JP2009300724A - Ink for color filter, color filter, image display device, and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink for a color filter in an inkjet system, the ink that can be stably and suitably used for the manufacture of a color filter suppressing color unevenness and density unevenness in each portion and having excellent uniformity of characteristics in individual products, and to provide a color filter suppressing color unevenness and density unevenness in each portion and having excellent durability as well as excellent uniformity of characteristics in individual products, and to provide an image display device and electronic equipment having the color filter. <P>SOLUTION: The ink 2 for a color filter for forming a colored portion 12 on a substrate 11 by an inkjet system is characterized in that: the ink contains a colorant and a liquid medium in which the colorant is dissolved/dispersed; and that when a film comprising a polyphenylene sulfide resin is left to stand in the above liquid medium in a sealed state in an environment of the atmospheric pressure at 40°C for 10 days, the weight increase rate of the film is not more than 7.0%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a color filter ink, a color filter, an image display device, and an electronic apparatus.

A color filter is generally used for a liquid crystal display (LCD) or the like that performs color display.
A color filter has conventionally formed a coating film composed of a material (colored layer forming composition) containing a colorant, a photosensitive resin, a functional monomer, a polymerization initiator, etc. on a substrate, and then a photomask. It has been manufactured by using a so-called photolithography method in which a photosensitive process, a developing process, and the like are performed. In such a method, the colors are usually overlapped by repeating the operation of forming a coating film corresponding to each color on almost the entire surface of the substrate, curing only a part thereof, and removing most of the other part. Manufacture color filters so that they do not match. For this reason, only a part of the coating film formed in the manufacture of the color filter remains as a colored layer in the finally obtained color filter, and most of it is removed in the manufacturing process. Become. For this reason, not only the manufacturing cost of the color filter increases, but also from the viewpoint of resource saving.

  On the other hand, in recent years, a method of forming a colored layer of a color filter using an ink jet head (droplet discharge head) has been proposed (see, for example, Patent Document 1). Such a method can easily control the discharge position of the droplets of the colored layer forming material (colored layer forming composition) and can reduce waste of the colored layer forming composition. The manufacturing cost can also be suppressed. However, in the method of manufacturing a color filter using an inkjet head, when droplets are ejected for a long period or when droplets are ejected continuously, the trajectory of the ejected droplets changes (so-called flight curve). In some cases, the liquid droplets cannot be landed on the target site, or the discharge amount of the liquid droplets becomes unstable. When such a problem occurs, a plurality of types of inks used to form colored portions of different colors may be mixed (mixed) on the substrate on which the droplets are to be landed, or may be the same in nature. Variations in color density between multiple colored parts that are required to have a color density occur, resulting in color unevenness, density unevenness, etc. in each part of the color filter, Variations in characteristics (particularly, color characteristics such as contrast ratio and color reproduction range) among a large number of color filters result in low reliability of the color filters. Also, the droplet discharge device (industrial use) used in the manufacture of color filters is completely different from that applied to printers (consumer use). For example, mass production or large workpieces (substrates) are used. Therefore, it is required to discharge a large amount of droplets over a long period of time. In addition, liquid droplet ejection devices (industrial) used for manufacturing color filters generally have higher viscosity and higher specific gravity than inks used in printers (consumer products). The load applied to the droplet discharge head is much larger than that of a consumer printer. Since it is used under such severe conditions, in the production of a color filter by the conventional ink jet method, the ink jet head is rapidly deteriorated, and it is necessary to replace or repair the ink jet head at a relatively high frequency. When the inkjet head is replaced or repaired, adjustment of droplet discharge conditions (for example, adjustment of voltage waveform, etc.) is performed again in order to suppress variation in characteristics among a number of manufactured color filters. It was necessary, and this was a factor that lowered the productivity of the color filter.

JP 2002-372613 A

  An object of the present invention is an ink-jet color filter that can be stably and suitably used for the production of a color filter that suppresses uneven color and density unevenness at each site and has excellent uniformity of characteristics among individuals. Providing a color filter that suppresses color unevenness and density unevenness in each part, is excellent in durability, and has excellent uniformity of characteristics among individuals, An object of the present invention is to provide an image display device and an electronic device including a color filter.

