JP2006301040A - Method for manufacturing deep color pixel barrier and pixel barrier, method for manufacturing color filter having the barrier and color filter, and display apparatus having the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a deep color pixel barrier for manufacturing a color filter having pixels without color mixing, to provide a deep color pixel barrier manufactured by the method, to provide a color filter manufactured by the method, and to provide a display apparatus having the color filter. <P>SOLUTION: The deep color pixel barrier is formed by exposing and developing a photosensitive resin composition layer containing a colorant in an oxygen poor atmosphere, and the wall has ≥1.0 μm height and satisfies the following conditions (1). (1) Intersections A<SB>1</SB>, A<SB>2</SB>of a substrate and the cross section of the deep color pixel barrier are determined, as well as the highest point H of the deep color pixel barrier, an intersection G of the substrate with a vertical line from the point H, a straight line L<SB>0</SB>passing H and parallel to the substrate surface, a point P internally dividing between H and G into a proportion of HP:PG=1:3, a straight line L<SB>2</SB>passing P and parallel to the substrate, and intersections B<SB>1</SB>, B<SB>2</SB>of L<SB>2</SB>with the cross section of the deep color pixel barrier; wherein the distance (a) between A<SB>1</SB>and A<SB>2</SB>and the distance b between B<SB>1</SB>, B<SB>2</SB>satisfy b/a≥0.8. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a dark color separation partition wall used for a color filter particularly suitable for a display device and a manufacturing method thereof, a color filter using the same, a manufacturing method thereof, and a display device having a color filter.

  The color filter for a display device has a structure in which red, green, and blue dot-like images are arranged in a matrix on a substrate such as glass, and the boundary is divided by a dark color separation wall such as a black matrix. As a manufacturing method of such a color filter, conventionally, a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development. Colored photosensitive resin liquid method (colored resist method) (see, for example, Patent Document 1) 4) Method of sequentially transferring images formed on a temporary support onto the final or temporary support 5) Pre-coloring A method in which a colored layer is formed by applying the photosensitive resin liquid on a temporary support, and the photosensitive colored layer is sequentially transferred directly onto the substrate, exposed, and developed for the number of colors. There is known a method (transfer method) for forming a multicolor image by the above (see, for example, Patent Document 2). A method using an ink jet method (see Patent Document 3) is also known.

Among these methods, although the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive layer resin solution. On the other hand, the ink-jet method has a problem that the positional accuracy of the pixels is poor, although the loss of the resin liquid is small and advantageous in terms of cost.
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 proposed. Since the edges are rounded and each of the color inks that are subsequently ejected easily passes over the black matrix, color mixing occurs with adjacent pixels and the display quality is degraded. In order to prevent this, a method is disclosed in which the black matrix and the ink have a repelling property or the ink wettability of the black matrix gap is increased (see Patent Documents 4 to 6). However, these methods require special materials for the black matrix coloring resist and ink, and require a step of increasing the surface energy of the black matrix gap (surface modification treatment), which is a cost problem. It is still left.
JP-A-1-152449 JP-A-61-99102 JP-A-8-227010 JP-A-6-347637 JP-A-7-35915 JP-A-10-142418

  The present invention relates to a method for producing a dark color separation wall for producing a color filter having pixels having no color mixture, and a production of a color filter having pixels having no color mixture and the dark color separation wall produced by the production method. It is an object to provide a method, a color filter manufactured by the manufacturing method, and a display device having the color filter.

In view of the above circumstances, the present inventors have conducted intensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> A method for producing a dark color separation wall formed on a substrate, wherein the dark color separation wall exposes and develops a photosensitive resin composition layer containing a colorant in an oxygen-poor atmosphere. A method for producing a dark color separation wall, characterized by having a height of 1.0 μm or more and satisfying the following condition (1).
(1) Let the intersections of the cross-section of the substrate and the dark color separation wall be A ₁ and A ₂ . Let H be the highest point of the dark color separation wall, G be the leg of the perpendicular line from H to the substrate, and L ₀ be a straight line passing through H and parallel to the substrate surface. A point that internally divides H and G into HP: PG = 1: 3 is defined as P, a straight line passing through P and parallel to the substrate surface is defined as L ₂ , and a point where L ₂ intersects the cross section of the dark color separation wall is represented by B _1. , and B _2. When the distance between A ₁ and A ₂ is a and the distance between B ₁ and B ₂ is b, the value of b / a is 0.8 or more.
<2> The method for producing a dark color separation wall according to <1>, wherein the value of b / a is 0.85 or more.
<3> The method for producing a dark color separation wall according to <1> or <2>, wherein the optical density of the dark color separation wall is 2.5 or more.
<4> A dark color separation wall produced by the production method according to any one of <1> to <3>.
<5> On the said board | substrate, it is the dark color separation wall manufactured by the manufacturing method of the dark color separation wall of any one of Claims 1-3, and several color which has two or more colors A method of manufacturing a color filter having a pixel group consisting of pixels, wherein the plurality of pixels are formed by applying droplets of a colored liquid composition after forming the dark color separation wall. A method for producing a color filter.
<6> The method for producing a color filter according to <5>, wherein the plurality of pixels are formed by an inkjet method.
<7> A color filter produced by the production method according to <5> or <6> above.
<8> A display device comprising the color filter according to <7>.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the color filter which manufactures the color filter which has a pixel without defects, such as color mixing, at low cost and high efficiency can be provided.
Furthermore, according to this invention, it aims at providing the color filter manufactured by the said manufacturing method.

