JP2007127814A - Method of manufacturing partition wall, substrate and color filter with partition wall produced by using method of manufacturing partition wall, display device having color filter, and method of manufacturing optical element using method of manufacturing partition wall - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the method of manufacturing a partition wall useful for manufacturing a color filter in which display quality which has been a problem is improved. <P>SOLUTION: The method of manufacturing the partition wall for forming a pixel by giving droplets of a colored liquid composition at least includes: a photosensitive resin layer forming process of forming a photosensitive resin layer which contains at least a photopolymerization initiator or an initiation system, a monomer and a binder at least on one surface of a substrate; an exposing process of exposing at least the photosensitive resin layer so as to correspond to a partition wall pattern; a developing process of developing the exposed photosensitive resin layer to form the partition wall; and a heat treatment process of carrying out post-baking of the photosensitive resin layer after development. In the manufacturing method of the partition wall, molten viscosity of the photosensitive resin layer at 220°C before post-baking is 1,000 Pa s or more. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method of manufacturing a partition wall used for a color filter particularly suitable for a display device, a substrate with a partition wall and a color filter manufactured using the partition wall manufacturing method, a display device having the color filter, and the The present invention relates to a method for manufacturing an optical element using a method for manufacturing a partition wall.

  The color filter for a display device has a structure in which red, green, and blue dot images are arranged in a matrix on a substrate such as glass, and the boundaries are divided by partition walls 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 RGB pixels are manufactured by an ink jet method has been proposed. However, when observing the cross-sectional shape of the produced black matrix, the upper end and its edge are rounded, and each color ink that is ejected later easily crosses the black matrix, causing color mixing with adjacent pixels and improving the display quality. Reduce.

In order to prevent this, a method is disclosed in which the black matrix and the ink have properties of repelling each other or the wettability of the ink in the black matrix gap is increased (see Patent Documents 4 to 7). However, these methods require a special material 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 JP-A-8-166507

  INDUSTRIAL APPLICABILITY The present invention is suitable for forming a color pixel by applying a droplet of a colored liquid composition (particularly, an ink jet method), and useful for producing a color filter in which the above-described display quality problem is improved. A partition wall manufacturing method, a substrate with a partition wall and a color filter manufactured by using the partition wall manufacturing method, a display device having the color filter, and an optical element manufacturing method using the partition wall manufacturing method are provided. For the purpose.

In view of the above circumstances, the present inventors have conducted extensive 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 photosensitive resin layer forming step of forming a photosensitive resin layer containing at least a photopolymerization initiator or an initiation system, a monomer, and a binder on at least one surface on the substrate; and at least the photosensitive resin layer with a partition pattern An exposure process for exposing so as to correspond to the above, a development process for developing the exposed photosensitive resin layer to form partition walls, and a heat treatment process for post-baking the photosensitive resin layer after development. In a method for manufacturing a partition wall for applying a droplet of a colored liquid composition to form a pixel,
The manufacturing method of the partition characterized by the melt viscosity in 220 degreeC of the said photosensitive resin layer before performing the said post-baking being 1000 Pa.s or more.

<2>
The method for producing a partition wall according to <1>, wherein the photosensitive resin layer is formed by the following method (A) or (B).
(A) A photosensitive resin composition containing a colorant is applied to a substrate and dried.
(B) Using a transfer material in which a photosensitive transfer layer containing a colorant is formed on a temporary support, the photosensitive transfer layer is transferred to a substrate.

<3>
An oxygen blocking layer is provided on the photosensitive resin layer before the exposure step,
The method for manufacturing a partition wall according to any one of <1> and <2>, wherein the exposure step is performed through the oxygen blocking layer provided on the photosensitive resin layer.

<4>
A substrate with a partition, comprising: a substrate; and a partition formed on the substrate by the method for manufacturing a partition according to any one of <1> to <3>.

<5>
A color filter having, on a substrate, a partition wall produced by the method for manufacturing a partition wall according to any one of <1> to <3>, and a pixel group composed of a plurality of pixels of two or more colors,
The color filter, wherein the plurality of pixels are formed by applying droplets of a colored liquid composition between the partition walls after the partition walls are formed.

<6>
<5> The color filter according to <5>, wherein the method of applying the droplets is an inkjet method.

<7>
A display device comprising the color filter according to <5> or <6>.

<8>
<1>-<3> It is a manufacturing method of an optical element using the board | substrate with a partition produced by the manufacturing method of the partition of any one of <1>,
A water repellency treatment step of performing a water repellency treatment on the surface of the partition wall of the substrate with the partition wall, and then a step of forming a pixel by applying droplets of a colored liquid composition between the water repellent partition walls. A method for manufacturing an optical element.

  According to the present invention, it is suitable for producing a color filter that is suitable for forming colored pixels by applying droplets of a colored liquid composition (particularly, an ink jet method) and having improved display quality problems. A partition wall manufacturing method, a substrate with a partition wall and a color filter manufactured by using the partition wall manufacturing method, a display device having the color filter, and an optical element manufacturing method using the partition wall manufacturing method are provided. be able to.

