for one hydrogen atom having 1 to 20 carbon atoms. The thing which shows the fluorinated alkyl group is mentioned.
As an embodiment of X and Y in Formula 1, more preferably, X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and represents the same group or a different group for each unit surrounded by n. , Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.
When the aspect of X and Y is as described above, the fluororesin (A) exhibits good ink repellency.
In Formula 1, n shows the integer of 2-50. n is preferably from 2 to 30, and more preferably from 2 to 15. When n is 2 or more, the ink falling property is good. When n is 50 or less, the fluororesin (A) is formed by copolymerization of a monomer having an Rf group (a) with a monomer having an acidic group (b) or other monomer. In the case of synthesis, the compatibility of the monomers becomes good.
Moreover, 2-50 are preferable and, as for the total number of the carbon atoms in Rf group (a) which consists of a polyfluoroether structure represented by Formula 1, 2-30 are more preferable. Within this range, the fluororesin (A) exhibits good ink repellency, particularly organic repellency. In addition, when the fluororesin (A) is synthesized by copolymerization with a monomer having an Rf group (a), a monomer having an acidic group (b), and another monomer, Good compatibility.

Examples of _{X, -CF 2 -, - CF} 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 CF (CF 3) -, - CF 2 CF 2 CF 2 CF 2 -, - _{CF 2 CF 2 CF (CF 3} ) -, and _{CF 2 CF (CF 3) CF} 2 - and the like.
Specific examples of _{Y, -CF 3, -CF 2 CF} 3, -CF 2 CHF 2, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, - (CF 2) 4 CF 3, _{- (CF 2) 5 CF 3} , - (CF 2) 6 CF 3, - (CF 2) 7 CF 3, - (CF 2) 8 CF 3, - (CF 2) 9 CF 3, (CF 2) 11 CF _3, and _- the like _{(CF 2)} 15 _{CF 3.}

  A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by Formula 1 includes the Rf group (a) represented by Formula 2.

_{-C p-1 F 2 (p} -1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 2
In Formula 2, p represents an integer of 2 or 3, and is the same group for each unit enclosed by n, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

As Rf group represented by Formula 2 (a), the _{specific, -CF 2 O (CF 2 CF} 2 O) n-1 CF 3 (n is _{2~9), - CF (CF 3} ) O ( _{CF 2 CF (CF 3) O} ) n-1 C 6 F 13 (n is _{2~6), - CF (CF 3} ) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n 2 to 6) are preferable from the viewpoint of ease of synthesis.
The Rf groups (a) in the fluororesin (A) may all be the same or different.
1-60 mass% is preferable and, as for content of the fluorine atom in a fluorine-containing resin (A), 5-40 mass% is more preferable. Within such a range, the fluororesin (A) exhibits good ink repellency and the developability of the photosensitive resin composition of the present invention is good.

The fluororesin (A) has an acidic group (b).
As the acidic group (b), at least one acidic group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group or a salt thereof is preferable.

The acid value of the fluororesin (A) is preferably 1 to 300 mgKOH / g, more preferably 5 to 200 mgKOH / g, and particularly preferably 10 to 150 mgKOH / g. Within this range, the developability of the photosensitive resin composition of the present invention will be good. In addition, an acid value is the mass (unit mg) of potassium hydroxide required in order to neutralize 1 g of resin, and a unit is described in this specification as mgKOH / g.
The number average molecular weight of the fluororesin (A) is preferably 500 or more and less than 20000, and more preferably 2000 or more and less than 15000. Within this range, the developability of the photosensitive resin composition of the present invention is good. The number average molecular weight is measured using polystyrene as a standard substance by gel permeation chromatography.

The fluororesin (A) is a monomer unit based on a monomer having an ethylenic double bond and the Rf group (a), and a single unit having an ethylenic double bond and the acidic group (b). It is a copolymer containing a monomer unit based on a monomer, and preferably has an acid value of 1 to 300 mgKOH / g.
Examples of the group having an ethylenic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group.
As the monomer having the ethylenic double bond and the Rf group (a), CH ₂ = CR ¹ COOQ ² Rf, CH ₂ = CR ¹ OCOQ ¹ Rf, CH ₂ = CR ¹ OQ ¹ Rf, CH ₂ = CR ¹ CH ₂ OQ ¹ Rf, CH ₂ = CR ¹ COOQ ² NR ¹ SO ₂ Rf, CH ₂ = CR ¹ COOQ ² NR ¹ CORf, CH ₂ = CR ¹ COOQ ² NR ¹ COOQ ² Rf, CH ₂ = CR ¹ COOQ ² OQ ¹ Rf, and the like. Here, R ¹ represents a hydrogen atom or a methyl group, Q ¹ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and Q ² represents a divalent organic group having 1 to 6 carbon atoms. Q ¹ and Q ² may have a cyclic structure.
Specific examples of the divalent organic group having 1 to 6 carbon atoms represented by Q ¹ and Q ² are each independently —CH ₂ —, —CH ₂ CH ₂ —, —CH (CH ₃ ) —, —CH. ₂ CH ₂ CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₂ CH ₃ ) —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH (CH ₂ CH ₂ CH ₃ ) —, — _{CH 2 (CH 2) 3 CH} 2 -, - CH (CH 2 CH (CH 3) 2) -, - CH 2 CH (OH) CH 2 -, - CH 2 CH 2 NHCOOCH 2 -, - CH 2 CH ( _OH) CH ₂ OCH 2 - and the like. Among these, —CH ₂ —, —CH ₂ CH ₂ —, and —CH ₂ CH (OH) CH ₂ — are preferable from the viewpoint of ease of synthesis.

