JP2007163978A - Color filter for multi-domain vertical alignment liquid crystal display device and method for manufacturing the same, and multi-domain vertical alignment liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter suited for an MVA-LCD (Multi-domain Vertical Alignment-Liquid Crystal Display). <P>SOLUTION: The method for manufacturing the color filter for the MVA-LCD provided with. a coloring pixel layer having partition walls and coloring pixels arranged in gaps between the partition walls; and protrusions for multi-domain arranged on the coloring pixel layer, on a transparent substrate, has at least the steps of: forming the partition walls on the transparent substrate; and forming the respective coloring pixels in the gaps between the partition walls. When a height of the partition wall from the transparent substrate at a highest point is represented by h, a line parallel to the transparent substrate and 0.8h distant therefrom is represented by L<SB>1</SB>, a tangent line at a point where L<SB>1</SB>is tangent to the partition wall is represented by L<SB>2</SB>, and a line parallel to the transparent substrate and distant therefrom by h is represented by L<SB>3</SB>, a value d/h obtained by dividing a distance d from an intersection of L<SB>2</SB>and L<SB>3</SB>to the partition wall by h satisfies inequality ≤0.04. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter for an alignment division vertical alignment type liquid crystal display device, a method for manufacturing the same, and an alignment division vertical alignment type liquid crystal display device.

  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 boundary is divided by a separation wall such as a black matrix. As a manufacturing method of such a color filter, conventionally, a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development. Colored photosensitive resin liquid method (colored resist method) (see, for example, Patent Documents 1, 2, and 3), 4) A method of sequentially transferring an image formed on a temporary support onto a final or temporary support ( For example, see Patent Documents 4, 5 and 6.) 5) A colored layer is formed by coating a preliminarily colored photosensitive resin solution on a temporary support, and this photosensitive colored layer is formed directly on the substrate in sequence. A method (transfer system) for forming a multicolor image by a method of repeating transfer, exposure and development by the number of colors is known (for example, see Patent Document 7). A method using an ink jet method (for example, see Patent Document 8) is also known.

Among these methods, although the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive layer resin solution. On the other hand, the ink-jet method has a problem that the positional accuracy of the pixels is poor, although the loss of the resin liquid is small and advantageous in terms of cost. In order to overcome these problems, a color filter manufacturing method in which a black matrix is formed by a colored resist method and an RGB pixel is manufactured by an ink jet method has been proposed. Since the edges are rounded and each of the color inks that are subsequently ejected easily passes over the black matrix, there is a possibility that bleeding, bleeding, color mixing with adjacent pixels, white spots, etc. may occur. In order to prevent this, a method has been disclosed in which the black matrix and the ink have a repelling property or the ink wettability of the black matrix gap is increased (for example, Patent Documents 9 and 10). However, in these methods, a special material is required for the black matrix coloring resist or ink, or a step of increasing the surface energy of the black matrix gap (surface modification treatment) is required. Cost issues still remain.
In addition, a method of performing water-repellent treatment on a separation wall by plasma treatment is known (for example, see Patent Document 12).

Among display devices, an alignment-divided vertical alignment liquid crystal display device (Multi-domain Vertical Alignment-Liquid Crystal Display, hereinafter sometimes referred to as MVA-LCD as appropriate) has a very large cell gap effect, and is therefore used as a color filter. High smoothness is required. Since the separation wall used in the conventional ink jet method has a gentle cross-sectional edge, the ink runs on the separation wall at the time of pixel ejection, and a color filter with many irregularities is completed. For this reason, when an MVA-LCD is produced using a conventional color filter with many irregularities, many display unevenness due to cell gap unevenness occurs, making it difficult to manufacture a high-quality MVA-LCD.
JP-A-63-298304 JP-A 63-309916 Japanese Patent Laid-Open No. 1-152449 JP-A-61-99103 JP-A-61-233704 JP-A 61-279802 JP-A-61-99102 JP-A-8-227010 JP-A-6-347637 JP-A-7-35915 JP-A-10-142418 JP 2001-343518 A

  The present invention has been made in view of the above-described conventional problems, and a color filter suitable for an alignment division vertical alignment type liquid crystal display device, a manufacturing method thereof, and an alignment division vertical alignment type liquid crystal display device using the color filter. The purpose is to provide.

That is, the present invention
<1> A colored pixel layer having at least red, green, and blue colored pixels provided in a gap between the separation wall and the separation wall on a transparent substrate, and an alignment division provided on the colored pixel layer A color filter for an alignment-divided vertical alignment type liquid crystal display device, comprising: a step of forming the separation wall on the transparent substrate; and the coloring pixels in a gap between the separation walls. And forming a height from the transparent substrate at a point where the height of the separation wall from the transparent substrate is the highest in the cross section of the separation wall from the transparent substrate. L ₁ is a line parallel to the transparent substrate at a position of 0.8 h, L ₂ is a tangent line at a point where L ₁ and the separation wall are in contact, and L ₃ is a line parallel to the transparent substrate at a position of h. The distance from the intersection of L ₂ and L ₃ to the separation wall A method of manufacturing a color filter for an alignment-divided vertical alignment type liquid crystal display device, wherein a value d / h obtained by dividing the separation d by h satisfies 0.04 or less.

  <2> The alignment-divided vertical alignment according to <1>, wherein the step of forming the colored pixel is a step of applying a droplet of the colored liquid composition to a gap between the separation walls by an inkjet method. It is a manufacturing method of the color filter for type | mold liquid crystal display devices.

  <3> A color filter for an alignment division vertical alignment type liquid crystal display device manufactured by the method for manufacturing a color filter for alignment division vertical alignment type liquid crystal display device according to <1> or <2>.

  <4> An alignment division vertical alignment type liquid crystal display device having the color filter for alignment division vertical alignment type liquid crystal display device according to <3>.

  ADVANTAGE OF THE INVENTION According to this invention, the color filter suitable for an alignment division | segmentation vertical alignment type liquid crystal display device, its manufacturing method, and the alignment division vertical alignment type liquid crystal display device using this color filter can be provided.

Hereinafter, the present invention will be described in detail.
The manufacturing method of the color filter for MVA-LCD of the present invention includes a colored pixel layer having a separation wall and a colored pixel of red, green, and blue provided in a gap between the separation walls on a transparent substrate, and the coloring A color filter for an alignment division vertical alignment type liquid crystal display device, comprising: an alignment division protrusion provided on a pixel layer, the step of forming the separation wall on the transparent substrate; and Forming each of the colored pixels in the gap of the image wall, and in the cross section of the image separation wall, the height of the image separation wall from the transparent substrate is the highest from the transparent substrate. and the height h, the said transparent substrate and a line parallel to L ₁ to the position of 0.8h from the transparent substrate, the tangential and L ₂ at the point of L ₁ and the Hanarega wall is in contact, wherein the position of h when the transparent substrate and a line parallel to the L _3, L ₂ The value d / h to the distance d divided by h from the intersection of the L ₃ to the Hanarega wall and satisfies 0.04 or less.