The method for producing a partition wall of the present invention comprises a photosensitive resin layer forming step of forming a photosensitive resin layer containing at least a photopolymerization initiator or an initiation system, a monomer, and a binder on at least one surface on a substrate; An exposure step of exposing at least the photosensitive resin layer so as to correspond to a partition pattern; a development step of developing the exposed photosensitive resin layer to form a partition; and post-developing the photosensitive resin layer In the method for producing a partition for forming a pixel by applying droplets of a colored liquid composition having at least a baking heat treatment step, the melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking Is 1000 Pa · s or more.
Therefore, in the present invention, after post-baking, the deformation of the edge of the photosensitive resin layer constituting the partition walls is suppressed, and the droplets of the colored liquid composition are applied between the partition walls to form pixels. Since the color mixture can be prevented from being formed when the film is formed, a good display quality can be obtained.
The melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking is required to be 1000 Pa · s or more, but 3000 Pa · s or more is more preferable. However, when the melt viscosity is too large, the adhesion to the substrate is deteriorated. Therefore, the melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking is preferably 10,000 Pa · s or less.
In addition, the melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking can be obtained using a Koka type flow tester. For example, using a CFT-500D manufactured by Shimadzu Corporation, a 1 mm diameter This can be determined by performing a temperature rise test at a pressure of 100 kg / cm ^{2 using} a nozzle.

As a method of adjusting the melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking to 1000 Pa · s or more, (A) increasing the concentration of fine particles such as pigments contained in the photosensitive resin composition, (B) Use of a binder having a high glass transition temperature as the binder contained in the photosensitive resin composition may be mentioned.
In addition to this, it can also be achieved by increasing the degree of polymerization of the photosensitive resin composition when exposed to (C). Specific examples in this case include (C1) light contained in the photosensitive resin composition. In terms of materials such as increasing the addition ratio of the polymerization initiator and the initiation system, (C2) using a photopolymerization initiator and initiation system with high initiation efficiency, and (C3) using a binder having a polymerizable group in the side chain. And (C4) approach methods on the process side such as increasing the exposure amount and / or illuminance at the time of exposure. You may implement these methods demonstrated above in combination of 2 or more types. Details of these methods will be described later.

The method for producing the partition wall is a method in which a photosensitive resin layer (dark color photosensitive resin layer) containing a colorant is formed on the substrate and then exposed and developed in an oxygen-poor atmosphere. Here, the photosensitive resin layer may be formed by applying a photosensitive resin composition to a substrate (drying method) or a transfer material (photosensitive material) in which a photosensitive transfer layer containing a colorant is formed on a temporary support. The transferable material is formed by a transfer method.
Hereinafter, the dark color photosensitive resin composition and the photosensitive transfer material will be described.

[Dark color photosensitive resin composition]
The partition on the substrate is preferably formed using 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 at 555 nm, and its value is preferably 2.5 or more, more preferably 2.5 to 10.0, and more preferably 2.5 to 6 0.0 is more preferable, and 3.0 to 5.0 is particularly preferable. In addition, since the dark color composition is preferably cured with an initiator or 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 partition may not be as desired, and if it exceeds 10.0, polymerization cannot be started and it is difficult to produce the partition 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.
Organic pigments, inorganic pigments, dyes, and the like can be suitably used for the dark color composition used in the present invention. When the photosensitive resin layer is required to have light shielding properties, carbon black, titanium oxide, 4 In addition to light-shielding agents such as metal oxide powder such as iron oxide, 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.
The ratio of the colorant in the solid content of the dark color composition is generally preferably in the range of about 30 to 70% by mass from the viewpoint of sufficiently shortening the development time, but post-baking is performed. From the viewpoint of adjusting the melt viscosity at 220 ° C. of the previous photosensitive resin layer to 1000 Pa · s or more, it is preferable to use a pigment as a colorant, and to adjust the concentration of the pigment within a range of 30 to 60% by mass. Is preferred. When the concentration of the pigment is less than 30% by mass, it may be difficult to obtain the above-described melt viscosity. On the other hand, when the concentration of the pigment exceeds 60% by mass, it may be difficult to obtain the above-described melt viscosity because polymerization due to exposure is inhibited and curing is insufficient.

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.

  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 dark composition in the present invention preferably comprises at least a binder (resin, polymer), an 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.

  In addition, in terms of adjusting the melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking to 1000 Pa · s or more, it is preferable to use a binder having a polymerizable group in the side chain, for example, allyl acrylate, And / or a polymer having allyl methacrylate as one of monomer components, a polymer having glycidyl methacrylate as one of monomer components, and the like.

  From the same viewpoint, the binder preferably has a high glass transition temperature, specifically 60 degrees or higher, and more preferably 70 degrees or higher. When the glass transition temperature of the binder is less than 60 degrees, it may be difficult to obtain a high melt viscosity as described above.

(Initiator and initiator system)
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 (also referred to as exposure) of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. 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, a trihalomethyl oxazole 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. 4239850 A trihalomethyl group-containing compound such as a trihalomethyloxadiazole compound 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, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;

  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 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'-bisimidazole.

The said initiator may be used independently and may use 2 or more types together. The total amount of the initiator in the dark color composition is generally preferably 0.1 to 20% by mass of the total solid content (mass) of the dark color composition, but the photosensitive resin layer before post-baking. From the viewpoint of adjusting the melt viscosity at 220 ° C. to 1000 Pa · s or more, 0.5 to 10% by mass is particularly 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. Moreover, when it is less than 0.5 mass%, the high melt viscosity mentioned above may not be obtained. On the other hand, if it exceeds 20% by mass, the formed image pattern may be lost or the pattern surface may be roughened during development.