The method for producing a dark color separation wall according to the present invention is a method for producing a dark color separation wall formed on a substrate, wherein the dark color separation wall comprises a photosensitive resin composition layer containing a colorant. It is characterized in that it is exposed and developed in a poor oxygen atmosphere, has a height of 1.0 μm or more, and satisfies the following condition (1).
(1) The intersections of the cross section of the substrate and the dark color separation wall are A ₁ and A ₂ . Let H be the highest point of the dark color separation wall, G be the leg of the perpendicular line from H to the substrate, and L ₀ be a straight line passing through H and parallel to the substrate surface. A point that internally divides H and G into HP: PG = 1: 3 is defined as P, a straight line passing through P and parallel to the substrate surface is defined as L ₂ , and a point where L ₂ intersects the cross section of the dark color separation wall is represented by B _1. , and B _2. When the distance between A ₁ and A ₂ is a and the distance between B ₁ and B ₂ is b, the value of b / a is 0.8 or more.

The method for producing the dark color separation wall is a method in which a photosensitive resin composition layer (dark color photosensitive resin composition layer) containing a colorant is formed on the substrate and then exposed and developed in an oxygen-poor atmosphere. is there. The photosensitive resin composition layer is formed by a method of applying a dark photosensitive resin composition (coating method) and a method of transferring a photosensitive transfer material (transfer method).
Hereinafter, the dark color photosensitive resin composition and the photosensitive transfer material will be described.

[Dark color photosensitive resin composition]
The dark color separation wall on the substrate is formed from a photosensitive resin composition containing a colorant (also referred to as “dark color photosensitive resin composition” or “dark color composition”). Here, the dark color composition is a composition having a high optical density, and the value is preferably 2.5 or more, more preferably 2.5 to 10.0, and 2.5 to 6.0. Is more preferable, and 3.0 to 5.0 is particularly preferable. Further, since this dark color composition is preferably cured by a photoinitiating system as described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is 2.0 to 10.0, preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the shape of the separation wall may not be as desired, and if it exceeds 10.0, polymerization cannot be started and it is difficult to produce the separation wall itself.
Hereinafter, the components in the composition will be described.

(Coloring agent)
Specific examples of the colorant used in the present invention include those given the color index (CI) numbers described in the following dyes and pigments.
For the dark color composition of the present invention, organic pigments, inorganic pigments, dyes, and the like can be suitably used. When light-shielding properties are required for the photosensitive resin layer, carbon black, titanium oxide, and iron oxide tetraoxide. In addition to light-shielding agents such as metal oxide powder, metal sulfide powder, and metal powder, a mixture of pigments such as red, blue, and green can be used. Known colorants (dyes and pigments) can be used. Among the known colorants, when a pigment is used, it is preferably dispersed uniformly in the dark color composition.
From the viewpoint of sufficiently shortening the development time, the ratio of the colorant in the solid content of the dark color composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and 50 More preferably, it is -55 mass%.
Examples of the known dyes or pigments include Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 5, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185;
C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73; C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97, C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment Blue 60
C. I. Pigment green 7, C.I. I. Pigment Green 36
C. I. Pigment brown 23, C.I. I. Pigment Brown 25
C. I. Pigment black 1, C.I. I. Pigment black 7 and the like.
In the present invention, among the colorants, a black colorant is preferable. Illustrative examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.
The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state. The portion is a liquid that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.
The colorant (pigment) used in the present invention preferably has a number average particle size of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. On the other hand, if the number average particle diameter of the pigment exceeds 0.1 μm, the polarization is canceled by the pigment, and the contrast is lowered. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, This 100 average value is said.

  The dark composition in the present invention preferably comprises at least a binder / resin / polymer, a polymerization initiator, and a monomer in addition to the colorant. Further, if necessary, a known additive such as a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter, and the like can be further contained. Furthermore, the dark color 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)
The binder used in the dark color composition is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 A coalescence etc. can be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. These binder polymers having a polar group may be used alone or in a composition used in combination with a normal film-forming polymer.

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

  For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

  Specifically, the trihalomethyl group substituted trihalomethyloxazole derivatives or s-triazine derivatives described in JP-A No. 2001-117230, trihalomethyl-s-triazine compounds described in US Pat. No. 4239850, Trihalomethyl group-containing compounds such as the trihalomethyloxadiazole compounds described in US Pat. No. 4,212,976;

  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, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,1,2-bis (9-acridinyl) Acridine compounds such as bis (9-acridinyl) alkane, such as 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; 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbisimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2, 2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole and the like.

  Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a bisimidazole 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 the acridine compound is 9-phenylacridine. 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′-bisimidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. The total amount of the photopolymerization initiator in the dark color composition is 0. 0 of the total solid content (mass) of the dark color composition. 1 to 20% by mass is preferable. 5 to 10% by mass is particularly preferable. The total amount is 0. If the amount is less than 1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. If the amount exceeds 20% by mass, the formed image pattern may be lost or the pattern may be lost during development. Roughness may occur on the surface.