  The separation wall used in the method for manufacturing a color filter for MVA-LCD of the present invention has a sharp edge at the cross section in order to satisfy the d / h value of 0.04 or less. It is possible to prevent the ink from climbing onto the separation wall. Therefore, the color filter manufactured by the method for manufacturing a color filter for MVA-LCD of the present invention has high smoothness.

  The MVA-LCD of the present invention has the color filter for MVA-LCD of the present invention. Since the MVA-LCD of the present invention having the MVA-LCD color filter of the present invention having high smoothness has high cell gap uniformity, it can display a high-quality image without display unevenness.

(Deep color composition)
The separation wall according to the present invention is formed from a dark color composition. Here, the dark color composition is a composition having a high optical density, and the value thereof is 2.0 to 10.0. The optical density of the dark color composition is preferably 2.5 to 6.0, particularly preferably 3.0 to 5.0. Further, since this dark color composition is preferably cured by a photoinitiating system as described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is 2.0 to 10.0, preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the shape of the separation wall may not be as desired, and if it exceeds 10.0, polymerization cannot be started and it is difficult to produce the separation wall itself. As long as it has such properties, the dark body in the composition may be an organic substance (various dyes such as dyes and pigments), or each form of carbon. May be. Such a dark body is not particularly limited, but a black body is most often used.
The optical density (OD) of the separation wall can be measured by a general optical densitometer (for example, D200-II manufactured by Gretag Macbeth Co.) or a spectrophotometer UV-2100 [manufactured by Shimadzu Corporation]. .
As a specific measuring method, first, a thin-film measurement light-shielding layer having an OD of 3.0 or less is formed. In order to measure with higher accuracy, the OD is preferably 3 or less.
Next, using a spectrophotometer UV-2100 (manufactured by Shimadzu Corporation), the transmission optical density (OD) of the substrate with the light-shielding layer for measurement was measured at a wavelength of 555 nm. The transmission optical density (OD ⁰ ) of each glass substrate used is measured by the same method. Then, a value obtained by subtracting OD ⁰ from OD (transmission OD; = OD−OD ⁰ ) is set as the transmission optical density of the measurement light-shielding layer.
Using a contact-type surface roughness meter P-10 (manufactured by TENCOR), the thickness of the light-shielding layer for measurement is measured. From the relationship between the transmission optical density and the thickness of the measurement result, the thickness of the actually produced film is separated. The optical density of the drawing wall can be calculated.

  Specific examples of the dark color used in the present invention include pigments and dyes described in JP-A-2005-17716 [0038] to [0054], and JP-A-2004-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

For the dark color composition of the present invention, organic pigments, inorganic pigments, dyes, and the like can be suitably used. When light shielding properties are required for the separation wall, carbon black, titanium oxide, iron oxide, etc. In addition to the light-shielding agent such as metal oxide powder, metal sulfide powder and metal powder, a mixture of pigments such as red, blue and green can be used. Known colorants (dyes and pigments) can be used. Among the known colorants, when a pigment is used, it is preferably dispersed uniformly in the dark color composition.
From the viewpoint of sufficiently shortening the development time, the ratio of the dark color body in the solid content of the dark color composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, More preferably, it is 50-55 mass%.
Further examples of the dark black colored body include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.

The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle). The vehicle refers to a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid portion 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 color body (pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, This 100 average value is said.

  The dark color composition preferably contains at least a polymerization initiator and a polyfunctional monomer in addition to the dark color body. 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.

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, but in the present invention, the shape of the separation wall after curing is described later. Therefore, it is preferable to use a photoinitiating system. The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray (also referred to as exposure). It is a compound to be obtained and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.
For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

  Specifically, a trihalomethyl group-substituted trihalomethyloxazole derivative or s-triazine derivative described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, A trihalomethyl group-containing compound such as the trihalomethyloxadiazole compound described in Japanese Patent No. 4221976;

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, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and particularly selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.
Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. The total amount of the photopolymerization initiator in the dark color composition is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

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

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

  Specific examples of the mercaptan 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 difficult to drop 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 preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition.

  As the polyfunctional monomer of 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.

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

  As content in the dark composition of a polyfunctional 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 an alkaline developer at the exposed portion of the composition may be inferior, and when it exceeds 80% by mass, the tackiness of a dark color composition increases. Therefore, the handleability may be inferior.

(Illustrated wall)
The image separation wall according to the present invention is formed from the dark color composition. The image separation wall separates two or more pixel groups and is generally black, but is not limited to black. The dark colored product is preferably an organic material (various dyes such as dyes and pigments). The separation wall is preferably formed by exposing the dark color composition in an oxygen-poor atmosphere and then developing it.
Under an oxygen-poor atmosphere when photocuring such a dark-colored composition means an inert gas, a reduced pressure, or a protective layer that can block oxygen, and these are described in detail below. .

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.

  Under reduced pressure refers to a state of 500 hPa or less, preferably 100 hPa or less.

Examples of the protective layer capable of blocking oxygen include, for example, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose described in JP-A Nos. 46-2121 and 56-40824. Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches And a group of water-soluble salts thereof, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably the alkali-soluble resin layer solid content. It is 10-40 mass%.
In addition, various films can be used as the layer capable of blocking oxygen. For example, polyesters such as PET, polyamides such as nylon, and ethylene-vinyl acetate copolymers (EVAs) are also preferably used. be able to. These films may be stretched as necessary, and the thickness is suitably 5 to 300 μm, preferably 20 to 150 μm. When the separation wall is produced using a transfer material, the temporary support described below can be suitably used as a layer capable of blocking oxygen.

The oxygen permeability coefficient of the protective layer capable of blocking oxygen produced in this way is preferably 2000 cm ³ / (m ² · day · atm) or less, but 100 cm ³ / (m ² · day · atm) or less. Is more preferably 50 cm ³ / (m ² · day · atm) or less.
When the oxygen permeability is higher than 2000 cm ³ / (m ² · day · atm), oxygen cannot be effectively blocked, and it may be difficult to make the separation wall into a desired shape.