  The initiator may be configured with a hydrogen donor. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. The “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

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

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2. , 5-dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

  Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.

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

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

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. The total amount of the hydrogen donor in the dark color composition is generally preferably 0.1 to 20% by mass of the total solid content (mass) of the dark color composition, but the photosensitive resin before post-baking. From the viewpoint of adjusting the melt viscosity at 220 ° C. of the layer to 1000 Pa · s or more, 0.5 to 10% by mass is particularly preferable.

  Among the various initiators described above, from the viewpoint of adjusting the melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking to 1000 Pa · s or higher, it is preferable to use one having high starting efficiency. Trihalomethyl group-containing compounds and bisimidazole compounds are preferably used. Among them, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 6- [p- (N, N -Bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bisimidazole may be used. It is particularly preferred.

(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-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, and the like.

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

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

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

(solvent)
In the dark color composition used in 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 the partition wall or the photosensitive transfer material in the present invention, the dark color composition can be applied to the substrate or the temporary support by using a slit-like nozzle, which will be described later. By containing the surfactant, 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.
In addition, 0.001-1 mass% is common, as for content of surfactant with respect to the total solid of a dark color composition, 0.01-0.5 mass% is preferable, and 0.03-0. 3% by mass is particularly preferred.

(UV absorber)
The dark color composition used in 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% by mass, preferably 1 to 12% by mass, and particularly preferably 1.2 to 10% by mass. .

(Other)
-Thermal polymerization inhibitor-
Moreover, it is preferable that the dark color composition used for 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% by mass, preferably 0.02 to 0.7% by mass, and 0.05 to 0%. .5% by mass is particularly preferred.
In addition, the dark color composition used in the present invention may contain “adhesion aid” described in JP-A No. 11-133600, other additives and the like in addition to the above-mentioned additives.

  The thickness of the dark color photosensitive resin layer in the present invention is not particularly limited depending on the solid content of the dark color photosensitive resin composition and the thickness of the partition wall to be formed. 1 to 12 μm is preferable, 1.5 to 12 μm is more preferable, 1.8 to 8 μm is still more preferable, and 2.0 to 6.0 μm is particularly preferable.

[Photosensitive transfer material]
In order to realize the shape of the partition wall in the present invention easily and at low cost, a layer (sometimes referred to as a photosensitive transfer layer or a photosensitive resin layer) made of at least a dark photosensitive resin composition on a temporary support. There are methods (3) and (4) described later in which the provided dark color photosensitive transfer material (hereinafter also referred to as “photosensitive transfer material”) is used. The photosensitive transfer material may be one in which an oxygen blocking layer is provided between the temporary support and the photosensitive transfer layer. When a photosensitive transfer 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 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 photosensitive transfer layer in the above-described 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, and the preferred embodiments are also included. It is the same.

(Oxygen barrier layer)
In the photosensitive resin transfer material in the present invention, for the purpose of blocking oxygen during exposure, it is preferable to form an oxygen blocking layer on the temporary support and further provide a photosensitive resin layer thereon. The oxygen barrier layer has the same physical properties and characteristics as the oxygen barrier layer described in the section of the partition 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, good adhesion to a permanent support (substrate) can be exhibited in the partition wall forming method described later.

  Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.

For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.
In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.
Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.

(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.

(Method for producing photosensitive transfer material)
The photosensitive transfer material used in the present invention is obtained by applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support and drying the thermoplastic resin layer. After that, apply a solution of oxygen blocking layer material consisting of a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, dry, and then do not dissolve the oxygen blocking layer with the coating solution for the dark photosensitive resin composition It is preferable that the material is prepared by coating with a solvent and drying. In the case where the thermoplastic resin layer is not provided, there is no particular restriction on the solvent of the oxygen blocking layer.

The above photosensitive transfer material is prepared by preparing a sheet having a thermoplastic resin layer and an oxygen blocking layer provided on the temporary support, and a sheet having a photosensitive resin layer provided on a protective film. And a dark-colored photosensitive resin layer on the protective film, and a sheet provided with a thermoplastic resin layer on the temporary support, and a dark-colored photosensitive resin layer and a protective film. It can also be produced by preparing a sheet provided with an oxygen blocking layer 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.

[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. In addition, the suitable aspect of the board | substrate used for this invention is mentioned later.

[Partition wall]
The partition of each pixel may be formed 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. The formation may be performed in an oxygen-poor atmosphere. Alternatively, an oxygen blocking layer may be provided.
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.

Usually, the partial pressure of oxygen is 0.21 atm under the atmosphere (1 atm). Therefore, in order to lower the oxygen partial pressure to 0.15 atm or less, (a) the atmosphere at the time of exposure is reduced to 0 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 value of b / a becomes less than 0.8, which may cause inconvenience during pixel formation.
There is no restriction | limiting in particular in the minimum of oxygen partial pressure. By substituting the vacuum or atmosphere with a gas other than air (eg, nitrogen), the oxygen partial pressure can be reduced to virtually 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 partition wall in the present invention is formed using the dark color composition, and is manufactured by the following coating methods (1) and (2) and the following (3) and (4) transfer methods. Is preferred.
That is, (1) the partition wall was developed by applying a dark photosensitive resin composition containing a colorant to a substrate, drying it, and then exposing and developing it in an oxygen-poor atmosphere (oxygen partial pressure of 0.15 atm or less). Form.
(2) The partition walls were coated with a dark color photosensitive resin composition containing a colorant and dried on a substrate, and then in an oxygen-poor atmosphere (an oxygen barrier layer was provided on the dark color photosensitive resin layer). ) To be exposed and developed.
(3) After transferring the photosensitive transfer material having the dark color photosensitive transfer layer (dark color photosensitive resin layer) formed on the temporary support by the dark color photosensitive resin composition onto the substrate, It is formed by exposure and development in an oxygen-poor atmosphere (oxygen partial pressure of 0.15 atm or less).
(4) After transferring the photosensitive transfer material having the dark color photosensitive transfer layer (dark color photosensitive resin layer) formed on the temporary support by the dark color photosensitive resin composition onto the substrate, It is formed by exposure and development in an oxygen-poor atmosphere (a state in which an oxygen blocking layer is provided on the dark color photosensitive resin layer).