Such an object is achieved by the present invention described below.
The color filter ink of the present invention is a color filter ink used for manufacturing a color filter that forms a colored portion on a substrate by an ink jet type droplet discharge device,
A colorant and a liquid medium in which the colorant is dissolved and / or dispersed,
When the film made of polyphenylene sulfide resin is allowed to stand in an atmosphere of 40 ° C. for 10 days in the sealed liquid medium, the weight increase rate of the film is 7.0% or less. It is characterized by being.
As a result, color unevenness, density unevenness, and the like at each part are suppressed, and ink for color filters of an ink jet method that can be stably and suitably used for producing a color filter having excellent uniformity of characteristics among individuals. Can be provided.

In the color filter ink of the present invention, the polyphenylene sulfide resin preferably has a weight average molecular weight of 5,000 to 100,000.
A film made of such a polyphenylene sulfide resin has particularly high chemical stability and is particularly excellent in mechanical strength. Therefore, as a member constituting a diaphragm of a droplet discharge device as described later. It can be used suitably. Furthermore, it is difficult to be affected by the liquid medium, and the discharge stability of the color filter ink can be made particularly excellent over a long period of time.

In the color filter ink of the present invention, the liquid medium preferably contains an alkoxyl group and / or an acetyl group at the end of the molecular chain.
This effectively prevents deterioration and clogging of the droplet discharge head (inkjet head) that discharges the color filter ink, and makes the manufactured color filter more individual and individual. It can be made excellent in uniformity.

In the color filter ink of the present invention, the liquid medium preferably has an acetyl group at both ends of the molecular chain.
This effectively prevents deterioration and clogging of the droplet discharge head (inkjet head) that discharges the color filter ink, and makes the manufactured color filter more individual and individual. It can be made excellent in uniformity.

In the color filter ink of the present invention, the liquid medium preferably contains an ether oxygen atom bonded to the second carbon atom in the molecule.
This effectively prevents deterioration and clogging of the droplet discharge head (inkjet head) that discharges the color filter ink, and makes the manufactured color filter more individual and individual. It can be made excellent in uniformity.

The color filter ink of the present invention is preferably used for manufacturing a color filter by being ejected from a droplet ejection head in which at least a part of the diaphragm is composed of the polyphenylene sulfide resin.
This effectively prevents deterioration and clogging of the droplet discharge head (inkjet head) that discharges the color filter ink, and makes the manufactured color filter more individual and individual. It can be made excellent in uniformity.

The color filter ink of the present invention preferably contains a polyhydric alcohol.
Thereby, the discharge stability over a long period of time can be effectively improved, and deterioration or clogging of a droplet discharge head (inkjet head) that discharges color filter ink can be effectively prevented. The produced color filter can have higher quality and excellent uniformity of characteristics among individuals.

The color filter ink of the present invention contains a resin material,
The resin material preferably includes a polymer A containing at least an epoxy group-containing vinyl monomer a1 as a monomer component.
Thereby, the discharge stability over a long period of time can be effectively improved, and deterioration or clogging of a droplet discharge head (inkjet head) that discharges color filter ink can be effectively prevented. The produced color filter can have higher quality and excellent uniformity of characteristics among individuals.

In the color filter ink of the present invention, the polymer A includes, as a monomer component, an isocyanate group or a blocked isocyanate group in which the protective group is protected in addition to the epoxy group-containing vinyl monomer a1. A copolymer containing the vinyl monomer a2 is preferred.
Thereby, the discharge stability over a long period of time can be effectively improved, and deterioration or clogging of a droplet discharge head (inkjet head) that discharges color filter ink can be effectively prevented. The produced color filter can have higher quality and excellent uniformity of characteristics among individuals.