Specific examples of the monomer having the ethylenic double bond and the Rf group (a) include the following.
_{CH 2 = CHCOOCH 2 CF 2 O} (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = CHCOOCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n _-1 C ₆ F ₁₃ (n is 2 to 6), CH ₂ = CHCOOCH ₂ CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₃ F ₇ (n is 2 to 6), _{CH 2 = C (CH 3)} COOCH 2 CH 2 NHCOOCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH _{2 CF (CF 3) O (} CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is _{2~6), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH 2 CF (CF 3 _{) O (CF 2 CF (CF} 3 _{O) n-1 C 6 F} 13 (n is _{2~6), CH 2 = C (} CH 3) COOCH 2 CH (OH) CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH 2 CH (OH) CH 2 OCH 2 CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 6 F 13 ( n is _{2~6), CH 2 = C (} CH 3) COOCH 2 CH (OH) CH 2 OCH 2 CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n 2-6).

  The content of the monomer unit based on the monomer having the ethylenic double bond and the Rf group (a) in the fluororesin (A) is preferably 1 to 95 mol%, preferably 5 to 80 mol%. Is more preferable, and 20 to 60 mol% is more preferable. Within such a range, the fluororesin exhibits good ink repellency and the developability of the photosensitive resin composition of the present invention is good.

Examples of the monomer having an acidic group (b) include a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, and a monomer having a sulfonic acid group.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These may be used alone or in combination of two or more.

  Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, one or more hydrogen atoms of these benzene rings are an alkyl group such as a methyl group, an ethyl group or an n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group, a halogen atom or an alkyl group. Also included are compounds in which one or more hydrogen atoms are substituted with halogen atoms, haloalkyl groups, nitro groups, cyano groups, amide groups, and the like. These may be used alone or in combination of two or more.

  Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth) acrylic acid-2-sulfoethyl. , (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, or salts thereof. These may be used alone or in combination of two or more.

  0.1-40 mol% is preferable, as for content of the monomer unit based on the monomer which has an acidic group (b) in a fluorine-containing resin, 0.5-30 mol% is more preferable, and 1-20 mol % Is more preferable. Within such a range, the fluorine-containing resin exhibits good ink repellency and the developability of the photosensitive resin composition becomes good.

Monomer based on a monomer unit in which the fluororesin is based on a monomer having an ethylenic double bond and an Rf group (a), and a monomer having an ethylenic double bond and an acidic group (b) In the case of a copolymer having a body unit, it has a monomer unit based on a monomer having no Rf group (a) and an acidic group (b) (hereinafter referred to as “other monomer”). You may do it.
Other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, (meth) acrylamides, aromatic Examples include vinyl compounds, chloroolefins, fluoroolefins, and conjugated dienes.

These compounds may contain a functional group, and examples of the functional group include a hydroxyl group, a carbonyl group, an alkoxy group, and an amide group. Moreover, you may have group which has a polysiloxane structure. However, the monomer unit based on these other monomers does not have the Rf group (a) and the acidic group (b). These may be used alone or in combination of two or more. In particular, (meth) acrylic acid esters and (meth) acrylamides are preferable because they are excellent in heat resistance of a coating film formed from the photosensitive resin composition of the present invention.
In the fluororesin, the proportion of monomer units based on other monomers is preferably 80 mol% or less, and more preferably 70 mol% or less. Within this range, the developability of the photosensitive resin composition of the present invention will be good.

  The fluororesin in the present invention is a monomer unit based on a monomer having the above ethylenic double bond and Rf group (a), and a single unit having an ethylenic double bond and an acidic group (b). In addition to being obtained by synthesizing a copolymer containing monomer units based on a monomer, a compound having an Rf group (a) and / or a compound having an acidic group (b) in a polymer having a reactive site It can also be obtained by various modification methods to be reacted.

  As various modification methods for reacting a compound having an Rf group (a) with a polymer having a reactive site, for example, a monomer having an epoxy group is copolymerized in advance, and then an Rf group (a) and a carboxyl group are later included. Examples thereof include a method of reacting a compound and a method of previously copolymerizing an epoxy group-containing monomer and then reacting a compound having an Rf group (a) and a hydroxyl group.

  Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

  Examples of the compound having an Rf group (a) and a carboxyl group include compounds represented by the following formula 3.

_{HOOC-C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 3
In Formula 3, p is an integer of 2 or 3, q is an integer of 1 to 20, and n is an integer of 2 to 50.

  Examples of the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following formula 4.

_{HOCH 2 -C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 4
In Formula 4, p represents an integer of 2 or 3, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

  Examples of various modification methods for reacting a polymer having a reactive site with a compound having an acidic group (b) include a method in which a monomer having a hydroxyl group is copolymerized in advance and then an acid anhydride is reacted. Moreover, the method of making the acid anhydride which has an ethylenic double bond copolymerize previously, and making the compound which has a hydroxyl group react later is mentioned.

Specific examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydro Shimechiru (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.
Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (where g is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) g H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) g H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) g H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _k H (where h is 0 or an integer from 1 to 100, k is an integer from 1 to 100, h + k is from 1 to 101. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) h (C 3 H 6 O) k H and the like. These may be used alone or in combination of two or more.

Specific examples of the acid anhydride include phthalic anhydride, 3-methylphthalic anhydride, trimellitic anhydride, and the like.
Specific examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, anhydrous methyl-5-norbornene-2,3-dicarboxylic acid, anhydrous 3,4,5,6 -Tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, etc. are mentioned.
The compound having a hydroxyl group may be a compound having one or more hydroxyl groups. Specific examples of the monomer having a hydroxyl group shown above, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol and ethylene glycol; cellsolves such as 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol; 2- (2-ethoxyethoxy) ethanol; And carbitols such as (2-butoxyethoxy) ethanol. A compound having one hydroxyl group in the molecule is preferred. These may be used alone or in combination of two or more.