(Oxygen barrier layer)
The oxygen barrier layer referred to in the present invention is a layer having an oxygen transmission rate of 500 cm ³ / (m ² · day · atm) or less, and the oxygen transmission rate is 100 cm ³ / (m ² · day · atm) or less. It is preferable that it is 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 partition wall into 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 used for 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, the height of the partition wall is preferably 1.0 μm or more, more preferably 1.5 μm or more and 10 μm or less, still more preferably 1.8 μm or more and 7.0 μm or less, and particularly preferably 2. It is 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 dark color barrier ribs.

The optical density at 555 nm of the partition wall is preferably 2.5 or more, more preferably 2.5 to 10.0, still more preferably 2.5 to 6.0, and particularly preferably 3.0 to 5.0.
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 partition is black from the point of the display quality of a display apparatus.
The partition wall preferably has a value of “absorbance at 600 nm ÷ absorbance at 500 nm” in the range of 0.7 to 1.4. Above all, from the viewpoint of display quality of the display device, it is in the range of 0.75 to 1.2. Is preferable, and the range of 0.77 to 1.15 is more preferable.
If the absorbance ratio is outside the above preferred range, the partition may appear colored.
In order to make the ratio of the absorbance within a preferable range, it can be achieved by adjusting the colorant species.

(Formation of partition walls)
-Formation of partition walls 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, unnecessary coating liquid around the substrate is removed by EBR (edge bead remover), etc., and pre-baked to dark-color photosensitive resin. Get a layer.
The application is not particularly limited, and can be performed using a known coater for glass substrates having a slit-like nozzle (for example, product name: MH-1600, manufactured by F.S. Japan).
The drying can be performed using a known drying apparatus (for example, VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)).
Although it does not specifically limit as prebaking, For example, it can achieve by baking at 120 degreeC for 3 minute (s). The film thickness of the obtained dark color photosensitive resin layer is as described above.

Subsequently, in a state where a mask (for example, a quartz exposure mask) having a substrate and a partition pattern (image pattern) is vertically set, a distance between the exposure mask surface and the dark color photosensitive resin layer is appropriately set (for example, 200 μm). ), And purging with nitrogen to control the oxygen partial pressure and exposing in a nitrogen atmosphere.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp. Moreover, the oxygen partial pressure at this time can be measured using an oximeter (G-102, manufactured by Iijima Electronics Co., Ltd.).
The exposure amount and illuminance at the time of exposure are preferably set larger than usual from the viewpoint of adjusting the melt viscosity at 220 ° C. of the photosensitive resin layer before post-baking to 1000 Pa · s or more. . For example, when the photosensitive resin layer is formed by a coating method, the exposure amount is preferably 100 mJ / cm ² or more, and more preferably 300 mJ / cm ² or more. Further, as the exposure amount in the case of forming the photosensitive resin layer by a transfer method, and is preferably 20 mJ / cm ² or more as illuminance, 40 mJ / cm ² or more is more preferable.
Examples of the light source used for light irradiation at the time of exposure include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

Next, it develops with a developing solution, a patterning image is obtained, it wash-processes with water as needed continuously, and the photosensitive resin layer (partition) patterned by finally carrying out post-baking is obtained.
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 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 include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (for example, sodium bicarbonate, Potassium hydrogen carbonate), 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 of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In any case, it is difficult to make the partition shape suitable.

  Further, after the development step, post-baking is performed after washing with water as necessary. Post bake is heat-treated at a temperature of about 200 to 260 ° C. for about 10 to 60 minutes.

-Formation of partition walls using photosensitive transfer material-
First, after peeling off and removing the protective film of the photosensitive transfer material described above, the exposed surface of the dark 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, the temporary support is removed. Subsequently, a desired photomask is disposed above the removal surface after removal of the temporary support, irradiated with ultraviolet rays from a light source in an oxygen-poor atmosphere, and developed using a predetermined processing solution after irradiation, A patterning image is obtained, followed by washing with water if necessary, and finally post-baking to obtain a partition 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. Further, the post-bake treatment is performed in the same manner as in the case of using the coating method.

(Water repellent treatment)
For the substrate with partition walls obtained through the process described above, it is preferable to perform a water-repellent treatment step of performing water-repellent treatment on the partition wall surface of the substrate with partition walls.
In this water repellency treatment step, it is preferable to perform treatment so that at least a part of the partition wall is in a water-repellent state. This is to eliminate the inconvenience that the ink passes over the partition wall and is mixed with the adjacent color when droplets of the colored liquid composition are subsequently applied between the partition walls by a method such as inkjet.