これにより、カラーフィルター用インクを吐出する液滴吐出ヘッド（インクジェットヘッド）の劣化や目詰まり等を効果的に防止することができ、製造されるカラーフィルターの各部位での色むら、濃度むら等をより効果的に防止し、個体間での特性の均一性を特に優れたものとすることができるとともに、形成される着色部の基板に対する密着性を特に優れたものとし、製造されるカラーフィルターの耐久性（耐光性、耐熱性等）を特に優れたものとすることができる。また、カラーフィルター用インクが、着色剤として顔料を含む場合においては、カラーフィルター用インク中における顔料の分散安定性（カラーフィルター用インクの長期保存性）を特に優れたものとすることができる。 The color filter ink of the present invention contains a resin material,
The resin material preferably includes a polymer B containing at least an alkoxysilyl group-containing vinyl monomer represented by the following formula (1) as a monomer component.

As a result, it is possible to effectively prevent deterioration and clogging of a droplet discharge head (inkjet head) that discharges color filter ink, and color unevenness, density unevenness, etc. at each part of the manufactured color filter. Color filter that can be more effectively prevented, the uniformity of characteristics among individuals can be made particularly excellent, and the adhesion of the formed colored part to the substrate is particularly excellent. Can be made particularly excellent in durability (light resistance, heat resistance, etc.). Further, when the color filter ink contains a pigment as a colorant, the dispersion stability of the pigment in the color filter ink (long-term storage stability of the color filter ink) can be made particularly excellent.

In the color filter ink of the present invention, the colorant contains a pigment,
The pigment is C.I. I. Pigment Green 58 is preferably included, and a sulfonated pigment derivative is preferably included as a secondary pigment.
C. I. Although Pigment Green 58 has a feature of excellent brightness, conventionally, it has been an extremely difficult material to stably disperse in color filter inks. Conventionally, the color filter ink used in the ink jet system is C.I. I. When the pigment green 58 is included, there is a problem that the discharge stability of the droplet is remarkably lowered. On the other hand, according to the present invention, it is difficult to stably disperse C.I. I. Even in the case of CI Pigment Green 58, the long-term dispersion stability of the pigment in the color filter ink can be made particularly excellent, and the droplet ejection stability can also be made excellent. That is, C.I. I. By including the pigment green 58, the effect of the present invention is more remarkably exhibited.

The color filter of the present invention is manufactured using the color filter ink of the present invention.
As a result, it is possible to provide a color filter that suppresses color unevenness, density unevenness, and the like in each part of the display unit, is excellent in durability, and is excellent in uniformity of characteristics among individuals.

An image display device according to the present invention includes the color filter according to the present invention.
As a result, it is possible to provide an image display device that suppresses uneven color, uneven density, and the like in each part of the display unit, is excellent in durability, and has excellent uniformity of characteristics among individuals.
An electronic apparatus according to the present invention includes the image display device according to the present invention.
As a result, it is possible to provide an electronic device that suppresses uneven color, uneven density, and the like in each part of the display unit, is excellent in durability, and is excellent in uniformity of characteristics among individuals.

Hereinafter, preferred embodiments of the present invention will be described in detail.
《Color filter ink》
The color filter ink of the present invention is an ink used for the production of a color filter (formation of a colored portion of a color filter), and is particularly used for the production of a color filter by an ink jet method.
The color filter ink includes a colorant, a liquid medium in which the colorant is dissolved and / or dispersed, a curable resin material, and the like.

<Colorant>
A color filter usually has different colored portions (generally, three colors corresponding to RGB). The colorant is usually selected according to the color tone of the colored portion to be formed. As a colorant constituting the color filter ink, for example, various pigments and various dyes can be used.

  Examples of the pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 21, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 108: 1, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193 194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265; C. I. Pigment Green 7, 36, 15, 17, 18, 19, 26, 50, 58; I. Pigment blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6, 17: 1,18,60,27,28,29,35,36,60,80; I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 34, 35, 35: 1, 37, 37: 1, 42, 43, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 157, 166, 168, 175, 180, 184, 185; I. Pigment violet 1, 3, 14, 16, 19, 23, 29, 32, 36, 38, 50; C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 20, 20: 1, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, 104; C. I. Pigment brown 7, 11, 23, 25, 33; I. Pigment Black 1 and 7 and derivatives thereof may be used, and one or more selected from these may be used in combination.