  The polymer having the reactive site, which is a fluorine-containing resin or a precursor of the fluorine-containing resin, is reacted by dissolving the monomer in a solvent together with a chain transfer agent as necessary and heating, and adding a polymerization initiator. It can be synthesized by the method.

  0.01-50 mass% is preferable with respect to solid content in the photosensitive resin composition, 0.1-30 mass% is more preferable, and the compounding quantity of a fluorine-containing resin (A) has 0.2-10 mass. % Is particularly preferred. Within this range, the dark color separation wall exhibits good ink repellency and ink falling properties, and developability becomes good.

(2) <Method of providing ink repellent layer>
As means for preventing “color mixing”, a partition wall (hereinafter also referred to as “ink-repellent layer”) having ink repellency at a position matching the dark color separation wall on the substrate on which the dark color separation wall is formed. There is a way to do it.
A silicone rubber layer is preferably used as the partition wall having ink repellency. It is essential that the silicone rubber layer coated on the surface layer has a repulsive effect on the ink used for coloring. Although not particularly limited, it is preferable that the main component is a linear organic polysiloxane having a molecular weight of several thousands to several hundreds of thousands having the following repeating unit.

  Here, n is an integer of 2 or more, and R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a phenyl group.

Silicone rubber can be obtained by sparsely cross-linking such a linear organic polysiloxane.
Examples of cross-linking agents include acetoxy silane, ketoxime silane, alkoxy silane, amino silane, amido silane, and alkenoxy silane used in so-called room temperature (low temperature) curable silicone rubber. In combination with a hydroxyl group, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamide type, and a deketone type silicone rubber are obtained. Moreover, a small amount of an organic tin compound or the like can be added to the silicone rubber as a catalyst.

Various adhesive layers may be used between the photosensitive resin layer and the silicone rubber layer, and aminosilane compounds and organic titanate compounds are particularly preferable.
Instead of providing an adhesive layer between the photosensitive resin layer and the silicone rubber layer, an adhesive component may be added to the silicone rubber layer. As this additional adhesive component, an aminosilane compound or an organic titanate compound can be used.

In order to produce the partition wall, first, a silicone rubber layer is formed on the substrate on which the dark color separation wall is formed.
The exposure for producing the partition wall is performed from the back side of the substrate using the dark color separation wall as a mask, and further, the irradiation UV light is scattered to enlarge the incident light from the size of the transmission part and to act on the photosensitive resin. The portion of the resin that is solubilized by photoreaction is made larger on the silicone rubber layer side. After exposure in this way, a partition wall having a silicone rubber layer can be produced by developing with an n-heptane / ethanol mixture.

(3) <Method of imparting ink repellency by plasma treatment>
As a means for preventing “color mixing”, there is a method of performing ink repellent treatment by plasma on a substrate on which a dark color separation wall is formed.
As the gas containing at least fluorine atoms introduced in this step, one or more halogen gases selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ are used. It is preferable. In particular, C ₅ F ₈ (octafluorocyclopentene) has an ozone depletion ability of 0, and at the same time has an atmospheric life of 0. 0 as compared with conventional gases (CF ₄ : 50,000 years, C ₄ F ₈ : 3200). It is very short with 98 years. Therefore, the global warming potential is 90 (100-year integrated value assuming CO ₂ = 2), which is very small compared to conventional gases (CF ₄ : 6500, C ₄ F ₈ : 8700), and the ozone layer and the global environment. It is extremely effective for protection and is desirable for use in the present invention.

Further, as the introduced gas, a gas such as oxygen, argon, helium or the like may be used in combination as necessary. In this step, when a mixed gas of at least one halogen gas selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ and O ₂ is used, It becomes possible to control the degree of ink repellency on the surface of the deep color separation wall to be processed. However, in the mixed gas, the oxidation reaction mixture ratio by O ₂ exceeds 30 vol% of O ₂ is dominant, because the ink repellency enhancing effect is prevented, also because the damage to the resin is remarkable When the mixed gas is used, it is preferable that the O ₂ mixing ratio is 30% by volume or less.

  In addition, plasma generation methods such as low frequency discharge, high frequency discharge, and microwave discharge can be used. Conditions such as pressure, gas flow rate, discharge frequency, and processing time during plasma processing are arbitrarily set. can do.

(4) <Method of applying an ink repellent material to the surface of the dark color separation wall>
As a means for preventing “color mixing”, there is a method of applying a material having ink repellency to the surface of a substrate on which a dark color separation wall is formed.
Materials that have ink repellency are generally considered to be ink repellent materials such as fluororesin such as polytetrafluoroethylene, silicon rubber, perfluoroalkyl acrylate, hydrocarbon acrylate, methyl siloxane, etc., and have a contact angle of 60 ° or more with respect to ink. If it is a thing, it will not specifically limit.

  The ink-repellent material can be applied by dissolving or dispersing the ink-repellent material in a solvent as it is, and any method that does not affect the substrate, the separation wall, etc. It is possible to select an optimum method for each material such as a coat and a roll coat.

In this method, UV / O ₃ treatment is performed through the dark color separation wall from the back side of the substrate on which the dark color separation wall is formed, and the ink repellent film other than the dark color separation wall is selectively removed. Alternatively, the ink repellent material can be applied by a hydrophilic treatment (the contact angle with respect to the colorant is 30 ° or more before and after the treatment).

  When removing or hydrophilizing the ink repellent material, the patterning method can be selected according to the material, such as laser ablation, plasma ashing, dry treatment such as corona discharge treatment, and wet treatment using alkali. It is. Further, when an ink repellent material is formed on the dark color separation wall, a lift-off method or the like is also effective.

  Among the ink repellent treatment methods (1) to (4) above, (3) an ink repellent treatment method using plasma is particularly preferable from the viewpoint of “simpleness of the process”.