Examples of the water repellent treatment include a method of applying a water repellent material on the upper surface of the partition, a method of newly providing a water repellent layer, a method of imparting water repellency by plasma treatment, and a method of kneading a water repellent substance into the partition. .
Hereinafter, the water repellent treatment will be described in detail.

(1) <Method of kneading a water-repellent substance into the partition wall>
As a means for preventing “color mixing”, there is a method of producing partition walls using a photoresist obtained from a photosensitive resin composition (dark color photosensitive resin composition) containing a fluororesin (A).
The fluorine-containing resin includes a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a), and a single unit based on a monomer having an ethylenic double bond and an acidic group (b). It is a copolymer containing a monomer unit, and it is preferable that an acid value is 1-300 mgKOH / g. Examples of the ethylenic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group.

As a monomer having an ethylenic double bond and an 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.

However, 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 Q 1, ^{Q 2} _{are, -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. Q ¹ may be a single bond. From the viewpoint of ease of synthesis, —CH ₂ —, —CH ₂ CH ₂ —, and —CH ₂ CH (OH) CH ₂ — are preferable.

Specific examples of the monomer having an ethylenic double bond and an 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 _{2~6), CH 2 = CHCOOCH 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 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 is 2-6).

  The content of the monomer unit based on the monomer having an ethylenic double bond and Rf group (a) in the fluororesin is preferably 1 to 95%, more preferably 5 to 80%, and more preferably 20 to 20%. 60% 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.

Examples of the monomer having an acidic group (b) include a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, a sulfonic acid group, and a monomer having a hydroxyl 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 alkyl groups such as methyl, ethyl and n-butyl groups, alkoxy groups such as methoxy, ethoxy and n-butoxy groups, halogen atoms and alkyl groups. Examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, a haloalkyl group, a nitro group, a cyano group, or an amide group. 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.

  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 100. 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.

  The content of the monomer unit based on the monomer having an acidic group (b) in the fluororesin is preferably 0.1 to 40%, more preferably 0.5 to 30%, and 1 to 20%. Further preferred. 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 monomer unit based on monomer having fluorine-containing resin having ethylenic double bond and Rf group (a), and monomer having ethylenic double bond and 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 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 esters, (meth) acrylamides, aromatic Examples include vinyl compounds, chloroolefins, fluoroolefins, and conjugated dienes. These compounds may contain a functional group, and examples thereof 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, monomer units based on these other monomers do not have an Rf group (a) and an 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% or less, and more preferably 70% 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 general formula (1).
・ General formula (1)
_{HOOC-C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1
In general formula (1), 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 the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following general formula (2).
・ General formula (2)
_{HOCH 2 -C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1
In general formula (2), 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 100. 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.

  The acid value of the fluororesin 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 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 blending amount of the fluororesin (A) is preferably 0.01 to 50%, more preferably 0.1 to 30%, and particularly preferably 0.2 to 10% with respect to the solid content in the photosensitive resin composition. preferable. Within such a range, the photosensitive resin composition exhibits good ink repellency and ink tumbling properties and good developability.

(2) <Method of providing a water repellent layer>
As a means for preventing “color mixing”, there is a method of producing a partition wall having ink repellency at a position matching the partition on the substrate on which the partition is formed.
A silicone rubber layer is preferably used as the partition wall having ink repellency. The silicone rubber layer coated on the surface layer is required to have a repulsive effect on the solution and ink used for coloring, but is not limited to this, but the number of molecular weights having the following repeating units: The main component is one thousand to several hundred thousand linear organic polysiloxane.

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. Cross-linking agents are acetoxysilane, ketoxime silane, alkoxysilane, aminosilane, amidosilane, alkenoxysilane, etc., used for so-called room temperature (low temperature) curable silicone rubbers. In combination with these, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamid type, and a deketone type silicone rubber are obtained.
In addition, a small amount of an organic tin compound or the like is 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.

  The exposure for producing the partition wall is performed from the back side of the substrate using the partition wall as a mask, and further, the irradiated UV light is scattered to expand the incident light from the size of the transmission part and act on the photosensitive resin to cause a photoreaction. The portion of the resin to be solubilized is made larger on the silicone rubber surface layer side. After exposure in this manner, a partition wall having a silicone rubber surface layer can be produced by developing with an n-heptane / ethanol mixture.

(3) <Method of imparting water repellency by plasma treatment>
As a means for preventing “color mixing”, there is a method of performing water repellency treatment by plasma on a substrate on which a partition 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 (CF ₄ : 50,000 years, C ₄ F ₈ : 3200 years) as compared with conventional gases. 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 (CF ₄ : 6500, C ₄ F ₈ : 8700) compared to conventional gases, 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, or helium 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 partition treated in this step. However, in the mixed gas, the oxidation reaction mixture ratio by O ₂ exceeds 30% of O ₂ is dominant, because the ink repellency enhancing effect is prevented, also, O ₂ mixing ratio is more than 30% When the mixed gas is used, it is necessary to use O ₂ in a range where the mixing ratio of O ₂ is 30% 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 a water repellent material to the upper surface of the partition wall>
As a means for preventing “color mixing”, there is a method in which a water repellent material is applied to the entire surface of a substrate on which a partition wall is formed.
Water repellent materials such as fluoropolymers such as polytetrafluoroethylene, silicone rubber, perfluoroalkyl acrylate, hydrocarbon acrylate, methyl siloxane, etc. are generally considered to be water repellent materials and have a contact angle of 60 ° or more to the colorant. If it is a thing, it will not specifically limit.