  The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan-based compound or an amine-based compound defined below from the viewpoint that sensitivity can be further improved. Here, the “hydrogen donor” refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

  The mercaptan compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor). In addition, the amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as the following). "Amine-based hydrogen donor"). These hydrogen donors may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-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. -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 donors can be used alone or in admixture of two or more, and the formed image is difficult to drop off from the permanent support at the time of 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-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like. A more preferable combination is 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferable combination is 2-mercaptobenzo 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 to 4: 4 are preferable, and 1: 1 to 1: 3 are more preferable. The total amount of the hydrogen donor in the dark color composition is 0. 0 of the total solid content (mass) of the dark color composition. 1 to 20% by mass is preferable. 5 to 10% by mass is particularly preferable.

(monomer)
As the polyfunctional monomer used in the dark color composition, the following compounds can be 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-diisopropenyl vinyl Zen, 1,4-dihydroxybenzene di (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitic acid, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide , Etc.

  Reaction of a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate with a diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate Things can also be used.

  Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  The content of the polyfunctional monomer in the dark color composition is preferably 5 to 80% by mass, particularly preferably 10 to 70% by mass, based on the total solid content (mass) of the dark color composition. When the content is less than 5% by mass, the resistance to an alkali developer at the exposed portion of the composition may be inferior. When the content exceeds 80% by mass, the tackiness when a dark color composition is obtained is obtained. It may increase and may be inferior in handleability.

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

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

(Other)
-Thermal polymerization inhibitor-
Moreover, it is preferable that the dark color 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 with respect to the total solid content of the dark color composition is generally 0.01 to 1%, preferably 0.02 to 0.7%, and preferably 0.05 to 0.5. % Is particularly preferred.
In addition to the above additives, the dark color composition of the present invention may contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like.

[Photosensitive transfer material]
In order to realize the shape of the separation wall in the present invention easily and at low cost, a layer comprising at least a dark color photosensitive resin composition on the temporary support, and an oxygen blocking layer as necessary, There are methods (3) and (4) described later in which a dark color photosensitive transfer material (hereinafter, also referred to as “photosensitive transfer material”) is used. When a material having an oxygen blocking layer is used, the layer made of the dark color photosensitive resin composition is protected by the oxygen blocking layer and thus automatically becomes in an oxygen-poor atmosphere. Therefore, there is no need to carry out the exposure process under an inert gas or under reduced pressure, so that there is an advantage that the current process can be used as it is.

(Temporary support)
The temporary support in the above photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. The thickness of the temporary support is suitably 5 to 300 μm, preferably 20 to 150 μm. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

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

(Oxygen barrier layer)
In the photosensitive resin transfer material in the present invention, it is preferable to provide an oxygen blocking layer on the photosensitive resin layer formed on the temporary support for the purpose of blocking oxygen during exposure. The oxygen barrier layer has the same physical properties and characteristics as the oxygen barrier layer described in the section of the deep color separation wall described later, and the preferred embodiment is also the same.

(Thermoplastic resin layer)
The photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is preferably alkali-soluble and comprises at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, it is possible to exhibit good adhesion to a permanent support in the dark color separation wall forming method described later.
Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate esters, vinyltoluene and (meth) acrylic. Examples include saponified products of acid ester copolymers, saponified products such as poly (meth) acrylic acid esters, (meth) acrylic acid ester copolymers such as (meth) butyl acrylate and vinyl acetate, and the like.
For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Furthermore, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of organic polymers having a softening point of about 80 ° C. or less according to 1 9 6 8 1/25 25) can be used.
In addition, for an organic polymer material having a softening point of 80 ° C. or higher, various plasticizers compatible with the polymer material are added to the organic polymer material, so that the substantial softening point is 80 ° C. It can also be used as lowered below. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers, or interfaces within a range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.
Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate.

(Protective film)
It is preferable to provide a thin protective film on the photosensitive resin composition layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin composition 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.

(Method for producing photosensitive transfer material)
The photosensitive transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating liquid (thermoplastic resin layer coating liquid) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. After that, 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 coating solution for the dark color photosensitive resin composition with a solvent that does not dissolve the intermediate layer. It can be prepared by drying. In the case where the thermoplastic resin layer is not provided, there is no particular restriction on the solvent for the oxygen blocking layer.
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 an intermediate layer and a dark photosensitive resin composition layer are prepared. Further, the sheet is provided with a thermoplastic resin layer on the temporary support, and a dark photosensitive resin composition layer and an oxygen blocking layer are provided on the protective film. It is also possible to prepare the sheet by sticking 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.

[substrate]
As the substrate (permanent support), a metallic support, a metal bonded support, glass, ceramic, a synthetic resin film, or the like can be used. Particularly preferred is a glass or a transparent synthetic resin film having transparency and good dimensional stability.