When the color filter ink is a pigment containing a pigment as a colorant (pigment ink), the manufactured color filter has excellent light resistance and the like compared to a pigment containing a dye as a colorant (dye ink). be able to.
In particular, the color filter ink is used as a pigment (red pigment) as C.I. I. Pigment Red 177 and its derivatives, and / or C.I. I. When the pigment red 254 and derivatives thereof are included, the color developability of the color filter ink (red color filter ink) can be made particularly excellent. In addition, the effect of using in combination with a dispersant and a curable resin material (curable resin composition), which will be described in detail later, is more prominent, and the dispersion stability of the pigment particles in the color filter ink is excellent. Can be. As a result, when the ink is applied to the cells, the discharge stability of the color filter ink can be made particularly excellent, and color unevenness and density unevenness in each colored portion can be suppressed. The contrast ratio can be particularly excellent.
C. I. Pigment Red 177 derivatives, C.I. I. When the compound of Pigment Red 254 contains a compound (derivative) represented by the following formula (2) or the following formula (3), the above-described effects are more remarkably exhibited.

  In particular, the color filter ink is used as a pigment (green pigment) as C.I. I. When it contains CI Pigment Green 58 (brominated zinc phthalocyanine pigment), the color developability of the color filter ink (green color filter ink) can be made particularly excellent. In addition, C.I. I. Although Pigment Green 58 has a feature of excellent brightness, conventionally, it has been an extremely difficult material to stably disperse. However, the present inventor I. It has been found that even when Pigment Green 58 is included, the dispersion stability in the color filter ink can be improved by simultaneously including a sulfonated pigment derivative as a sub-pigment. Thereby, the color developability of the color filter ink can be further improved. In addition, the long-term storage stability of the pigment in the color filter ink and the discharge stability of the color filter ink can be made particularly excellent.

  As a pigment, C.I. I. When the pigment green 58 and the sulfonated pigment derivative are included, it is preferable to contain a compound (derivative) represented by the following formula (5) as the sulfonated pigment derivative. Thereby, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent, and an image with a better contrast can be displayed on the manufactured color filter.

In this way, a pigment derivative (sub-pigment) having a specific chemical structure is converted into C.I. I. By using together with Pigment Green 58 (main pigment), the above-described excellent effect is obtained as a result of intensive studies by the present inventors, and details of the mechanism are unknown. However, it is thought that this is due to the following reasons.
C. I. The brominated phthalocyanine constituting the pigment green 58 has a highly conjugated system as a whole molecule, and has a planar structure, which is stable in terms of energy. The brominated phthalocyanine is placed in a stable state in which the conjugated π electrons between the molecules overlap each other by arranging (parallel) the planar molecules. For this reason, C.I. I. Pigment Green 58 inherently tends to agglomerate and is difficult to stably disperse in a liquid medium.

  On the other hand, in the pigment derivative as described above, the hydrogen atom bonded to the nitrogen atom in the formula (5) forms a hydrogen bond with the oxygen atom constituting the phthalimide structure. For this reason, the hydrogen atom bonded to the nitrogen atom in formula (5) is substantially bonded to the oxygen atom constituting the phthalimide structure together with the nitrogen atom constituting the quinoline structure. In the pigment derivative (sulfonated pigment derivative) as described above, a stable ring structure (7-membered ring structure) with 7 atoms numbered 1 to 7 in the formula (5) is formed. By forming such a seven-membered ring structure, the plane due to the quinoline structure and the plane due to the phthalimide structure are in a non-parallel state.