<Colored layer>
As described above, the ink in the present invention includes a colorant, a polymerizable compound, and a polymerization initiator, and is a polymerizable ink in which the amount of solvent in the ink is 50% by mass or less. It is required that the colored layers are formed by spraying the G and B inks and then curing them with active energy rays.

In the present invention, each polymerizable ink is fixed by UV curing after recording, so that there are few volatile components, and since volume shrinkage after curing is small, the film thickness is uniform within the effective range of the colored layer, The uniformity of the color and the thickness of the liquid crystal layer can be improved.
On the other hand, in a system that uses diluted ink (ink whose amount of solvent exceeds 50% by mass), it is necessary to eject a large amount of ink in order to obtain the required optical density of the RGB colored layer, thus preventing color mixing. In order to achieve this, it is necessary to impart sufficient ink repellency to the partition walls. However, in the present invention, solvent-free polymerizable ink is used, and the amount of droplet ejection can be reduced. Therefore, the manufacturing process can be shortened and the cost can be reduced.
Further, in the present invention, it is preferable to perform a thermal effect after curing with an active energy ray, but by combining a curing step with an active energy ray and a thermosetting step, both the production efficiency and characteristics of the color filter are achieved. Can be made.
Hereinafter, the polymerizable ink will be described first.

[Polymerizable ink]
The polymerizable ink used in the present invention comprises a polymerizable coloring composition that contains a colorant, a polymerizable compound, and a polymerization initiator and that is cured by a polymerization reaction caused by active energy rays.

(Coloring agent)
A known colorant (dye, pigment) can be added to the polymerizable coloring composition. In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the polymerizable coloring composition, so that the particle diameter is 0.1 μm or less, particularly 0.08 μm or less. preferable.

  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 Leck 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.

  As the colorant in the present invention, among the above-mentioned colorants, (i) R (red) polymerizable color composition is C.I. I. Pigment Red 254 is C.I. in (ii) G (green) polymerizable coloring composition. I. In the polymerizable coloring composition of (iii) B (blue), CI Pigment Green 36 is C.I. I. Pigment Blue 15: 6 is a preferable example. Furthermore, the above pigments may be used in combination.

  In the present invention, the combination of the above-described pigments preferably used in combination is C.I. I. In pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment yellow 139, or C.I. I. A combination with Pigment Violet 23; I. In Pigment Green 36, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138, or C.I. I. A combination with CI Pigment Yellow 180, and C.I. I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23, or C.I. I. A combination with Pigment Blue 60 is mentioned.

  C. in the pigment when used together in this way. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. The content of Pigment Blue 15: 6 is C.I. I. The pigment red 254 is preferably 80% by mass or more, particularly preferably 90% by mass or more. C. I. The pigment green 36 is preferably 50% by mass or more, particularly preferably 60% by mass or more. C. I. Pigment Blue 15: 6 is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

  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 to a polymerizable compound described later. 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 (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. 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, The average value of 100 is said.

  The contrast of the colored layer can be improved by reducing the particle size of the dispersed pigment. Reduction of the particle size can be achieved by adjusting the dispersion time of the pigment dispersion. For dispersion, the known disperser described above can be used. The dispersion time is preferably 10 to 30 hours, more preferably 18 to 30 hours, and most preferably 24 to 30 hours. When the dispersion time is less than 10 hours, the pigment particle size is large, the polarization due to the pigment is canceled, and the contrast may be lowered. On the other hand, if it exceeds 30 hours, the viscosity of the dispersion increases, and it may be difficult to discharge from the inkjet head. Further, in order to make the difference in contrast between the colored layers of two or more colors within 600, the pigment particle diameter is adjusted to obtain a desired contrast.

  The contrast of each colored layer of the color filter formed from the polymerizable ink is preferably 2000 or more, more preferably 2800 or more, still more preferably 3000 or more, and most preferably 3400 or more. When the contrast of each colored layer constituting the color filter is 2000 or less, when an image of a liquid crystal display device having the color layer is observed, an overall whitish impression is obtained, which is not preferable. Further, the difference in contrast between the colored layers is preferably within 600, more preferably within 410, still more preferably within 350, and most preferably within 200. It is preferable that the difference in contrast between the colored layers is within 600 because the amount of light leakage from each colored layer portion during black display is not significantly different, and the color balance of black display is good.

  In this specification, the “contrast of the colored layer” means a contrast that is individually evaluated for each color of R, G, and B constituting the color filter. The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. The polarizing plate used for the contrast measurement is the same as the polarizing plate used for the liquid crystal display device using the color filter.

(Polymerizable compound)
As the polymerizable compound used in the present invention, a radical polymerizable compound that is cured by a polymerization reaction by a radical active species and a cationic polymerizable compound that is cured by a cationic polymerization reaction by a cationic active species can be used.

(Radically polymerizable compound)
Specific examples of the radical polymerizable compound used in the present invention include the following compounds, but are not limited thereto.
Monofunctional monomers having one ethylenically unsaturated double bond used in the present invention include butanediol monoacrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate 2-methoxyethyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, glycidyl acrylate, isobornyl acrylate, isodecyl acrylate, phenoxy Methacrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, 2- Droxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate Benzyl acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, dipropylene glycol acrylate and the like.

Bifunctional or higher functional monomers and oligomers that are another curing component of the ink used in the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, ethoxylated 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate, tetraethyleneglycol Diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, 1,3-butylene glycol di (meth) acrylate , Ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, trimethylol propane triacrylate, ethoxylated trimethylol propane tri Acrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetra Tyrolmethane triacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, tetramethylol methane tetraacrylate, Pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylol Propane oligoacrylate , Pentaerythritol oligoacrylate, urethane acrylate, epoxy acrylate, polyester acrylate and the like.
These compounds may be used alone or in combination of two or more as required.