[Dark color separation wall]
A mode in which the dark color separation wall of each pixel is formed in a poor oxygen atmosphere by a coating method using the above-described dark color photosensitive resin composition (dark color composition) or a transfer method using a photosensitive transfer material described later. There is.
Here, under the oxygen-poor atmosphere, the partial pressure of oxygen at the time of photocuring the dark color composition or the dark color composition layer in the present invention is 0.15 atm or less, or an oxygen barrier capable of blocking oxygen. Refers to the layer below, and these are as follows in detail.
Normally, the partial pressure of oxygen is 0.21 atm under the atmosphere (1 atm). Therefore, in order to reduce the partial pressure of oxygen to 0.15 atm or less, (a) the atmosphere at the time of exposure is reduced to 0 0.7 b or less, or (b) a gas other than air and oxygen (for example, an inert gas such as nitrogen or argon) is mixed by 40 vol% or more with respect to air.
The poor oxygen atmosphere in the present invention is not particularly limited, and any of the above methods can be used.
When using the method in which the oxygen partial pressure is 0.15 atm or less, 0.10 atm or less is preferable, 0.08 atm or less is more preferable, and 0.05 atm or less is particularly preferable. If the oxygen partial pressure is higher than 0.15 atm, the b / a value is less than 0.8, which may cause inconvenience during pixel formation.
There is no particular limitation on the lower limit of the oxygen partial pressure. By substituting the vacuum or atmosphere with a gas other than air (eg, nitrogen), the oxygen partial pressure can be effectively reduced to zero, which is also a preferred method. The oxygen partial pressure can be measured using an oximeter.

The inert gas refers to a general gas such as N ₂ , H ₂ , or CO ₂ or a rare gas such as He, Ne, or Ar. Among these, N ₂ is preferably used because of safety, availability, and cost.

  The term “under reduced pressure” refers to a state of 500 hPa or less, preferably 100 hPa or less.

As described above, the dark color separation wall of the present invention is formed using the dark color composition, and the following (1) and (2) coating methods, and the following (3) and (4) transfer methods. It is preferable to manufacture by.
That is, (1) the dark color separation wall is exposed to an oxygen-poor atmosphere (oxygen partial pressure of 0.15 atm or less) after the dark color photosensitive resin composition containing the colorant is applied to the substrate and dried. And developed to form.
In addition, (2) the dark color separation wall is formed by applying a dark photosensitive resin composition containing a colorant onto a substrate and drying it, and then in an oxygen-poor atmosphere (on the dark photosensitive resin composition layer, oxygen It is formed by exposure and development in a state in which a blocking layer is provided.
(3) A photosensitive transfer material having a dark color photosensitive transfer layer (dark color photosensitive resin composition layer) formed on a temporary support by the dark color photosensitive resin composition was transferred onto the substrate. Thereafter, it is formed by exposure and development in an oxygen-poor atmosphere (oxygen partial pressure of 0.15 atm or less).
(4) A photosensitive transfer material having a dark color photosensitive transfer layer (dark color photosensitive resin composition layer) formed on a temporary support by the dark color photosensitive resin composition was transferred onto the substrate. Thereafter, it is formed by exposure and development in an oxygen-poor atmosphere (in the state where an oxygen blocking layer is provided on the dark color photosensitive resin composition layer).
The dark color separation wall separates two or more pixel groups and is generally black in many cases, but is not limited to black.

(Oxygen barrier layer)
The oxygen barrier layer referred to in the present invention is a layer having an oxygen permeability of 500 cm ³ / (m ² · day · atm) or less, but the oxygen permeability is 100 cm ³ / (m ² · day · atm) or less. It is preferably 50 cm ³ / (m ² · day · atm) or less.
When the oxygen permeability is higher than 500 cm ³ / (m ² · day · atm), it is difficult to efficiently block oxygen, so that it is difficult to make the separation wall have the desired shape.
Specifically, a layer mainly composed of polyethylene, polyvinylidene chloride, polyvinyl alcohol or the like is preferable, and among these, a layer mainly composed of polyvinyl alcohol is preferable.
The polyvinyl alcohol preferably has a saponification degree of 80% or more. As content of the said polyvinyl alcohol in the oxygen interruption layer of this invention, 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.

In the present invention, as shown in FIG. 1, the cross-sectional shape of the dark color separation wall formed on the substrate is defined as A ₁ and A _{2 at} the intersection of the cross section of the substrate and the dark color separation wall. The vertical point of the vertical line from H to the substrate is G, the straight line passing through H and parallel to the substrate surface is L ₀ , and H and G are internally divided into HP: PG = 1: 3. A point is P, a line passing through P and parallel to the substrate surface is L ₂ , and a point where L ₂ intersects the cross section of the dark color separation wall is B ₁ and B _2, and the distance between A ₁ and A ₂ is a, B ₁ When the distance between B and B ₂ is b, the value of b / a is 0.8 or more.

On the substrate, when the high optical density photosensitive dark composition as described above is photopolymerized under the poor oxygen atmosphere described above, the composition itself absorbs from the surface of the composition toward the substrate. Since the exposure dose is attenuated, the surface is hardened as a result. Furthermore, since it is under an oxygen-poor atmosphere, inhibition of polymerization on the surface of the composition is suppressed, and as a result, the surface is further cured.
In the cross-sectional shape of the dark color separation wall formed on the substrate, the intersection points of the cross section of the substrate and the dark color separation wall are A ₁ and A ₂ , and the highest point of the dark color separation wall is H, A vertical line extending from H to the substrate is G, a straight line passing through H and parallel to the substrate surface is L ₀ , and a point dividing H and G into HP: PG = 1: 3 is P, and P is passed through P to the substrate surface. When the parallel straight line is L ₂ , the point where L ₂ intersects the cross section of the dark separation wall is B ₁ and B ₂ , the distance between A ₁ and A ₂ is a, and the distance between B ₁ and B ₂ is b The value of b / a can be adjusted to 0.8 or more by two contributions under the poor oxygen atmosphere.
These values are measured by actually observing the dark color separation wall formed on the substrate vertically by cutting the substrate vertically to expose the cross section and directly observing with a microscope or the like. By passing through the step of fixing the shape of the separation wall obtained in this way, for example, when used in a color filter, it is difficult for the ink once deposited in the gap to get over the dark separation wall. As a result, it is possible to obtain a good color filter while preventing color mixing with adjacent pixels. The b / a value needs to be 0.8 or more, preferably 0.8 or more and 1.4 or less, more preferably 0.85 or more and 1.2 or less. It is particularly preferable that the ratio is from 9 to 1.1.