In the present invention, the cross-sectional shape of the separation wall formed on the transparent substrate is the height from the transparent substrate 200 at the highest point of the separation wall 100 from the transparent substrate 200 as shown in FIG. A line parallel to the transparent substrate 200 at a position 0.8 h from the transparent substrate 200 is L ₁ , a tangent line at a point where L ₁ and the separation wall 100 are in contact with each other, L _2, and a line parallel to the transparent substrate 200 at the position h. When the straight line is L ₃ , the value d / h obtained by dividing the distance d from the intersection of L ₂ and L ₃ to the separating wall 100 by h is 0.04 or less.

When a dark color composition as described above is photopolymerized on the substrate in an oxygen-poor atmosphere as described above, the exposure amount from the surface of the composition toward the substrate is attenuated by the absorption of the composition itself. As a result, the surface is further cured. Furthermore, since it is under an oxygen-poor atmosphere, inhibition of polymerization on the surface of the composition is suppressed, and as a result, the surface is further cured. Due to these two contributions, the d / h value in the cross section of the separation wall formed on the substrate can be made 0.04 or less.
These values are actually measured by cutting the separation wall formed on the substrate vertically with the substrate cut vertically to expose the cross section and directly observing with a microscope or the like. Through the process of fixing the shape of the separation wall obtained in this way, the ink once deposited in the gap becomes difficult to get over the separation wall, and as a result, bleeding, protrusion, color mixing with adjacent pixels and white A good color filter can be obtained while preventing omission.
In the present invention, the d / h value is 0.04 or less, preferably 0.038 or less, particularly preferably 0.035 or less.

(Photosensitive transfer material)
In order to realize such a separating wall shape easily and at low cost, it comprises a protective layer capable of blocking at least oxygen (hereinafter sometimes referred to as an oxygen blocking layer) on the temporary support and a dark color composition. There is a technique of using a photosensitive transfer material having layers (dark color composition layers) in this order. When such a material is used, since the dark color composition layer is protected by the oxygen blocking layer, it automatically becomes an oxygen-poor atmosphere. Therefore, it is not necessary to perform the exposure process under an inert gas or under reduced pressure, and there is an advantage that the current process can be used as it is. The materials constituting the oxygen blocking layer and the dark color composition layer in the photosensitive transfer material are as described above.
Alternatively, a photosensitive transfer material having at least a dark color composition layer on the temporary support may be used, and the temporary support may be used as a “protective layer capable of blocking oxygen”. In this case, it is not necessary to provide the oxygen barrier layer, and the number of steps can be reduced.

  The photosensitive transfer material may have a thermoplastic resin layer between the temporary support and the oxygen barrier layer as necessary. Such a thermoplastic resin layer is alkali-soluble and includes at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, good adhesion to the permanent support can be exhibited.

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

  For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.

  In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.

  Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.

The 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, polyester, 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. If the thickness is less than 5 μm, the temporary support tends to be easily broken when peeled off, and if the exposure is performed via the temporary support, the resolution tends to be lowered if the thickness exceeds 300 μm.
Among the above specific examples, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  A thin cover sheet is preferably provided on the dark color composition layer in order to protect it from contamination and damage during storage. The cover sheet may be made of the same or similar material as the temporary support, but it must be easily separated from the dark color composition layer. As the cover sheet material, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable. The thickness of the cover sheet is generally 4 to 40 μm, preferably 5 to 30 μm, particularly preferably 10 to 25 μm.

(Transparent substrate)
As the transparent substrate (permanent support) constituting the color filter, glass, ceramic, synthetic resin film or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

(Formation of a separation wall)
Hereinafter, a case where a separation wall is formed using a photosensitive transfer material will be described. A photosensitive transfer material in which an oxygen blocking layer, a dark color composition layer, and a cover sheet is provided on the dark color composition layer is prepared on a temporary support. First, after removing and removing the cover sheet, the surface of the exposed dark color composition layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to further increase the productivity.

Subsequently, it peels between a temporary support body and an oxygen barrier layer, and a temporary support body is removed. Subsequently, in a state where a desired photomask (for example, quartz exposure mask) is vertically set above the removal surface after the temporary support is removed, an appropriate distance between the exposure mask surface and the oxygen blocking layer (for example, 200 μm) for exposure. Next, after the irradiation, development processing is performed using a predetermined processing solution to obtain a patterning image, and subsequently, washing treatment is performed as necessary to obtain a separation wall.
When the temporary support is used as a protective layer capable of blocking oxygen, a desired photomask (for example, a quartz exposure mask) is provided above the temporary support while leaving the temporary support (without peeling). In a state in which is vertically set, the distance between the exposure mask surface and the temporary support is appropriately set (for example, 200 μm) and exposed. Next, the temporary support is removed, and after irradiation, development processing is performed using a predetermined processing liquid to obtain a patterning image. Subsequently, if necessary, washing treatment is performed to obtain a separation wall.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ). it can.
After irradiation, development processing is performed using a predetermined processing solution. 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.
Prior to the development, pure water is preferably sprayed with a shower nozzle or the like to uniformly wet the surface of the dark color composition layer or the oxygen barrier 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.

  Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Examples include 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 dark color composition layer, methods such as rubbing with a rotating brush or a wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, although it depends on the composition of the dark color composition layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the separation wall shape suitable. It is also possible to put a water washing step after the development processing. In this developing step, the separating wall shape is formed as described above.

  An ink repellent compound is preferably present on the upper surface of the separation wall according to the present invention. In the present invention, it is preferable that the separation wall is subjected to a water-repellent treatment so that the upper surface of the separation wall has a water-repellent state (a state in which an ink-repellent compound exists). Thereby, when a droplet of a colored liquid composition (ink) is applied between the separation walls by a method such as an ink jet, the inconvenience that the ink gets over the separation wall and mixes with the adjacent color is eliminated. be able to.

  In the present invention, the upper surface refers to the surface of the separation wall, and the angle formed between the tangent to the surface and the substrate surface is 10 ° or less.

  As the water repellent treatment, a method of applying a water repellent material on the upper surface of the separation wall, 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 on the separation wall Etc.

Hereinafter, the water repellent treatment will be described in detail.
(1) <Method of kneading a water-repellent substance into the separation wall>
As a means for preventing “color mixing”, there is a method of adding the fluororesin (A) to the above-described dark color composition.

  The fluorine-containing resin is composed of a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a) having a polyfluoroether structure represented by the following formula 1, an ethylenic double bond, and an acidity. A copolymer containing a monomer unit based on a monomer having a group (b) and having an acid value of 1 to 300 mgKOH / g is preferable. Examples of the ethylenic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group.