As a method for applying the water repellent material, it is possible to select an optimum method for each material such as slit coating, spin coating, dip coating, and roll coating as long as the method does not affect the substrate, partition walls, and the like.
Next, UVO ₃ treatment is performed from the back side of the substrate through the partition, and the water-repellent film other than the partition is selectively removed or hydrophilized (the contact angle with the colorant is 30 ° or more before and after the treatment). Yes)

If the water repellent material can be removed or hydrophilized, 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. Is possible. In addition, if it is possible to form a pattern of a water repellent material on the partition wall, a lift-off method or the like is also effective.
Among the water repellent treatment methods (1) to (4), the water repellent treatment method using plasma is particularly preferred from the viewpoint of “simpleness of the process”.

[Color filter manufacturing method]
(Formation of each pixel)
The color filter manufacturing method of the present invention includes a partition wall manufactured by the partition wall manufacturing method and a pixel group including a plurality of pixels of two or more colors on the substrate, and the plurality of pixels are After the partition walls are formed, the colored liquid composition is formed by applying droplets.
That is, a dark color is formed by applying a droplet of a colored liquid composition for forming pixels of two or more colors (for example, RGB pixels) into the gaps between the partition walls formed on the substrate in the development step. A plurality of pixels having two or more colors are formed by invading the gaps between the separated walls.
As a method for causing the colored liquid composition to enter the partition 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, the shape of the partition wall may be fixed before forming each pixel in this way, and the means is not particularly limited, and examples thereof include 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 partition wall in an electric furnace, a drier 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 curing of the partition walls does not proceed, and when the temperature is higher than 120 ° C., there is a concern that the shape of the partition walls may collapse.

  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.

[Method for Manufacturing Optical Element]
The optical element manufacturing method of the present invention uses a substrate with a partition wall manufactured by the method for manufacturing a partition wall of the present invention. And forming a pixel by applying a droplet of a colored liquid composition between the partition walls.
The optical element (color filter) thus manufactured 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.

In addition, as one of the liquid crystal display elements, at least one of the liquid crystal layer and the liquid crystal driving means (simple matrix driving method and active matrix driving) is interposed between a pair of substrates that transmit light (including the substrate with the light shielding film of the present invention). Including at least a method).
In this case, the color filter of the present invention has a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a partition wall (in this case, preferably a black matrix). Configured as a filter.
Since this color filter has little color mixing that is likely to occur when pixels are formed, a liquid crystal display element using this color filter can obtain good display quality.

  Further, as another aspect of the liquid crystal display element, at least one of them includes a liquid crystal layer and a liquid crystal driving means between a pair of light transmissive substrates (including the substrate with a light-shielding film of the present invention), and the liquid crystal driving means Has an active element (for example, TFT), and a partition portion (in this case, preferably a black matrix) constituting the color filter of the present invention is arranged between each active element It is. Also in this case, the color filter of the present invention has a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a partition wall (in this case, preferably a black matrix). Configured as a color filter.

Examples of liquid crystals that can be used in the liquid crystal display element include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.
In addition, the pixel group of the color filter may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used.

  As the light transmissive substrate, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.

[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 color filter 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” represents “weight average molecular weight”.

[Production method of photosensitive resin composition]
The photosensitive resin composition is first weighed in the amounts of carbon black dispersion and propylene glycol monomethyl ether acetate described in the following photosensitive resin composition formulation, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred 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.

<Photosensitive resin composition prescription K1>
・ Carbon black dispersion (carbon black particle size 20 nm) 38.7 parts ・ Propylene glycol monomethyl ether acetate 19.8 parts ・ Methyl ethyl ketone 35.5 parts ・ Binder P-1 2.61 parts ・ Hydroquinone monomethyl ether 0.003 parts -DPHA solution 3.21 parts-2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine 0.17 parts・ Surfactant 1 0.04 parts

<Carbon black dispersion>
・ Carbon black (Nexex 35, manufactured by Degussa) 13.1 parts ・ Dispersant (see below) 0.65 parts

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

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

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

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

[Example 1]
(Formation of partition walls)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the photosensitive resin composition was prepared using a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. 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 film thickness of 2.2 μm. A resin layer was obtained.

With 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 photosensitive resin The distance between the layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 800 mJ / cm ² .

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer, and then a KOH developer (KOH, containing a nonionic surfactant, product names: CDK-1, Fuji) The film was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa using a film electronics materials, to obtain a patterning image.

Here, the melt viscosity at 220 ° C. of the photosensitive resin layer after development (before host baking) was measured. The melt viscosity was measured by a temperature rise test at a pressure of 100 kg / cm ² with a 1 mm diameter nozzle using CFT-500D manufactured by Shimadzu Corporation.
In addition, for the measurement of melt viscosity, two substrates having been subjected to the above-described development process are prepared, one is used for sampling the photosensitive resin layer necessary for melt viscosity measurement, and the other is post-baked. The subsequent steps were used to produce a color filter.

  After development, ultrapure water was subsequently sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues, and subsequently heat treated (post-baked) at 220 ° C. for 30 minutes to obtain partition walls.