  In this way, the plane due to the quinoline structure and the plane due to the phthalimide structure are non-parallel, so that C.I. I. A pigment derivative (sulfonated pigment derivative) having an appropriate affinity for CI Pigment Green 58 (brominated phthalocyanine) is disclosed in C.I. I. Pigment Green 58 enters between the molecules, and as described above, C. I. It is possible to make the pigment green 58 difficult to aggregate. Furthermore, since the above pigment derivatives (sulfonated pigment derivatives) have a sulfo group in the molecule, they are excellent in dispersibility in a liquid medium described later. The above is considered to act synergistically and to obtain the above excellent effects.

  C. I. When the pigment green 58 and the pigment derivative (sulfonated pigment derivative) as described above are included, the content of the pigment derivative (sulfonated pigment derivative) in the color filter ink is not particularly limited. I. Pigment Green 58 (main pigment): It is preferably 2 to 32 parts by weight, more preferably 7 to 28 parts by weight with respect to 100 parts by weight. Thereby, the dispersion stability of the pigment particles in the color filter ink can be made excellent. Further, the contrast ratio and brightness of the manufactured color filter can be made particularly excellent.

  In particular, the color filter ink is used as a pigment (blue pigment). I. Pigment blue 15: 6 or C.I. I. When the pigment blue 15 derivative is included, the color developing property of the color filter ink (blue color filter ink) can be made particularly excellent. In addition, the dispersion stability of the pigment particles in the color filter ink can be made particularly excellent.

  When the color filter ink is a pigment containing a pigment as a colorant (pigment ink), the average particle diameter of the pigment is preferably 10 to 200 nm, and more preferably 20 to 180 nm. As a result, the durability (light resistance) of the color filter manufactured using the color filter ink while sufficiently improving the dispersion stability of the pigment in the color filter ink and the discharge stability of the color filter ink. Etc.) can be made sufficiently excellent, and the color developability, contrast, etc. in the color filter can be made particularly excellent.

  Examples of the dye include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine, and polymethine dyes. Specific examples of the dye include C.I. I. Direct Red 2, 4, 9, 23, 26, 28, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247; I. Acid Red 35, 42, 51, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 145, 151, 154, 157, 158, 211, 249, 254 257, 261, 263, 266, 289, 299, 301, 305, 319, 336, 337, 361, 396, 397; I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55; I. B. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46; I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101; I. Acid Violet 5, 9, 11, 34, 43, 47, 48, 51, 75, 90, 103, 126; I. Reactive violet 1,3,4,5,6,7,8,9,16,17,22,23,24,26,27,33,34; I. B. Basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48; I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163; I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195 196, 197, 199, 218, 219, 222, 227; I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42; I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40; I. Acid Green 16; C.I. I. Acid Blue 9, 45, 80, 83, 90, 185; I. Basic oranges 21, 23 and the like can be mentioned, and one or more selected from these can be used in combination.

  The content of the colorant in the color filter ink is preferably 2 to 25 wt%, and more preferably 3 to 20 wt%. When the content of the colorant is a value within the above range, the discharge property (discharge stability) from the droplet discharge head (inkjet head) for the color filter is particularly excellent, and the produced color filter The durability can be improved. Further, a sufficient color density can be secured in the manufactured color filter.

<Liquid medium>
The liquid medium (liquid medium) has a function of dissolving and / or dispersing the colorant as described above. That is, the liquid medium functions as a solvent and / or a dispersion medium. In general, most of the liquid medium is removed in the process of manufacturing the color filter.

  By the way, as will be described in detail later, a droplet discharge head (inkjet head) used for droplet discharge by the inkjet method is generally composed of a plurality of members such as a vibrator and a diaphragm. When manufacturing a color filter, ink is discharged from a droplet discharge head (inkjet head) by transmitting high-frequency vibrations of a vibrator to ink through a vibration plate. As a member constituting such a diaphragm, it is generally made of polyphenylene sulfide resin (PPS resin) from the viewpoint of being chemically stable and having high mechanical strength such as pulling and bending and high durability against heat and solvent. The film is used. That is, the PPS resin film is present at the interface between the ink and the vibrator and plays a role of accurately transmitting the mechanical vibration of the vibrator to the ink.