-(X-O) _n -Y Formula 1

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

  As an aspect of X and Y in Formula 1, Preferably, X is a C1-C10 hydrogen atom remove | excluded alkylene group or a C1-C10 perfluorinated alkylene group. Each of the units enclosed by n represents the same group or a different group, and Y represents a fluorinated alkyl group or a par group having 1 to 20 carbon atoms except for one hydrogen atom having 1 to 20 carbon atoms. The thing which shows the fluorinated alkyl group is mentioned.

  As an embodiment of X and Y in Formula 1, more preferably, X is a C 1-10 perfluorinated alkylene group, and represents the same group or different groups for each unit enclosed by n. , Y may be a perfluorinated alkyl group having 1 to 20 carbon atoms.

  When the aspect of X and Y is the above, the fluorine-containing resin exhibits good ink repellency.

  In Formula 1, n represents an integer of 2 to 50. n is preferably from 2 to 30, and more preferably from 2 to 15. When n is 2 or more, the ink falling property is good. When n is 50 or less, the fluorine-containing resin is a monomer having an ethylenic double bond and an Rf group (a), a monomer having an ethylenic double bond and an acidic group (b), and others. In the case of synthesis by copolymerization with a monomer, the compatibility of the monomer becomes good.

  Moreover, 2-50 are preferable and, as for the total number of the carbon atoms in Rf group (a) which consists of a polyfluoroether structure represented by Formula 1, 2-30 are more preferable. Within this range, the fluorine-containing resin exhibits good ink repellency, particularly organic repellency. In addition, the fluororesin is a copolymer of a monomer having an ethylenic double bond and an Rf group (a), a monomer having an ethylenic double bond and an acidic group (b), and other monomers. When synthesized by polymerization, the compatibility of the monomers is improved.

Examples of _{X, -CF 2 -, - CF} 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 CF (CF 3) -, - CF 2 CF 2 CF 2 CF 2 -, - _{CF 2 CF 2 CF (CF 3} ) -, and _{CF 2 CF (CF 3) CF} 2 - and the like.

Specific examples of _{Y, -CF 3, -CF 2 CF} 3, -CF 2 CHF 2, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, - (CF 2) 4 CF 3, _{- (CF 2) 5 CF 3} , - (CF 2) 6 CF 3, - (CF 2) 7 CF 3, - (CF 2) 8 CF 3, - (CF 2) 9 CF 3 and, _(CF 2) ₁₁ CF ₃ , — (CF ₂ ) ₁₅ CF ₃ may be mentioned.

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

As Rf group (a) represented by Formula 2, specifically,
_{-CF 2 O (CF 2 CF 2} O) n-1 CF 3 (n is 2-9),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) n-1 C 6 F 13 (n is 2-6),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6)
Is preferable from the viewpoint of ease of synthesis.

  The Rf groups (a) in the fluororesin may all be the same or different.

  The content of fluorine atoms in the fluorine-containing resin is preferably 1 to 60%, more preferably 5 to 40%. Within this range, the fluororesin exhibits good ink repellency.

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.

As specific examples of Q ¹ and Q ² ,
_{-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 -, - CH 2 CH (OH) CH 2 - is preferred.

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 fluororesin exhibits good ink repellency and the developability of the dark color 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 an alkyl group such as a methyl group, an ethyl group or an n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group, a halogen atom or an alkyl group. 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 fluororesin exhibits good ink repellency and the developability of the dark color 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 a dark color composition.

  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 dark color composition becomes good.

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

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

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

Examples of the compound having an Rf group (a) and a carboxyl group include compounds represented by the following formula 3.
_{HOOC-C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 Equation 3
In Formula 3, p is an integer of 2 or 3, q is an integer of 1 to 20, and n is an integer of 2 to 50.

Examples of the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following formula 4.
_{HOCH 2 -C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 Equation 4
In Formula 4, p represents an integer of 2 or 3, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

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

  Specific examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydro Shimechiru (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (where g is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) g H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) g H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) g H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _k H (where h is 0 or an integer from 1 to 100, k is an integer from 1 to 100, h + k is from 1 to 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, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6 anhydride -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 dark color composition 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 dark color composition 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 from 0.01 to 50%, more preferably from 0.1 to 30%, particularly preferably from 0.2 to 10%, based on the solid content in the dark color composition. . Within this range, the dark color 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 separation wall on the substrate on which the separation wall 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 acetoxy silane, ketoxime silane, alkoxy silane, amino silane, amido silane, alkenoxy silane, etc., used for so-called room temperature (low temperature) curable silicone rubber, and usually have a terminal hydroxyl group as a linear organic polysiloxane. In combination with these, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamide 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 dark color composition layer and the silicone rubber layer, and aminosilane compounds and organic titanate compounds are particularly preferred. Instead of providing an adhesive layer between the dark color composition 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 separation wall as a mask, and further, the irradiation UV light is scattered to expand the incident light from the size of the transmission part and to act on the photosensitive resin. The portion of the resin that is solubilized by reaction is made larger on the surface side of the silicone rubber. After exposure in this manner, a partition wall having a silicone rubber surface layer can be prepared 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 separation wall is formed.

As the gas containing at least fluorine atoms introduced in this step, one or more halogen gases selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ are used. It is preferable. In particular, C ₅ F ₈ (octafluorocyclopentene) has an ozone depletion ability of 0, and at the same time, has an atmospheric life (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 is possible to control the degree of ink repellency on the surface of the image separation wall processed 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 separation wall>
As 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 separation wall is formed.
As a material having water repellency, a fluorine resin such as polytetrafluoroethylene, silicone rubber, perfluoroalkyl acrylate, hydrocarbon acrylate, methyl siloxane, etc., which are generally considered to be water repellent materials, have a contact angle of 60 with a colored liquid composition. It is not particularly limited as long as it is at least °.

  As a method for applying the water repellent material, it is possible to select the most suitable method for each material such as slit coat, spin coat, dip coat, roll coat, etc., as long as it does not affect the substrate, separation wall, etc. is there.

Next, UVO ₃ treatment is performed from the back side of the substrate through the separation wall, and the water-repellent film other than the separation wall is selectively removed or hydrophilized (the contact angle with respect to the colorant is 30 ° before and after the treatment). (There is an opening above).

  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 separation wall, a lift-off method or the like is also effective.