  In the present invention, the height h of the dark color separation wall (the distance between the highest point of the dark color separation wall H and the foot G of the perpendicular line from the H to the substrate) is 1. Although it is necessary to be 0 μm or more, it is more preferably 1.5 μm or more and 10 μm or less, further preferably 1.8 μm or more and 7.0 μm or less, and particularly preferably 2.0 μm or more and 5.0 μm or less. Especially, color mixing can be more effectively prevented by setting the thickness to 1.5 μm or more and 10 μm or less. If the height is less than 1.5 μm, color mixing tends to occur, and if it exceeds 10 μm, it becomes difficult to form a dark color separation wall.

The optical density of the dark color separation wall of the present invention is preferably 2.5 or more, more preferably 2.5 to 10.0, further preferably 2.5 to 6.0, and 3.0 to 5.0. Particularly preferred.
By setting the optical density range, a display device having a high contrast is obtained. Moreover, it is preferable that the color of a dark color separation partition is black from the point of the display quality of a display apparatus.

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

Subsequently, with the substrate and a mask having an image pattern (for example, a quartz exposure mask) standing vertically, the distance between the exposure mask surface and the dark color photosensitive resin composition layer is appropriately set (for example, 200 μm). The exposure is performed in a nitrogen atmosphere by setting and purging with nitrogen to control the oxygen partial pressure.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, and the exposure amount can be appropriately selected (for example, 300 mJ / cm ² ). . Moreover, the oxygen partial pressure at this time can be measured using an oximeter (G-102, manufactured by Iijima Electronics Co., Ltd.).

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 dark color photosensitive resin composition 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.

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

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

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

-Formation of dark color separation walls using photosensitive transfer material-
First, after peeling off and removing the protective film of the photosensitive transfer material described above, the surface of the exposed dark photosensitive resin composition layer is bonded onto a permanent support (substrate), and heated and pressed through a laminator or the like for lamination. (Laminated body). 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, the temporary support is removed. Subsequently, a desired photomask is disposed above the removal surface after removal of the temporary support, irradiated with ultraviolet light from a light source in a poor oxygen atmosphere, and developed using a predetermined processing solution after irradiation, A patterning image is obtained and subsequently washed with water as necessary to obtain a dark color separation wall.
As the developer used for the development process and the light source used for the light irradiation, the developer and the light source in the formation using the coating method are similarly used.

[Color filter manufacturing method]
(Formation of each pixel)
The color filter manufacturing method of the present invention is a pixel group comprising a dark color separation wall manufactured by the dark color separation wall manufacturing method and a plurality of pixels having two or more colors on the substrate. The plurality of pixels are formed by applying a droplet of a colored liquid composition after forming the dark color separation wall.
That is, droplets of a colored liquid composition for forming pixels of two or more colors (for example, RGB pixels) are applied to the gaps between the dark color separation walls formed on the substrate in the development process. As a result, a plurality of pixels having two or more colors are formed by intruding into the gaps in the walls of the dark color separation.
As a method for causing the colored liquid composition to enter the separation wall gap, a known method such as an ink jet method or a stripe Geyser coating method can be used, and the ink jet method is preferable in terms of cost.
In addition, before forming each pixel in this way, the shape of the dark color separation wall may be fixed, and the means is not particularly limited, but includes the following.
That is, 1) re-exposure after development (sometimes referred to as post-exposure), and 2) heat treatment at a relatively low temperature after development. The heat treatment here refers to heating a substrate having a dark color separation wall in an electric furnace, a dryer or the like, or irradiating an infrared lamp.

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

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

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

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

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

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

The color filter in the present invention is preferably a color filter in which pixels are formed by an inkjet method, and it is preferable to form three color filters by spraying RGB three color inks.
This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.

[Display device]
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued 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 compensation film. The black matrix of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

[Target use]
The present invention can be applied to a use such as a portable terminal such as a television, a personal computer, a liquid crystal projector, a game machine, and a mobile phone, a digital camera, and a car navigation system without particular limitation.

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

[Production method of dark photosensitive resin composition]
The dark color photosensitive resin composition is first weighed in the amount of carbon black dispersion and propylene glycol monomethyl ether acetate described in the following dark color photosensitive resin composition formulation and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 RPM for 10 minutes, then methyl ethyl ketone, binder P-1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) -3' -Bromophenyl] -s-triazine and surfactant 1 are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM for 30 minutes.