(Cationically polymerizable compound)
The cationically polymerizable compound used in the present invention uses a cationically polymerizable compound as a compound that causes a polymerization reaction by a cationic active species generated from a photopolymerization initiator and cures.
As the cationically polymerizable compound, various known cationically polymerizable monomers known as photocationically polymerizable monomers can be used. Examples of the cationic polymerizable monomer include various publications such as JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-220526. And vinyl ether compounds, oxetane compounds, and oxirane compounds described in 1).

  Specific examples of the cationically polymerizable compound having vinyl ether as a functional group include urethane vinyl ether (vinyl ether urethane), ester vinyl ether, and the like. These oligomers can be used alone or in combination.

Specific examples of aromatic epoxy resins include polyphenols having at least one aromatic ring, or polyglycidyl ethers of alkylene oxide adducts thereof such as bisphenol A, bisphenol F, and further alkylene oxide added thereto. And glycidyl ether, epoxy novolac resin, bisphenol A novolac diglycidyl ether, and bisphenol F novolac diglycidyl ether.
Specific examples of the alicyclic epoxy resin include cyclohexene oxide obtained by epoxidizing a polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples thereof include a structure-containing compound, a cyclopentene oxide structure-containing compound, or a vinylcyclohexane oxide structure-containing compound obtained by epoxidizing a compound having a vinylcyclohexane structure with an oxidizing agent. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Meta Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methyl Cyclohexyl carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydro Examples include dioctyl phthalate and di-2-ethylhexyl epoxyhexahydrophthalate.

Specific examples of aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and aliphatic long-chain unsaturated hydrocarbons oxidized with an oxidizing agent. Examples thereof include epoxy-containing compounds, glycidyl acrylate or glycidyl methacrylate homopolymers, glycidyl acrylate or glycidyl methacrylate copolymers, and the like. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetra 1 in glycidyl ether of polyhydric alcohols such as glycidyl ether, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol and glycerin Polyglycidyl ethers of polyether polyols obtained by adding seeds or two or more alkylene oxides, aliphatic long-chain dibases Like diglycidyl ester of. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, polyether alcohol monoglycidyl ethers obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy stearin Examples include octyl acid, epoxy butyl stearate, and epoxidized linseed oil.
When the component having curability by irradiation of these active energy rays falls to 50% by mass or less of the total ink amount, curability becomes insufficient with the intensity of general active energy rays. Therefore, it is necessary to take measures such as extending the irradiation time. From the above, it is desirable that the amount of the curable component is 50% by mass or more, more preferably 60% by mass or more of the total ink.

(Polymerization initiator)
As the polymerization initiator used in the present invention, radical active species are generated by irradiation with active energy rays, radical polymerization initiators that initiate polymerization of radical polymerizable compounds, and cationic active species are generated, and cationic polymerization is performed. Any of the cationic polymerization initiators that initiate the polymerization of the polymerizable compound can be used in accordance with the polymerizable compound.

-Radical polymerization initiator-
Examples of the photopolymerization initiator that can be used in the present invention include the following. As benzophenone series, benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 4,4-diethylaminobenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, etc. Thioxanthone, 2-chlorooxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, isopropylxanthone, and the like are 2-methyl-1- (4-methylthio) phenyl-2-morpholine as acetophenone series. Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy Cyclohexyl Phenyl ketone, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and the like are Benzoin methyl ether, benzoin isobutyl ether, benzyl methyl ketal and the like are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) acylphosphine oxide, etc. as acylphosphine oxides Is mentioned.

-Cationic polymerization initiator-
As the cationic polymerization initiator, diazonium salts, iodonium salts, sulfonium salts, iron arene complexes, and organic polyhalogen compounds can be preferably used. Examples of the diazonium salt, iodonium salt and sulfonium salt include Japanese Patent Publication No. 54-14277, Japanese Patent Publication No. 54-14278, Japanese Patent Publication No. 51-56885, US Pat. Nos. 3,708,296 and 3,853,002. The compounds described in No. are listed.

  Examples of the photocationic polymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, silicon compounds / aluminum complexes, and the like.

(solvent)
The solvent as used in the present invention refers to a solvent described in "New Edition Solvent Pocket Book (edited by Organic Synthetic Science Association, published by Ohm)", such as water, alcohols, ketones, and the like. It is essential that 30% or less is preferable, and 20% is more preferable.

(Inkjet recording method)
In the present invention, the ink jet recording method is such that ink is ejected from an ink jet head to a recess (opening) on a substrate surrounded by a dark color separation partition to form a colored layer, and then irradiated with active energy rays such as ultraviolet rays. Then, the ink is cured.

  As the ink ejection conditions, it is preferable from the viewpoint of ejection stability that the ink is heated to 40 to 70 ° C. and ejected with the ink viscosity lowered. A polymerizable ink generally has a higher viscosity than a water-based ink, and thus has a large viscosity fluctuation range due to temperature fluctuations. Viscosity fluctuations directly affect the droplet size and droplet ejection speed, causing image quality degradation, so it is necessary to keep the ink temperature as constant as possible.

  As the ink jet head (hereinafter also simply referred to as a head) used in the present invention, a known one can be used, and a continuous type or a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

(Ink curing)
In curing the R, G, and B color inks, an exposure process that promotes polymerization and curing is performed using an energy source that emits active energy rays in a wavelength region corresponding to the sensitive wavelength of the polymerizable ink. As an energy source, for example, 200 to 450 nm ultraviolet ray, far ultraviolet ray, g-line, h-line, i-line, KrF excimer laser beam, ArF excimer laser beam, electron beam, X-ray, molecular beam, ion beam, etc. The agent to which the agent is sensitive can be appropriately selected and used. Specifically, a light source that emits actinic rays belonging to a wavelength region of 250 to 450 nm, preferably 365 ± 20 nm, for example, LD, LED (light emitting diode), fluorescent lamp, low pressure mercury lamp, high pressure mercury lamp, metal halide lamp, carbon arc lamp. , Xenon lamps, chemical lamps and the like. Preferred light sources include LEDs, high pressure mercury lamps, and metal halide lamps.