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

(Formation of colored pixels)
Next, a colored liquid composition for forming RGB colored pixels enters the gaps in the gaps between the separation walls formed in the developing step. Thereby, a colored pixel layer is formed. As a method for allowing the colored liquid composition to enter the gap between the separation walls, a known method such as an ink jet method or a stripe Geyser coating method can be used, and the ink jet method is preferable in terms of cost. Further, the shape of the separation wall may be fixed before forming each colored 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) 2) After development, heat treatment is performed at a relatively low temperature. The heat treatment here refers to heating a substrate having a separation wall in an electric furnace, a dryer or the like, or irradiating an infrared lamp.

Here, the exposure amount when performing the above 1) is 500 to 3000 mJ / cm ² , preferably 1000 to 2000 mJ / cm ² in the atmosphere, and lower exposure in the poor oxygen atmosphere. It is also possible to expose in quantity. Similarly, the heating temperature in the case of 2) is 50 to 250 ° C., preferably about 70 to 200 ° C., and the heating time is about 10 to 150 minutes. When the temperature is lower than 50 ° C., there is a concern that the separation wall will not be cured, and when it is higher than 250 ° C., there is a concern that the shape of the separation wall will collapse.

  Regarding the ink jet method used for forming each colored pixel, known methods such as a method of thermally curing ink, a method of photocuring, and a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance are used. Can be used.

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

  The pattern shape of the color filter formed in this way is not particularly limited, and even in a general delta arrangement as shown in FIG. 2 (FIG. 2A), it has a lattice structure or a stripe structure. (FIG. 2 (B)) may be sufficient.

(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.

(Overcoat layer)
After the color filter is manufactured, an overcoat layer may be provided on the entire surface to improve resistance. The overcoat layer can protect the colored pixels of the inks R, G, and B and can flatten the surface, but it is preferably not provided from the viewpoint of increasing the number of steps.

Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually mainly composed of an acrylic resin, so that the acrylic resin composition is excellent in adhesion. Things are desirable.
Examples of the overcoat layer include those described in JP-A No. 2003-287618, paragraphs 0018 to 0028, and commercially available overcoat agents such as “Optomer SS6699G” manufactured by JSR.

  A transparent electrode, an alignment film, and the like may be provided on the colored pixel layer as necessary. Specific examples of the transparent electrode include, for example, ITO. A specific example of the alignment film is polyimide.

  Next, the alignment dividing projection will be described. The alignment dividing projections according to the present invention can be formed in a desired pattern shape by forming a coating film using a photoresist, exposing the film using a stepper through a photomask, and subsequent development.

Phenol novolac resin can be suitably used as the photoresist used for forming the alignment dividing protrusions in the present invention. Further, in the present invention, in order to adjust the volume resistivity of the alignment dividing protrusions, it is preferable to add a conductive filler to the photoresist used for forming the alignment dividing protrusions. _{ITO, In 2 O 3, SnO} 2, TiO 2, ZnO and the like.

  The conductive filler is used alone or in combination with a photoresist. By adding a conductive filler to the photoresist, the post-baking temperature can be lowered, and the concentration of the alignment dividing projections is lowered, so that the transmittance of the color filter is improved. When the conductive filler is carbon black or the like, the concentration of the alignment dividing protrusions is increased and the transmittance of the color filter is decreased, but the contrast is improved.

In addition, the post-baking conditions for forming the alignment division protrusions of the present invention are preferably 240 ° C. × 20 minutes or more, and the post-baking is performed at 240 ° C. × 20 minutes or more for orientation division. The volume resistivity of the protrusion can be set to 1.0 × 10 ¹² Ωcm or less. In addition, about 240 degreeC x 20 minutes-about 300 degreeC x 20 minutes is enough for this post-baking.

  FIG. 3A is an enlarged plan view showing one pixel according to an embodiment of the color filter for MVA-LCD of the present invention. FIG. 3B is a cross-sectional view taken along line A-A ′ in FIG. As shown in FIGS. 3 (a) and 3 (b), in this example, a separation wall 2, a colored pixel 3, a transparent electrode 4, and an alignment dividing projection 5 having an arc-shaped cross section are sequentially formed on a glass substrate 1. It is an example of the formed color filter 6 for MVA-LCD.

  The orientation dividing projection 5 having a circular cross section is bent by an angle of 90 ° within one pixel. The alignment dividing projection 5 having a circular cross section in one pixel is represented by a solid line, and the alignment dividing projection 5 having a circular cross section in an adjacent pixel is represented by a dotted line. FIG. 4A is a plan view showing a state where the TFT side substrate is arranged on the MVA-LCD color filter shown in FIG. 3 to obtain an MVA-LCD. FIG. 4B is a cross-sectional view taken along line B-B ′ in FIG.

  As shown in FIG. 4A by the double-pointed line, the TFT side substrate is also bent by 90 ° in one pixel with the alignment dividing projection 7 having a circular cross section. The alignment dividing projections 5 having a circular cross section provided on the color filter 6 and the alignment dividing projections 7 having a circular cross section provided on the TFT side substrate are provided alternately.

  Accordingly, when a voltage is applied, as indicated by a white arrow in FIG. 4A, the liquid crystal molecules in the upper part of the pixel in one pixel are inclined in the direction of 45 ° to the upper left and 45 ° to the lower right. As indicated by the black arrows, the liquid crystal molecules in the lower part of the pixel are inclined in the direction of 45 ° on the upper right and 45 ° on the lower left. That is, this is an example in which one pixel is divided into four, and as shown in FIG. 4C, the liquid crystal molecules are inclined in four directions within one pixel, and the liquid crystal display device is further excellent in viewing angle characteristics.

  FIG. 5A is an enlarged plan view showing one pixel according to another embodiment of the color filter for MVA-LCD of the present invention. FIG. 5B is a cross-sectional view taken along line C-C ′ in FIG. As shown in FIGS. 5A and 5B, in this example, a separation wall 2, a colored pixel 3, a transparent electrode 4, and an alignment dividing projection 5 having a circular cross-sectional shape are sequentially formed on a glass substrate 1. This is a formed color filter. The orientation dividing projection 5 having a circular cross section is a protrusion having a circular planar shape and a circular cross section.

  When the MFT-LCD color filter is arranged with an opposing TFT side substrate to form an MVA-LCD, the liquid crystal molecules tilt in an infinite direction when a voltage is applied, that is, one pixel is infinite. As shown in FIG. 5C, the liquid crystal molecules are inclined in an infinite direction within one pixel, and the liquid crystal display device has particularly excellent viewing angle characteristics.