<Dark color photosensitive resin composition formulation>
・ Carbon black dispersion 25 parts ・ Propylene glycol monomethyl ether acetate 8 parts ・ Methyl ethyl ketone 53 parts ・ Binder P-1 9.1 parts ・ Hydroquinone monomethyl ether 0.002 parts ・ DPHA liquid 4.2 parts ・ 2,4-bis ( Trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) -3′-bromophenyl] -s-triazine 0.16 parts Surfactant 1 0.045 parts

<Carbon black dispersion>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant 0.65%

-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

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

<DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%

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

[Example 1]
(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 dark color photosensitive resin composition was prepared with a glass substrate coater (manufactured by FS Japan, trade name: MH-1600) having a slit-like nozzle. The object was applied. Subsequently, after part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the substrate periphery was unnecessary with EBR (edge bead remover). The coating solution was removed and prebaked at 120 ° C. for 3 minutes to obtain a dark photosensitive resin composition layer having a thickness of 2.2 μm.

With a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the dark color photosensitive The distance between the conductive resin composition layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² . The exposure was performed in a nitrogen atmosphere with a nitrogen purge. The oxygen partial pressure at this time (measured using Iijima Electronics Co., Ltd. oxygen meter G-102 type) was 0.01 atm.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark color photosensitive resin composition layer, and then a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1 and Fuji Film Electronics Materials Co., Ltd. were used for 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, and subsequently heat treated at 220 ° C. for 30 minutes to obtain a dark color separation wall.

(Pixel formation)
Next, each of R, G, and B inks was applied to the gaps between the black matrix pattern-like separation walls using an inkjet device, and colored.
In this ink, among the following components, first, a pigment, a polymer dispersant and a solvent are mixed, and a pigment dispersion is obtained using a three roll and a bead mill, and the pigment dispersion is sufficiently stirred with a dissolver or the like. While adding other materials little by little, R (red) ink was prepared.
<R ink composition>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 3 parts ・ First epoxy resin (novolak type epoxy resin) Epicoat 154 manufactured by Yuka Shell
2 parts, 2nd epoxy resin (neopentyl glycol diglycidyl ether) 5 parts, curing agent (trimellitic acid) 4 parts, solvent: 80 parts ethyl 3-ethoxypropionate

Further, C.I. I. Pigment Red 254 instead of C.I. I. G (green) ink was prepared in the same manner as the R ink except that the same amount of Pigment Green 36 was used. Further, C.I. I. Pigment Red 254 instead of C.I. I. B (blue) ink was prepared in the same manner as in the R ink except that the same amount of Pigment Blue 15: 6 was used.
The color filter after pixel coloring was baked in an oven at 230 ° C. for 30 minutes, whereby both the black matrix and each pixel were completely cured to obtain a color filter.

  In the color filter thus obtained, the ink constituting each pixel fits exactly in the dark color separation wall gap, and no defect such as a color mixture with adjacent pixels was found. In addition, the ITO resistance of the color filter was measured (Mitsubishi Yuka "Loresta"; the sheet resistance was measured by the four probe method), and it showed a very low value of 12Ω / □. This is presumably because the flatness of the black matrix surface was unexpectedly increased by using the present invention.

[Evaluation]
(B / a value)
The obtained color filter was cut vertically along with the substrate to expose the cross section, and photographed with a scanning electron microscope (magnification 20000 times). The intersections of the cross-section of the substrate and the dark separation wall are A ₁ and A ₂ , the highest point of the dark separation wall is H, and the perpendicular foot from H to the substrate passes through G and H A straight line parallel to the substrate surface is L ₀ , a point dividing H and G into HP: PG = 1: 3 is P, a straight line passing through P and parallel to the substrate surface is L ₁ , and L ₁ is a dark color separation wall B / a value was obtained by setting B ₁ and B _{2 as} the points crossing the cross section, a as the distance between A ₁ and A ₂ , and b as the distance between B ₁ and B ₂ . The measurement was performed on 10 points selected at random, and the values obtained by averaging these values are shown in Table 1.

(Evaluation of the shape of the upper corner of the dark separation wall)
From the above scanning electron micrograph, the shape of the upper corner of the dark color separation wall was evaluated by the following method. The height from the substrate at the highest height of the separation wall from the substrate is H, the foot of the perpendicular line from the H to the substrate is G, the line is on the straight line HG, and H and G are HP: PG = 1: A point that is internally divided into 4 is Q, and a straight line that passes through Q and is parallel to the substrate surface is L ₂ . Let R ₂ be the point where L ₂ intersects the cross section of the dark separation wall, and L ₃ be the tangent line at R. Let it be the intersection S of L ₃ and L ₀ . When the height of the dark color separation wall is h and the distance from S to the cross section of the dark color separation wall is d, the value of d / h is a measure of the shape of the upper corner of the dark color separation wall. . It can be seen that color mixing is unlikely to occur if the value of d / h is 0.06 or less, and color mixing is less likely to occur if this value is 0.04 or less.

(Evaluation of color mixture between pixels)
The obtained color filter was visually observed with a 200 × optical microscope to examine the presence or absence of color mixture between pixels. 1000 pixels were observed and divided into the following ranks. The results are shown in Table 1. Allowable are those of A rank and B rank.
Rank A: No color mixing B Rank: Color mixing 1-2 places C Rank: Color mixing 3-10 places D Rank: Color mixing 11 places or more

[Example 2]
In Example 1, the following oxygen blocking layer was provided on the dark color photosensitive resin composition layer K1 formed on the glass substrate, and nitrogen was exposed during the exposure of the dark color photosensitive resin composition layer K1. A color filter was obtained in the same manner as in Example 1 except that the purging was not performed, and was similarly evaluated. The results are shown in Table 1.