The irradiation time of the active energy ray, can be appropriately set in accordance with the combination of a polymerizable compound and a polymerization initiator, for example, when exposure at an intensity 20 mW / cm ^2, it is 1 to 30 seconds Can do.

(Heating process)
The temperature of the heat treatment is preferably in the range of 150 ° C. to 300 ° C., more preferably 170 ° C. to 280 ° C., and still more preferably 200 ° C. to 250 ° C., from the viewpoint of display unevenness of the color filter and color purity. If it is 150 ° C. or lower, a sufficient display unevenness improving effect may not be obtained, and if it is 300 ° C. or higher, the resin may be colored and the color purity may be deteriorated. The heat treatment time is not particularly limited but is preferably 10 minutes to 150 minutes. If it is less than 10 minutes, the effect may not be sufficiently exhibited. If it exceeds 150 minutes, the resin may be colored and the color purity may be deteriorated.
Among these, a preferable combination of temperature and time is 200 to 250 ° C. and 20 to 130 minutes.

  As the heat treatment means, a color filter in which a dark color separation wall and a colored layer are formed in a concave portion (opening portion) on a substrate is heated in an electric furnace or a dryer, or is irradiated with an infrared lamp. Is preferable.

(Overcoat layer)
After producing the color filter, an overcoat layer may be provided on the entire surface in order to improve solvent resistance or flatness. The overcoat layer can protect the colored layers of the inks R, G, and B and can flatten the surface, but it is preferably not provided from the viewpoint of increasing the number of steps.
Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually composed mainly of an acrylic resin and has excellent adhesion, so that the acrylic resin composition Things are desirable.
Examples of the overcoat layer include those described in paragraphs [0018] to [0028] of JP-A No. 2003-287618, and commercially available overcoat agents such as “Optomer SS6699G” manufactured by JSR Corporation.

<Liquid crystal display device>
There are no particular limitations on the liquid crystal display device to which the present invention can be applied. 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 / Chemicals Market (Kentaro Shima, CMC 1994)” and “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 wall by photosensitive resin transfer material>
-Production of photosensitive resin transfer material-
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, a colored photosensitive resin composition K1 having the composition shown in Table 1 below was applied and dried, and a thermoplastic resin layer having a dry film thickness of 15 μm and a dry film thickness of 1.6 μm were formed on the temporary support. An intermediate layer and a photosensitive resin layer were provided, and a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded.
In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer are integrated is prepared, and the sample name is the photosensitive resin transfer material. It was set as K1.

* Coating solution for thermoplastic resin layer: Formulation H1
Methanol 11.1 parts Propylene glycol monomethyl ether acetate 6.4 parts Methyl ethyl ketone 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.)
5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight = 10,000, Tg≈100 ° C.) 3.6 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl]
Propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts Surfactant 1 0.54 parts

The composition of the 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 of _{H (OCH (CH 3) CH} 2) 7 OCOCH = CH 2: 55 parts of _{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

* Coating solution formulation for intermediate layer (oxygen barrier layer): P1
-Polyvinyl alcohol ... 32.2 parts (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 14.9 parts (PVP, K-30; manufactured by IPS Japan Ltd.)
・ Methanol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 429 parts ・ Distilled water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・..... 524 parts

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 Methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3' in the amounts shown in Table 1 -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 (containing 500 ppm of polymerization inhibitor MEHQ,
Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts ・ Propylene glycol monomethyl ether acetate 24 parts

  The surfactant 1 is the same as the surfactant 1 used in the thermoplastic resin layer coating solution H1.

-Formation of dark color separation wall-
A glass detergent solution adjusted to 25 ° C. is sprayed on an alkali-free glass substrate with a shower for 20 seconds while being washed with a rotating brush having nylon bristles. After washing with pure water, a silane coupling solution (N-β (aminoethyl) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), rubber roller temperature 130 ° C., linear pressure Lamination was performed at 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 100 mJ / cm ² . The mask shape is a lattice shape, and the radius of curvature of the convex corner on the dark color separation wall side in the portion corresponding to the boundary line between the pixel and the dark color separation wall is 0.6 μm.

Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
Subsequently, a sodium carbonate-based developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) was used for shower development at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer to obtain a pattern separation wall.

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.)”), 33 ° C., 20 seconds, cone type Residue removal was performed with a rotating brush having a shower and nylon bristles at a nozzle pressure of 0.02 MPa to obtain a black (K) image. After that, post-exposure with 500 mJ / cm ² light from the resin layer side to the substrate with 500 mJ / cm ² light, and heat treatment at 220 ° C. for 30 minutes to produce a 2.4 μm thick color separation wall. did.

-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

<Formation of pixels with polymerizable ink>
[Preparation of radical polymerizable ink]
Preparation of pigment dispersion The compositions shown in Table 2 below were mixed and stirred with a stirrer for 1 hour. The mixture after stirring was dispersed with an Eiger mill to obtain R, G, and B pigment dispersions. Dispersion conditions were as follows: zirconia beads having a diameter of 0.65 mm were filled at a filling rate of 70%, the peripheral speed was 9 m / s, and the dispersion time was 1 hour.