[Alignment division vertical alignment type liquid crystal display device]
The alignment-divided vertical alignment liquid crystal display device of the present invention is not particularly limited as long as it has the color filter for MVA-LCD of the present invention.
FIG. 6 is a cross-sectional view showing an embodiment of the MVA-LCD of the present invention. Here, the liquid crystal display device 10 includes an array substrate 12 and a counter substrate 14 which are arranged to face each other with a predetermined cell gap, and a liquid crystal layer 16 is sandwiched between the array substrate and the counter substrate. The peripheral portions of the array substrate 12 and the counter substrate 14 are bonded to each other by a sealing material 18 arranged so as to surround the outer periphery of the display area of the liquid crystal display device. A liquid crystal injection port (not shown) is provided in a part of the sealing material 18, and the liquid crystal injection port is sealed with a sealing material after the liquid crystal is injected.

  The array substrate 12 includes a substrate 11 made of transparent glass, on which a plurality of scanning lines (not shown) and a plurality of signal lines 20 orthogonal to the scanning lines are arranged via an insulating film. Each of the regions surrounded by the scanning lines and the signal lines is provided with a substantially rectangular pixel electrode 22 to form a pixel portion. Here, each pixel electrode 22 is connected to a TFT 24 provided at the intersection of the scanning line and the signal line 20. Further, an alignment film 26 is formed on the entire surface of the glass substrate 11.

  The counter substrate 14 is configured by sequentially forming a colored pixel layer 30, a transparent counter electrode 32 made of ITO, and an alignment film 33 on a substrate 28 made of transparent glass. The colored pixel layer 30 includes a separation wall 34 formed in a matrix and stripe-shaped green coloring pixels 35G, a blue coloring pixel 35B, and a red coloring pixel 35R extending substantially parallel to each other between the separation walls 34. Is formed. A counter electrode 32 is formed on substantially the entire surface of the glass substrate 28 so as to cover these colored pixels 35G, 35B, and 35R, and an alignment film 33 is formed on the counter electrode.

  In the present embodiment, the alignment film 33 of the counter substrate 14 is formed to include the alignment dividing protrusions 40 and a plurality of columnar spacers 42. The alignment dividing projection 40 is provided at a position facing substantially the center of each of the colored pixels 35G, 35B, and 35R, and protrudes toward the array substrate 12 side. Each columnar spacer 42 is provided at a position facing the separation wall 34, protrudes toward the array substrate 12, and its tip abuts against the alignment film 26 on the array substrate side. Accordingly, the cell gap between the array substrate 12 and the counter substrate 14 is maintained at a predetermined value by the plurality of columnar spacers 42.

  Further, polarizing plates 44 and 45 are provided on the outer surfaces of the two substrates 11 and 28, respectively, and the liquid crystal display element 10 of the MVA-LCD of the present invention displays a color image as an optical shutter.

  Since the colored pixel layer 30 has high flatness, the liquid crystal display element 10 including the colored pixel layer does not cause cell gap unevenness between the colored pixel layer 30 and the substrate 11, and display defects such as color unevenness occur. There is nothing to do.

    The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

[Production method of dark color composition]
In the dark color composition K1, first, K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 were weighed, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 RPM for 10 minutes. 1, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) amino-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. In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>,
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant 0.65%

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

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

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

<Surfactant 1>
・ The following structure 1 30%

・ Methyl ethyl ketone 70%

[Example 1]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle has the composition described in the above table. Dark color composition K1 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum drying apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then prebaked at 120 ° C. for 3 minutes to form a dark photosensitive layer having a thickness of 2 μm. K1 was obtained.
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) that has an ultra-high pressure mercury lamp, the exposure mask surface and the dark color photosensitive film with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the layers K1 was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen atmosphere.

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark photosensitive layer K1, and then a KOH developer (KOH, containing nonionic surfactant, product names: CDK-1, Fuji). The film was diluted 100 times with Film Electronics Materials Co., Ltd., and was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post exposure was performed in the atmosphere with an exposure amount of 2000 mJ / cm ² to obtain an optical density of 3.9. A separation wall was obtained. The substrate with the separation wall thus obtained was cut vertically with the substrate to expose the cross section, and directly observed with a microscope or the like. The height from the transparent substrate at the highest point of the separation wall from the transparent substrate is h, and a line parallel to the transparent substrate at a position 0.8 h from the transparent substrate is L ₁ and L ₁ is separated. the tangent at the point where the wall is in contact with L _2, when a transparent substrate and a line parallel to the position of the h was L _3, and the distance from the intersection of the L ₂ and L ₃ until Hanarega wall is defined as d, h = 1.6 µm, d = 0.061 µm, and d / h = 0.038.

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

-Preparation of colored ink composition for pixels-
Of the following components, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.
<Composition of colored ink composition for red pixel>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 3 parts ・ First epoxy resin (novolak type epoxy resin) ,
Epicoat 154 manufactured by Yuka Shell Co., Ltd.) 2 parts, second epoxy resin (neopentyl glycol diglycidyl ether) 5 parts, curing agent (trimellitic acid) 4 parts, solvent: ethyl 3-ethoxypropionate 80 parts

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

  Next, using the color ink composition for R, G, and B pixels described above, within the region (the concave portion surrounded by the convex portion) divided by the separation wall of the color filter substrate obtained above, The ink composition was discharged using an inkjet recording apparatus until a desired concentration was obtained, and a color filter composed of R, G, and B patterns was produced. The color filter after image coloring was baked in an oven at 230 ° C. for 30 minutes to completely cure both the separation wall and each pixel.

In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the image separation walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found.
A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and separation wall of the color filter substrate obtained above.

When the ITO resistance of this color filter was measured ("Loresta" manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by the four-probe method), it showed a very low value of 12Ω / □.

  The following coating solution 1 for the photosensitive resin layer for the spacer was coated on the ITO of the color filter by the same slit coater as described above, and dried to form a photosensitive resin layer.

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

Next, proximity exposure was performed at 300 mJ / cm ² with an ultrahigh pressure mercury lamp through a predetermined photomask. After the exposure, the unexposed portion of the photosensitive resin layer was dissolved and removed using a KOH developer [CDK-1 (trade name) 100-fold diluted solution (pH = 11.8), manufactured by Fuji Photo Film Co., Ltd.]. .
Subsequently, baking was performed at 230 ° C. for 30 minutes, and a columnar spacer pattern having a diameter of 16 μm and an average height of 3.7 μm was formed on a portion located on the upper part of the separation wall on the ITO film on the glass substrate. An alignment film made of polyimide was further provided thereon.