(Formation of oxygen barrier layer)
On the dark color photosensitive resin composition layer K1, the following oxygen barrier layer was applied so that the dry film thickness was 1.6 μm and dried at 100 ° C. for 3 minutes. The application method is the same as that for the photosensitive resin layer.
<Prescription for oxygen barrier layer>
Polyvinyl alcohol 32.2 parts (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
-14.9 parts of polyvinylpyrrolidone (PVP, K-30; manufactured by ASP Japan)
・ Methanol 429 parts ・ Distilled water 524 parts

[Example 3]
(Preparation of dark photosensitive resin transfer material-1)
On the temporary support of polyethylene terephthalate film having a thickness of 75 μm, the dark color photosensitive resin composition K1 was applied using a slit-like nozzle and dried at 100 ° C. for 3 minutes to obtain a thick film having a dry film thickness of 2.2 μm. A color photosensitive resin composition layer was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded thereon to obtain a dark photosensitive resin transfer material-1.

(Formation of dark color separation wall)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane (trade name: KBM603, 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 dark color photosensitive resin transfer material-1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) has a rubber roller temperature of 130 ° C. Lamination was performed at a linear pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling the temporary support, the exposure mask with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp. The distance between the surface and the photosensitive resin composition layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² . The exposure was performed in a nitrogen atmosphere with a nitrogen purge. The oxygen partial pressure at this time was 0.02 atm.

Subsequently, a sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the dark color photosensitive resin composition layer to obtain a patterned pixel.
Thereafter, post-exposure is performed on the substrate from the dark color photosensitive resin composition layer side with an ultra-high pressure mercury lamp with light of 500 mJ / cm ² , followed by heat treatment at 220 ° C. for 15 minutes to obtain a dark color separation wall. It was.
Thereafter, a color filter was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

[Example 4]
(Preparation of dark photosensitive resin transfer material-2)
In Example 3, the same procedure as in Example 3 was performed except that the following thermoplastic resin layer and intermediate layer (oxygen barrier layer) were provided in the order closer to the temporary support between the temporary support and the photosensitive resin layer. Photosensitive resin transfer material-2 was obtained.

(Formation of thermoplastic resin layer)
The following thermoplastic resin layer coating solution was applied to a 75 μm thick polyethylene terephthalate film temporary support using a slit nozzle so that the dry film thickness was 3 μm and dried at 100 ° C. for 3 minutes.
<Coating liquid formulation for thermoplastic resin layer>
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.) 13.6 parts 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts Surfactant 1 0.54 parts * 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 Part copolymer, molecular weight 30,000 30 parts, methyl ethyl ketone 70 parts

(Formation of oxygen barrier layer)
The following oxygen barrier layer coating solution was applied onto the thermoplastic resin layer using a slit nozzle so that the dry film thickness was 1.6 μm and dried at 100 ° C. for 3 minutes.
<Prescription of coating solution for oxygen barrier layer>
Polyvinyl alcohol 32.2 parts (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
-14.9 parts of polyvinylpyrrolidone (PVP, K-30; manufactured by ASP Japan)
・ Methanol 429 parts ・ Distilled water 524 parts

(Formation of dark color separation wall)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane (trade name: KBM603, 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 dark color photosensitive resin transfer material-2, a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) and a substrate heated at 100 ° C. for 2 minutes to a rubber roller temperature of 130 ° C. Lamination was performed at a linear pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling the temporary support, the exposure mask with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp. The distance between the surface and the dark color photosensitive resin composition layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .
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 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 dark photosensitive resin composition layer to obtain a patterned pixel.

Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film)” at 33 ° C. for 20 seconds, cone type nozzle pressure of 0. Residue removal was performed with a rotating brush having a shower and nylon hair at 02 MPa to obtain a black (K) image.
Thereafter, post-exposure is performed on the substrate from the dark color photosensitive resin composition layer side with an ultra-high pressure mercury lamp with light of 500 mJ / cm ² , followed by heat treatment at 220 ° C. for 15 minutes to obtain a dark color separation wall. It was.
Thereafter, a color filter was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

[Example 5]
In Example 1, it was carried out in the same manner as Example 1 except that it was purged with a mixed gas of air and nitrogen at the time of exposure to make the oxygen partial pressure 0.08 atm, and the development conditions were changed as follows. , Evaluated in the same way. The results are shown in Table 1.
After spraying pure water with a shower nozzle to uniformly wet the surface of the dark color photosensitive resin composition layer, KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1) , Manufactured by Fuji Film Electronics Materials Co., Ltd.) and subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.10 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 residues.

[Example 6]
In Example 3, the same procedure as in Example 3 was performed except that the exposure was purged with a mixed gas of air and nitrogen to make the oxygen partial pressure 0.08 atm, and the development conditions were changed as follows. , Evaluated in the same way. The results are shown in Table 1.
Sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.22 MPa, and the dark photosensitive resin composition layer was developed and patterned.