[Plasma water repellency treatment]
The substrate on which the partition walls were formed was subjected to plasma water repellency treatment under the following conditions using a cathode coupling parallel plate type plasma processing apparatus.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

(Pixel formation)
Next, each of R, G, and B inks was applied to the gaps between the black matrix pattern-like partition walls using an ink jet 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 the partition walls (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 gap between the partition walls, and no defect such as a color mixture with adjacent pixels was found.

(Liquid crystal display device)
A transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above by sputtering. Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively.

A photo spacer was provided in a portion corresponding to the upper part of the partition wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
Then, after printing an epoxy resin sealant at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter and dropping the PVA mode liquid crystal and bonding it 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 an example cathode tube was constructed and arranged on the side of the liquid crystal cell on which the polarizing plate was provided to form a liquid crystal display device.

[Evaluation]
(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 2, a liquid crystal display device was produced in the same manner as in Example 1 except that the photosensitive resin composition formulation was changed to the following formulation and the exposure amount was changed to the conditions shown in Table 1.

<Photosensitive resin composition prescription K2>
・ Carbon black dispersion (carbon black particle size 20 nm) 25.8 parts ・ Propylene glycol monomethyl ether acetate 24.8 parts ・ Methyl ethyl ketone 35.5 parts ・ Binder P-2 9.48 parts ・ Hydroquinone monomethyl ether 0.003 parts DPHA solution 4.17 parts 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine 0.22 parts・ Surfactant 1 0.04 parts

<Binder P-2>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 38/25/37 molar ratio, molecular weight 37,000) 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts

[Example 3]
A liquid crystal display device was produced in the same manner as in Example 1 except that the photosensitive resin composition formulation K3 using the following binder P-3 was used instead of the binder P-2 in Example 2.

<Binder P-3>
・ Methacrylic acid / allyl methacrylate copolymer (methacrylic acid / allyl methacrylate = 20/80 molar ratio random copolymer, weight average molecular weight 36000) 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts

[Example 4]
The amount of 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine added in Example 2 was 0.17 part. A liquid crystal display device was produced in the same manner as in Example 1 except that the photosensitive resin composition formulation K4 changed to 0.85 parts was used.

[Example 5]
0.17 part of the amount of 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine in Example 2 was added. A liquid crystal was produced in the same manner as in Example 1 except that the photosensitive resin composition formulation K5 changed to 0.85 part of 2- (o-chlorophenyl) -4,5-diphenylimidazole dimmer (initiator: lophine dimer) was used. A display device was produced.

[Example 6]
In the same manner as in Example 1, except that the photosensitive resin composition formulation K6 using the binder P-1 instead of the binder P-2 in Example 2 was used and the exposure amount was changed to the exposure described in Table 1. A liquid crystal display device was produced.

[Example 7]
(Preparation of photosensitive resin transfer material-1)
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, the photosensitive resin composition formulation K1 was applied and dried. Thus, a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a photosensitive resin layer having a dry film thickness of 2.2 μm are provided on the temporary support. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded.
In this way, a photosensitive 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 dark photosensitive transfer material. It was set as K1.

<Coating liquid for thermoplastic resin layer: Formulation H1>
Methanol 11.1 parts Propylene glycol monomethyl ether acetate 6.36 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 bisphenol A with pentaethylene glycol monomethacrylate 2-Equivalent dehydrated compound: Shin-Nakamura Chemical Co., Ltd. 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane 9.1 parts / surfactant 1 0.54 parts

<Coating liquid for intermediate layer (oxygen barrier film): Formulation P1>
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Saponification degree = 88%, polymerization degree 550) 32.2 parts · Polyvinylpyrrolidone (manufactured by ASP Japan, K-30) 14.9 parts · Distilled water 524 parts · Methanol 429 parts

(Formation of partition walls)
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% 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-1, 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., wire Lamination was performed at a pressure of 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 at an exposure amount of 90 mJ / cm ² .

  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 photosensitive resin layer, thereby obtaining a patterned pixel.

Here, the melt viscosity at 220 ° C. of the photosensitive resin layer after development (before host baking) was measured. The melt viscosity was measured by a temperature rise test at a pressure of 100 kg / cm ² with a 1 mm diameter nozzle using CFT-500D manufactured by Shimadzu Corporation.
In addition, for the measurement of melt viscosity, two substrates having been subjected to the above-described development process are prepared, one is used for sampling the photosensitive resin layer necessary for melt viscosity measurement, and the other is post-baked. The subsequent steps were used to produce a color filter.

Thereafter, the substrate was further post-exposed with 500 mJ / cm ² light from the side of the photosensitive resin layer with an ultra-high pressure mercury lamp, and then heat treated (post-baked) at 220 ° C. for 15 minutes to obtain partition walls.

[Water repellent treatment by coating method]
Alkaline acceptable in which 0.5% by mass (based on the solid content of the photosensitive resin) of a fluorosurfactant (manufactured by Sumitomo 3M, Florard FC-430) is previously added on the substrate on which the partition walls are formed. A molten photosensitive resin (Positive photoresist AZP4210, manufactured by Hoechst Shapan Co., Ltd.) is applied using a slit nozzle so as to have a film thickness of 2 μm, and heat treatment is performed at 90 ° C. for 30 minutes in a hot air circulating dryer. It was.