(Formation of liquid crystal alignment split projections)
Prescription A of the following coating liquid for photosensitive resin layer for protrusions was applied onto the ITO of the color filter side substrate by a slit coater similar to the above, and dried to form a photosensitive resin layer for protrusions.
Next, an intermediate layer having a dry film thickness of 1.6 μm was provided on the protrusion photosensitive resin layer using an intermediate layer coating solution of the following formulation P1.

[Coating liquid for photosensitive resin layer for protrusions: Formulation A]
・ Positive resist solution 53.3 parts (FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.)
・ Methyl ethyl ketone 46.7 parts ・ Surfactant 1 0.04 parts

[Coating liquid for intermediate layer: prescription P1]
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts · Polyvinylpyrrolidone (manufactured by ASP Japan, K-30 14.9 parts · Distilled water 524 parts · Methanol 429 parts

Next, a proximity exposure machine is arranged so that the photomask is at a distance of 100 μm from the surface of the photosensitive resin layer for protrusions, and the proximity exposure is performed through the photomask with an irradiation energy of 150 mJ / cm ² by an ultrahigh pressure mercury lamp. did. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying on the substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions (exposed portions) of the photosensitive resin layer for protrusion were developed and removed. . As a result, a protrusion made of a photosensitive resin layer patterned in a desired shape was formed on a portion of the color filter side substrate located on the ITO film and above the R, G, and B pixels. Next, the color filter side substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes to form alignment dividing protrusions having a height of 1.5 μm and a vertical cross-sectional shape on the color filter side substrate. I was able to.

  Further, an alignment-divided vertical alignment type liquid crystal display element was produced by combining the drive side substrate and the liquid crystal material with the color filter side substrate obtained as described above. That is, a TFT substrate in which TFTs and pixel electrodes (conductive layers) are arrayed is prepared as a drive side substrate, the surface of the TFT substrate on which the pixel electrodes and the like are provided, and the color filter obtained from the above. The substrate was arranged so as to face the surface on which the alignment dividing projections were formed, and fixed by providing a gap by the spacer formed as described above. A liquid crystal material was sealed in the gap to provide a liquid crystal layer for image display. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and arranged on the side that would be the back side of the liquid crystal cell provided with the polarizing plate, thereby obtaining an alignment-divided vertical alignment type liquid crystal display device.

[Example 2]
Development was performed using the same materials and procedures as in Example 1, and a separation wall having an optical density of 4.0 was obtained without performing post-exposure. The shape of the separation wall thus obtained was observed in the same procedure as in Example 1. As a result, h = 1.7 μm, d = 0.065 μm, and d / h = 0.038. .

  Next, after coloring the R, G, and B pixels in the same manner as in Example 1, the color filter was baked in an oven at 230 ° C. for 30 minutes to completely cure both the separation wall and each pixel. A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and separation wall of the color filter substrate obtained above.

In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the image separation walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found. Further, the ITO resistance of the color filter was measured (“Loresta” manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by the four-probe method), and a very low value of 11Ω / □ was shown. This is presumably because the flatness of the surface of the separation wall was unexpectedly increased by using the present invention.
Next, an alignment-divided vertical alignment type liquid crystal display device was produced by the same method as in Example 1.

[Production Method of Photosensitive Transfer Material K1]
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 dark color composition K1 was applied and dried. In this way, 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 dark color composition layer having a dry film thickness of 2 μm are provided on the temporary support. Finally, a protective film (thickness 12 μm 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 dark color composition layer of black (K) are integrated is prepared, and the sample name is the photosensitive transfer material K1. It was.

<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, average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 1 part, 0.51 part of the surfactant 1

<Intermediate layer coating solution: Formulation P1>
PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550) 32.2 partsPolyvinylpyrrolidone (APS Japan, K-30) 14.9 partsDistilled water 524 parts・ 429 parts of methanol

[Example 3]
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.
The cover film is removed from the photosensitive transfer material K1 produced by the above-described manufacturing method on the obtained silane coupling treated glass substrate, and the surface of the dark color composition layer exposed after the removal and the silane coupling treated glass substrate. The substrate was heated to 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries (Lamic II type)), a rubber roller temperature of 130 ° C., and a linear pressure of 100 N / cm. Lamination was performed at a conveyance speed of 2.2 m / min. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. 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 dark color composition layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, development is performed with a 0.5% KOH aqueous solution to remove the unexposed portion of the dark color composition layer, the intermediate layer below it, and the thermoplastic resin layer to obtain a black matrix pattern-like separation wall on the glass substrate. It was. Subsequently, the entire surface of the substrate from the surface of the substrate was post-exposed at 2000 mJ / cm ² with an aligner in the atmosphere to obtain a separation wall having an optical density of 4.0.
The shape of the separation wall thus obtained was observed in the same procedure as in Example 1. As a result, h = 1.8 μm, d = 0.05 μm, and d / h = 0.028. .
Next, a water repellency treatment was performed by the following method.

[Water repellent treatment by coating method]
Alkaline in which 0.5% (based on the solid content of the photosensitive resin) of fluorine-based surfactant (manufactured by Sumitomo 3M, Fluorad FC-430) is previously added on the substrate on which the separation wall is formed. A soluble photosensitive resin (Positive photoresist AZP4210, manufactured by Hoechst Japan 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. went.
Next, exposure was performed through the separation wall from the back surface of the substrate on which the separation wall was formed with an exposure amount of 110 mJ / cm ² (38 mW / cm ² × 2.9 seconds), and an inorganic alkali developer (manufactured by Hoechst Japan, AZ400K developer, 1: 4) After immersing and shaking for 80 seconds, rinse with pure water for 30 to 60 seconds to form a water-repellent resin layer on the image separation wall, thereby changing the surface energy difference between the inside and outside of the pixel. Was provided. 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).

  Next, after coloring the R, G, and B pixels in the same manner as in Example 1, the color filter was baked in an oven at 230 ° C. for 30 minutes to completely cure both the separation wall and each pixel.

In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the image separation walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found. A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and separation wall of the color filter substrate obtained above.
When the ITO resistance of this color filter was measured ("Loresta" manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by the four probe method), it showed a very low value of 7Ω / □. This is considered to be because the flatness of the surface of the separation wall is increased by using the present invention.
Next, an alignment-divided vertical alignment type liquid crystal display device was produced by the same method as in Example 1.

[Example 4]
The same material and procedure as in Example 3 were used for development, post-exposure was not performed, and the substrate with the separation wall was baked in an oven at 80 ° C. for 40 minutes to advance the separation wall, thereby increasing the optical density. A separation wall of 4.1 was obtained. The shape of the separation wall thus obtained was observed in the same procedure as in Example 1. As a result, h = 1.6 μm, d = 0.052 μm, and d / h = 0.033. .