[Example 7]
The evaluation was performed in the same manner as in Example 4 except that the height of the dark color separation wall was 2.7 μm. The results are shown in Table 1.

[Example 8]
The evaluation was performed in the same manner as in Example 4 except that the height of the dark color separation wall was changed to 3.3 μm. The results are shown in Table 1.

[Example 9]
The evaluation was performed in the same manner as in Example 4 except that the height of the dark color separation wall was 4.5 μm. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, it implemented like Example 1 except having exposed without performing nitrogen purge, and evaluated similarly. The results are shown in Table 1.

  As is clear from Table 1 above, Comparative Example 1 having a b / a value of less than 0.8 was found to have a poor pixel surface shape and color mixing, but in any of Examples 1 to 9, the pixel surface Both the shape and color mixture were good.

[Example 10]
Using the color filters obtained in Examples 4 and 7 to 9, liquid crystal display devices 4 and 7 to 9 were prepared as follows.

(Overcoat layer formation)
The obtained color filter is cleaned with a low-pressure mercury lamp (effective wavelength 254 nm) UV cleaning device to remove residues and foreign matters, and then the following transparent overcoat agent is applied and baked. After coating the front surface so that the thickness of the film was 1.5 μm, it was baked at 230 ° C. for 40 minutes. At this time, the coating liquid for forming the transparent overcoat layer was prepared by mixing a polyamic acid of the following chemical formula 6 and an epoxy compound of the chemical formula 7 in a weight ratio of 3: 1.

(Formation of ITO)
ITO (indium tin oxide) was formed on the color filter on which the overcoat layer was formed by sputtering to obtain an ITO transparent electrode substrate.

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

(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / cm with an ultrahigh pressure mercury lamp through the photomask. Proximity exposure at ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. Display device substrates 4 and 7 to 9 were 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 type resist solution (FH-2413F manufactured by Fujifilm Electronics Materials Co., Ltd.) 53.3 parts ・ Methyl ethyl ketone 46.7 parts ・ Megafac F-780F (Dainippon Ink Chemical Co., Ltd.) 0.04 parts

(Creation of liquid crystal display device)
Using the liquid crystal display device substrates 4 and 7 to 9 obtained above, the liquid crystal display device 4 using the method described in the first embodiment [0079] to [0082] of JP-A-11-242243. 7-9 were produced.

(Evaluation)
The screens of the liquid crystal display devices 4 and 7 to 9 were all good colors with no color mixing. In addition, the black display quality improved in the order of the liquid crystal display devices 4, 7, 8, and 9.

It is an example of the schematic diagram which shows the cross-sectional shape of the deep color separation wall of this invention. It is another example of the schematic diagram which shows the cross-sectional shape of the deep color separation wall of this invention.

Explanation of symbols

Crossing point H of the cross section of A ₁ and A ₂ substrate and dark color separation wall H A straight line parallel to the substrate surface passing through leg L ₀ H of perpendicular line drawn from the highest point GH of dark color separation wall to substrate Points a ₁ and B ₂ L ₂ that internally divide a straight line passing through L ₁ P and parallel to the substrate surface into PH and PG = 1: 3 intersect with a cross section of the dark separation wall a A ₁ Distance B between B ₂ and A ₂ distance B between B ₁ and B ₂ tangent R on straight line L ₃ R passing through point L ₂ Q which is on straight line HG and HG is internally divided into HP: PG = 1: 4 Point S ₂ where L ₂ intersects the cross section of the dark color separation wall h Intersection point of L L ₃ and L ₀ Distance from the height d S of the dark color separation wall to the cross section of the dark color separation wall

Claims (8)

A method for producing a dark color separation wall formed on a substrate, wherein the dark color separation wall has a photosensitive resin composition layer containing a colorant exposed to light and developed in an oxygen-poor atmosphere. A method for producing a dark color separation wall, having a height of 0.0 μm or more and satisfying the following condition (1).
(1) Let the intersections of the cross-section of the substrate and the dark color separation wall be A ₁ and A ₂ . Let H be the highest point of the dark color separation wall, G be the leg of the perpendicular line from H to the substrate, and L ₀ be a straight line passing through H and parallel to the substrate surface. A point that internally divides H and G into HP: PG = 1: 3 is defined as P, a straight line passing through P and parallel to the substrate surface is defined as L ₂ , and a point where L ₂ intersects the cross section of the dark color separation wall is represented by B _1. , and B _2. When the distance between A ₁ and A ₂ is a and the distance between B ₁ and B ₂ is b, the value of b / a is 0.8 or more. 2. The method for producing a dark color separation wall according to claim 1, wherein the value of b / a is 0.85 or more. The method for producing a dark color separation wall according to claim 1 or 2, wherein the optical density of the dark color separation wall is 2.5 or more. A dark color separation wall produced by the production method according to claim 1. A dark color separation wall produced by the method of producing a dark color separation wall according to any one of claims 1 to 3 and a plurality of pixels having two or more colors on the substrate. A method of manufacturing a color filter having a pixel group, wherein the plurality of pixels are formed by forming droplets of a colored liquid composition after forming the dark color separation wall. A method for manufacturing a filter. The method for manufacturing a color filter according to claim 5, wherein the plurality of pixels are formed by an inkjet method. A color filter manufactured by the manufacturing method according to claim 5. A display device comprising the color filter according to claim 7.

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