The pigments in Table 2 above are respectively
・ C. I. Pigment. Red254
(Ciba Specialty Chemicals Co., Ltd., trade name: Irgaphor Red B-CF)
・ C. I. Pigment. Red177
(Ciba Specialty Chemicals Co., Ltd., trade name: Chromophthal Red A2B)
・ C. I. Pigment. Green36
(Toyo Ink Mfg. Co., Ltd., trade name: Rionol Green 6YK)
・ C. I. Pigment. Yellow150
(Product name: Bayplast Yellow 5GN 01, manufactured by Bayer Corporation)
・ C. I. Pigment. Blue15: 6
(Toyo Ink Mfg. Co., Ltd., trade name: Rionol Blue ES)
・ C. I. Pigment. Violet23
(Manufactured by Clariant Japan Co., Ltd., trade name: Hostaperm Violet RL-NF)

Preparation of ink liquid Each of the R, G, and B pigment dispersions was mixed with the composition shown in Table 3, and stirred for 1 hour with a stirrer to obtain inks of R, G, and B.

[Formation of RGB pixels by radical polymerizable ink]
The R ink 1, G ink 1 and B ink 1 obtained above were ejected into the recesses surrounded by the dark color separation wall using a piezo head as follows.
The head has a nozzle density of 150 per 25.4 mm, and has 318 nozzles. By fixing these two nozzles in the nozzle row direction with a shift of 1/2 the nozzle interval, 25 heads are arranged on the substrate in the nozzle array direction. . 300 drops per 4 mm. The head and ink are controlled so that the vicinity of the ejection portion is 50 ± 0.5 ° C. by circulating hot water in the head. Ink ejection from the head is controlled by a piezo drive signal applied to the head, and ejection of 6 to 42 pl per drop is possible. In this embodiment, the head is moved while the glass substrate is conveyed at a position 1 mm below the head. More drops. The conveyance speed was adjusted in the range of 50 to 200 mm / s, and the piezo drive frequency was set in the range up to 4.6 KHz, thereby controlling the droplet ejection amount.
In the present embodiment, the conveying speed and the driving frequency are set so that the pigment coating amounts are 1.1 g / m ² , 1.8 g / m ² , and 0.75 g / m ² for R, G, and B, respectively. Controlled, droplets of R, G, and B were ejected into the recesses corresponding to the desired R, G, and B.

The ejected ink is conveyed to an exposure unit and exposed by an ultraviolet light emitting diode (UV-LED). In this embodiment, NCC A03C manufactured by Nichia Chemical was used as the UV-LED. The LED outputs ultraviolet light having a wavelength of 365 nm from one chip. When a current of about 500 mA is applied, light of about 100 mW is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² can be obtained on the surface. The exposure time after the droplet ejection and the exposure time can be changed depending on the transport speed of the medium and the distance in the transport direction of the head and the LED. In this embodiment, the exposure was performed about 0.5 seconds after landing. Further, the exposure energy on the medium was adjusted between 0.01 and 15 J / cm ² according to the setting of the distance and the conveyance speed.

  For the measurement of the exposure power and exposure energy, a spectroradiometer URS-40D manufactured by USHIO INC. Was used, and a value obtained by integrating the wavelength between 220 nm and 400 nm was used.

  The glass substrate after droplet ejection was baked in an oven at 230 ° C. for 30 minutes, whereby both the dark color separation wall and each pixel were completely cured.

(Formation of ITO electrode)
The glass substrate on which the color filter 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, An ITO transparent electrode was formed.

(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. The following methods were used for the exposure, development, and baking steps.

A proximity exposure machine (manufactured by Hitachi High-Tech 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 / Proximity exposure was performed at cm 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, liquid crystal alignment control protrusions made of a photosensitive resin layer patterned in a desired shape are formed on the color filter side substrate by developing and removing unnecessary portions (exposed portions) of the photosensitive resin layer. A substrate for a display device 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 (Fuji Film Electro
FH-2413F manufactured by Nix Materials Co., Ltd. 53.3 parts ・ Methyl ethyl ketone 46.7 parts ・ Megafac F-780F (Dainippon Ink Chemical Co., Ltd.) 0.04 parts

(Production of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the side of the liquid crystal cell on which the polarizing plate was provided to obtain a liquid crystal display device.

(Example 2)
<Formation of dark color separation wall>
A dark color separation wall was formed in the same manner as in Example 1.

<Formation of pixels>
[Preparation of cationically polymerizable ink]
-Preparation of Pigment Dispersion First, the pigment, monomer and dispersant shown in Table 4 below were placed in a ball mill and dispersed for 16 hours using zircon beads having a diameter of 0.6 mm to obtain a pigment dispersion.

-Preparation of ink liquid The components shown in Table 5 were stirred and mixed, and filtered through a 5.0 µm membrane filter to obtain RGB ink.

[Formation of RGB pixels with cationically polymerizable ink]
A color filter was prepared and an ITO transparent electrode was formed in the same manner as in Example 1, except that the radical polymerizable ink in Example 1 was replaced with the above cationic polymerizable ink. Thus, a liquid crystal display device was produced.

(Example 3)
<Formation of dark color separation wall>
A dark color separation wall was formed in the same manner as in Example 1.

<Formation of pixels>
[Preparation of radical polymerizable ink]
-Preparation of Pigment Dispersion A radical polymerizable ink was prepared in the same manner as in Example 1 except that the composition of the pigment dispersion and the ink was changed to the following Tables 6 and 7, and pixels were formed.

  A liquid crystal display device was produced in the same manner as in Example 1.

Example 4
The same as in Example 1 except that the colored photosensitive resin composition K1 is changed to the colored photosensitive resin composition K2 shown in Table 1 and the film thickness of the dark color separation wall to be formed is 3.2 μm. A liquid crystal display device was produced by the method described above.

(Comparative Example 1)
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.