  Next, after coloring the R, G, and B pixels in the same manner as in Example 1, the color filter was baked in an oven at 230 ° C. for 30 minutes to completely cure both the separation wall and each pixel.

In the color filter thus obtained, the ink constituting each pixel fits exactly in the gap between the image separation walls, and no defects such as bleeding, protrusion, color mixture with adjacent pixels and white spots were found. A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and separation wall of the color filter substrate obtained above.
When the ITO resistance of the color filter was measured (“Loresta” manufactured by Mitsubishi Chemical Corporation; sheet resistance was measured by the four-probe method), it showed a very low value of 8Ω / □. This is considered to be because the flatness of the surface of the separation wall is increased by using the present invention.
Next, an alignment-divided vertical alignment type liquid crystal display device was produced by the same method as in Example 1.

[Example 5]
In Example 3, a separation wall was produced in the same manner as in Example 3 except that the photosensitive transfer material K1 was changed to the following photosensitive transfer material K2.
Next, an alignment-divided vertical alignment type liquid crystal display device was produced by the same method as in Example 1.

[Production Method of Photosensitive Transfer Material K2]
The dark color composition K1 was applied and dried on a 16 μm thick polyethylene terephthalate film (Tetron G2 manufactured by Teijin DuPont Films Ltd.) temporary support using a slit-shaped nozzle. In this way, a dark color composition layer having a dry film thickness of 2.0 μm was provided on the temporary support, and finally a protective film (thickness 12 μm polypropylene film) was pressure-bonded.
In this way, a photosensitive transfer material in which the temporary support and the dark color composition layer were integrated was prepared, and the sample name was designated as photosensitive transfer material K2.

[Comparative Example 1]
Instead of performing exposure under nitrogen in the exposure step of Example 1, a substrate with a black matrix-like separation wall was obtained by performing exactly the same processes and operations as in Example 1 except that exposure under the atmosphere was performed. The optical density of the separation wall thus obtained was 3.9.
The shape of the separation wall thus obtained was observed in the same procedure as in Example 1. As a result, h = 1.7 μm, d = 0.14 μm, and d / h = 0.082. Next, after coloring the R, G, and B pixels in the same manner as in Example 1, baking was performed under the same conditions. As a result, the ink got over the image separation wall, and color mixing with adjacent pixels had occurred. Further, when the ITO resistance was measured in the same manner as in the example, it was 22Ω / □, and the flatness of the black matrix surface was not so high.
Next, an alignment-divided vertical alignment type liquid crystal display device was produced by the same method as in Example 1.

[Evaluation]
-ITO resistance value-
The sheet resistance was measured for the ITO resistance of the color filter formed with the ITO film by “Loresta” manufactured by Mitsubishi Chemical Corporation;

-Display unevenness-
When a gray test signal was input to the liquid crystal display device, the presence or absence of unevenness was observed visually and with a magnifying glass, and judged according to the following criteria.
[Standard]
○: Unevenness was hardly observed.
Δ: Some unevenness was observed.
X: Unevenness was remarkably confirmed.
The above results are summarized in Table 2. Moreover, the conceptual diagram of the cross-sectional shape of the color filter of an Example and a comparative example is shown in FIG.

  It can be seen from Table 2 that the liquid crystal display device according to the present invention has a high quality with low ITO resistance and no display unevenness. This is considered to be one of the factors that the present invention has been able to suppress the overcoming of ink at the time of RGB ink ejection.

It is a schematic cross section for demonstrating the shape of a separation wall. FIG. 3 is a conceptual diagram showing a color filter pattern. (A) is a top view which expands and shows one pixel which concerns on one Embodiment of the color filter for MVA-LCD of this invention, (b) is sectional drawing of the AA 'line in (a). . (A) is a top view which shows the state at the time of arrange | positioning a TFT side board | substrate to the color filter for MVA-LCD shown in FIG. 3, and setting it as MVA-LCD, (b) is BB 'in (a). It is sectional drawing of a line, (c) is a figure which shows the inclination direction of the liquid crystal molecule in one pixel. (A) is a top view which expands and shows one pixel which concerns on other embodiment of the color filter for MVA-LCD, (b) is sectional drawing of CC 'line in (a), c) is a diagram showing the tilt direction of the liquid crystal molecules in one pixel. It is sectional drawing which shows one Embodiment of MVA-LCD of this invention. It is a conceptual diagram of the cross-sectional shape of the color filter of an Example and a comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Liquid crystal display device 11, 28 Glass substrate 12 Array substrate 14 Opposite substrate 16 Liquid crystal layer 18 Sealing material 20 Signal line 22 Pixel electrode 24 TFT
26, 33 Alignment film 30 Colored pixel layer 32 Counter electrode 34 Separation walls 35G, 35B, 35R Colored pixel 40 Projection for alignment division 42 Columnar spacers 44, 45 Polarizing plate

Claims (4)

A colored pixel layer having at least red, green, and blue colored pixels provided in a gap between the separation wall and the separation wall on the transparent substrate, and an alignment dividing protrusion provided on the colored pixel layer, A method for producing a color filter for an alignment-divided vertical alignment type liquid crystal display device, comprising:
Forming at least the separation wall on the transparent substrate; and forming each colored pixel in a gap between the separation walls;
In the cross section of the separation wall, the height of the separation wall from the transparent substrate at the highest height from the transparent substrate is h, and the transparent substrate is positioned at 0.8 h from the transparent substrate. When L ₁ is a parallel line, L ₂ is a tangent line at a point where L ₁ is in contact with the separation wall, and L ₃ is a line parallel to the transparent substrate at the position h, the relationship between L ₂ and L ₃ A method of manufacturing a color filter for an alignment-divided vertical alignment liquid crystal display device, wherein a value d / h obtained by dividing a distance d from the intersection point to the separation wall by h satisfies 0.04 or less.   2. The alignment-divided vertical alignment liquid crystal display according to claim 1, wherein the step of forming the colored pixels is a step of applying droplets of the colored liquid composition to the gap between the separation walls by an ink jet method. A method for producing a color filter for an apparatus.   A color filter for an alignment division vertical alignment type liquid crystal display device manufactured by the method for manufacturing a color filter for alignment division vertical alignment type liquid crystal display device according to claim 1.   4. An alignment division vertical alignment type liquid crystal display device comprising the color filter for alignment division vertical alignment type liquid crystal display device according to claim 3.

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