Next, the substrate was exposed from the rear surface of the substrate on which the partition walls were formed at an exposure amount of 110 mJ / cm ² (38 mW / cm ² × 2.9 seconds), and an inorganic alkaline developer (Az400K Developer, manufactured by Hoechst Japan Co., Ltd., 1 : 4) After immersing and shaking in 80 seconds, rinse treatment was performed in pure water for 30 to 60 seconds to form a water-repellent resin layer on the partition wall, thereby providing a surface energy difference between the inside and outside of the pixel. The surface energy inside and outside the pixel after forming the water-repellent resin layer was 10 to 15 dyne / cm outside the pixel (on the resin layer) and around 55 dyne / cm inside the pixel (on the glass substrate).

  Thereafter, RGB pixels were formed by the ink jet method in the same manner as in Example 1 to produce a liquid crystal display device, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

[Example 8]
In Example 7, a liquid crystal display device was produced in the same manner as in Example 7 except that the photosensitive resin composition formulation was changed to the photosensitive resin composition formulation K2 and the exposure amount was changed to the exposure described in Table 1. did.

[Example 9]
In Example 7, the liquid crystal display device was produced in the same manner as in Example 7 except that the photosensitive resin composition formulation was changed to the photosensitive resin composition formulation K3 and the exposure amount was changed to the exposure described in Table 1. .

[Example 10]
In Example 7, the liquid crystal display device was produced in the same manner as in Example 7 except that the photosensitive resin composition formulation was changed to the photosensitive resin composition formulation K4 and the exposure amount was changed to the exposure described in Table 1. .

[Example 11]
In Example 7, the liquid crystal display device was produced in the same manner as in Example 7 except that the photosensitive resin composition formulation was changed to the photosensitive resin composition formulation K5 and the exposure amount was changed to the exposure described in Table 1. .

[Example 12]
In Example 7, the liquid crystal display device was produced in the same manner as in Example 7 except that the photosensitive resin composition formulation was changed to the photosensitive resin composition formulation K6 and the exposure amount was changed to the exposure described in Table 1. .

[Comparative Example 1]
In Example 6, a liquid crystal display device was produced in the same manner as in Example 6 except that the exposure amount was changed to the exposure described in Table 1.

[Comparative Example 2]
In Example 12, a liquid crystal display device was produced in the same manner as in Example 12 except that the exposure amount was changed to the exposure described in Table 1.

[Example 13]
Using the color filters obtained in Examples 1 to 12 and Comparative Examples 1 and 2, liquid crystal display devices were produced 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 produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.

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

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

(Production of liquid crystal display device)
Using the liquid crystal display device substrate obtained above, liquid crystal display devices 1 to 14 were produced using the methods described in the first examples [0079] to [0082] of JP-A No. 11-242243. .

(Evaluation)
When the obtained liquid crystal display devices 1 to 14 were displayed in white and displayed black, the display quality was visually observed. The results are shown in Table 2.

  As is apparent from Table 2, the screens of the liquid crystal display devices provided with the color filters prepared in Examples 1 to 12 were all excellent in color mixing. The liquid crystal display devices 13 and 14 provided with the color filters prepared in Comparative Examples 1 and 2 were slightly reddish in both the white display and black display states, and the display quality was inferior.

Claims (8)

A photosensitive resin layer forming step of forming a photosensitive resin layer containing at least a photopolymerization initiator or an initiation system, a monomer, and a binder on at least one surface on the substrate; and at least the photosensitive resin layer with a partition pattern An exposure process for exposing so as to correspond to the above, a development process for developing the exposed photosensitive resin layer to form partition walls, and a heat treatment process for post-baking the photosensitive resin layer after development. In a method for manufacturing a partition wall for applying a droplet of a colored liquid composition to form a pixel,
The manufacturing method of the partition characterized by the melt viscosity in 220 degreeC of the said photosensitive resin layer before performing the said post-baking being 1000 Pa.s or more. The method for manufacturing a partition wall according to claim 1, wherein the photosensitive resin layer is formed by the following method (A) or (B).
(A) A photosensitive resin composition containing a colorant is applied to a substrate and dried.
(B) Using a transfer material in which a photosensitive transfer layer containing a colorant is formed on a temporary support, the photosensitive transfer layer is transferred to a substrate. An oxygen blocking layer is provided on the photosensitive resin layer before the exposure step,
3. The method for manufacturing a partition wall according to claim 1, wherein in the exposure step, exposure is performed through the oxygen blocking layer provided on the photosensitive resin layer. 4.   The board | substrate with a partition characterized by having a board | substrate and the partition produced by the manufacturing method of the partition of any one of Claims 1-3 on this board | substrate. A color filter having, on a substrate, a partition wall produced by the method for manufacturing a partition wall according to any one of claims 1 to 3, and a pixel group composed of a plurality of pixels of two or more colors,
The color filter, wherein the plurality of pixels are formed by applying droplets of a colored liquid composition between the partition walls after the partition walls are formed.   The color filter according to claim 5, wherein the droplet applying method is an ink jet method.   A display device comprising the color filter according to claim 5. A method for producing an optical element using the partition wall-made substrate produced by the method for producing a partition wall according to any one of claims 1 to 3,
A water repellency treatment step of performing a water repellency treatment on the surface of the partition wall of the substrate with the partition wall, and then a step of forming a pixel by applying droplets of a colored liquid composition between the water repellent partition walls. A method for manufacturing an optical element.