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

(Comparative Example 3)
In Example 3, a liquid crystal display device was produced in the same manner as in Example 3 except that the mask shape was a lattice and the radius of curvature was 0.3 μm.

(Comparative Example 4)
A liquid crystal display device was produced in the same manner as in Example 1 except that the mask shape was a grid, the radius of curvature was 0.3 μm, and the ink used to form the pixels was changed to an ink having the composition shown in Table 8 below.
In forming the pixels, ink corresponding to the R, G, and B patterns was ejected into the recesses surrounded by the dark color separation partition so that the amount of pigment applied was the same as in Example 1. .

Here, preparation of the R ink 4 shown in Table 8 will be described. The composition of Table 8 is mixed, stirred with a stirrer for 1 hour, and the stirred mixture is dispersed with an Eiger mill to obtain R ink 4. It was. Dispersion conditions were as follows: zirconia beads having a diameter of 0.65 mm were filled at a filling rate of 70%, the peripheral speed was 9 m / s, and the dispersion time was 1 hour.
G ink 4 and B ink 4 were prepared in the same manner except that the compositions shown in Table 8 were used.

  After droplet ejection, it was naturally dried for 30 minutes and further dried at 150 ° C. Thereafter, baking was performed in the same manner as in Example 1 to obtain a color filter. Next, a liquid crystal display device was produced in the same manner as in Example 1.

[Evaluation methods]
<Curvature radius>
As seen in FIG. 5, each corner that is convex from the pixel forming side of the substrate in the thickness direction to the dark color separation wall side is 1 μm on both sides centered on the corner vertex as shown in FIG. The radius of curvature of the boundary line of the length was obtained.

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

<Mixed colors and white spots>
Observation was performed with an optical microscope (× 100) from the pixel forming side of the substrate in the thickness direction, and color mixing and white spots were evaluated. For color mixing, observe whether the color mixture generated by mixing ink between adjacent pixels of different colors is seen in the pixel, and for white spots, there is a portion where no ink is attached in the pixel. In addition, it was observed whether ink remained on the upper surface of the dark color separation wall.
The observation of the mixed color was performed for arbitrary 100 pixels (total 300 pixels) of each color of RGB.
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 results are shown in Table 10.

<Measurement of contrast>
The difference between the luminance when the liquid crystal display devices manufactured in the above Examples and Comparative Examples were displayed in black and the luminance when displayed in white was measured, and Table 10 shows the results.
For the measurement of contrast, “BM-5” manufactured by TOPCON CORPORATION JAPAN was used as a luminance meter, and this was installed at a distance of 50 cm in the vertical direction from the panel surface. The measurement was performed in a dark room.

(Example 5)
A liquid crystal display device was produced in the same manner as in Example 1 except that the method for forming the dark color separation wall was changed to the following method.
<Formation of dark color separation wall>
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 above was applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K2 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a photosensitive resin layer of 3.0 μm. K2 was obtained.

On the photosensitive resin layer K2 produced above, an intermediate layer coating solution having the same formulation P1 as in Example 1 was applied and dried to form a 1.6 μm intermediate layer.
In a proximity type exposure machine (manufactured by Hitachi High-Tech 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 intermediate layer The distance was set to 200 μm, and pattern exposure was performed with an exposure amount of 100 mJ / cm ² . The mask shape was a lattice and the curvature radius of the curved portion was 1.1 μm.
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the intermediate layer, and then a KOH-based developer (KOH, containing a nonionic surfactant, trade names: CDK-1, Fuji Film) (Electronic 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 ultrahigh pressure washing nozzle to remove the residue, thereby obtaining a deep color separation wall. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes to obtain a deep color separation wall having a film thickness of 2.4 μm.

  Evaluation was performed in the same manner as in Example 1 using the liquid crystal display device obtained above. The same effect as in Example 1 was obtained even with the above-described dark-colored separation wall produced by the coating method.

(A) is a conceptual diagram at the time of observing the colored layer and the deep color separation wall in which the white spot has generate | occur | produced from the thickness direction with respect to a board | substrate, (b) is AB of (a). It is a conceptual diagram at the time of observing the cross section in a line 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.

Explanation of symbols

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

Claims (9)

Forming a dark color separation wall having a light-shielding property on the substrate, and spraying and depositing R, G, and B inks by an ink jet method on the recesses defined by the dark color separation wall; and forming a colored layer; and A method for producing a color filter, characterized by satisfying the following (a), (b) and (c).
(A) The ink contains a colorant, a polymerizable compound, and a polymerization initiator, and the amount of solvent in the ink is 50% by mass or less.
(B) When the boundary line between the colored layer and the dark color separation wall is observed from the colored layer forming side in the thickness direction of the substrate, a corner convex toward the dark color separation wall side has a radius of curvature of 0.5 μm. It must be the above curve shape.
(C) The R, G, and B inks are sprayed and deposited, and then cured by active energy rays to form the colored layer.   The method for producing a color filter according to claim 1, wherein the colored layer is formed by further curing with heat after curing with the active energy ray.   The method for producing a color filter according to claim 1, wherein the polymerizable ink is a radical polymerizable composition.   The method for producing a color filter according to claim 1, wherein the polymerizable ink is a cationic polymerizable composition.   The formation of a dark color separation wall on the substrate is performed using a photosensitive composition containing a colorant, a polymerizable compound, and a photopolymerization initiation system. A method for producing a color filter according to one item.   The method for producing a color filter according to claim 1, wherein the dark color separation wall has a height of 1 to 10 μm.   7. The formation of a dark color separation wall on the substrate is carried out by transferring a photosensitive transfer material having a light-shielding layer onto a temporary support, onto the substrate. A method for producing a color filter according to any one of the above.   A color filter produced by the production method according to claim 1.   A liquid crystal display device comprising the color filter according to claim 8.

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