  The droplet discharge device (industrial use) used in the manufacture of color filters is completely different from that applied to printers (consumer use). Since it is used for droplet ejection, it is required to eject a large amount of droplets for a long time, and it is used under severe conditions. In addition, a droplet discharge device (for industrial use) used for manufacturing a color filter needs to have a stable droplet discharge amount with high accuracy over a long period of time.

  However, since the conventional color filter ink is used under the severe conditions as described above, the influence on the PPS resin constituting the diaphragm becomes remarkable, the deterioration of the ink jet head is accelerated, and the ink jet head is relatively frequently used. There was a need to replace or repair. When the inkjet head is replaced or repaired, adjustment of droplet discharge conditions (for example, adjustment of voltage waveform, etc.) is performed again in order to suppress variation in characteristics among a number of manufactured color filters. It was necessary, and this was a factor that lowered the productivity of the color filter.

Therefore, the present inventor has conducted intensive research for the purpose of solving the above problems. As a result, it has been found that the above problems can be solved by using a liquid medium as described below.
The color filter ink of the present invention is characterized in that a liquid medium having the following characteristics is used. That is, the liquid medium used in the present invention is an increase in the weight of the PPS resin film when the PPS resin film is allowed to stand in a sealed liquid medium at 40 ° C. for 10 days under atmospheric pressure. The rate (hereinafter also referred to as “weight increase rate of PPS resin”) is 7.0% or less. By using a liquid medium that satisfies these conditions, even when droplets are ejected for a long period of time in the production of a color filter using an ink jet method, the conditions such as the droplet ejection amount are stabilized. Therefore, a stable color filter can be manufactured over a long period of time. That is, color unevenness, density unevenness and the like in each part are suppressed, and a color filter excellent in the uniformity of characteristics among individuals can be stably manufactured over a long period of time. In addition, by satisfying the above conditions, it is possible to effectively prevent deterioration of the droplet discharge head used for droplet discharge. For this reason, even when a large number of color filters are manufactured, the frequency of maintenance such as replacement and repair of the droplet discharge head can be reduced, so that the productivity of the color filter can be improved. it can.

  On the other hand, if the swelling rate of the PPS resin for the liquid medium is too large, the PPS resin film becomes an ink solvent when droplet discharge is performed for a long time in the production of a color filter using an ink jet method. It absorbs and absorbs a little and increases its weight, and wrinkles are generated and the shape is distorted and anisotropy occurs in the tension in the film surface, affecting the natural frequency transmitted from the vibrator to the ink. Appears, the droplet discharge conditions become unstable, and it becomes difficult to sufficiently suppress color unevenness, density unevenness and the like in each part of the manufactured color filter. In addition, when a large number of color filters are manufactured, the variation in characteristics among individuals increases, and it becomes difficult to stably manufacture color filters of excellent quality. The swelling rate of the PPS resin film can be measured using, for example, a film-like test piece of 150 mm × 150 mm × thickness 0.1 mm.

As described above, in the present invention, the weight increase rate of the PPS resin film when the PPS resin film is allowed to stand in a sealed liquid medium at 40 ° C. under atmospheric pressure for 10 days. Is 7.0% or less, but the weight increase rate of the PPS resin film when left in the above-mentioned environment is preferably 5.0% or less, more preferably 4.0% or less. preferable. Thereby, the effect of the present invention as described above becomes more remarkable. Here, the weight increase rate means that when the weight before immersion in the liquid medium is w _B [g] and the weight after the immersion treatment under the above conditions is w _A [g], [(w _A / w _B ) −1] Indicates a value (%) represented by × 100.

  The PPS resin preferably has a weight average molecular weight of 5,000 to 100,000. A film made of such a PPS resin has a particularly high chemical stability and is particularly excellent in mechanical strength, and is therefore suitable as a member constituting a diaphragm of a droplet discharge device as described later. Can be used. Furthermore, it is difficult to be affected by the liquid medium, and the discharge stability of the color filter ink can be made particularly excellent over a long period of time.

  In the present invention, it is particularly preferable to use a liquid medium having an alkoxyl group and / or an acetyl group at the end of the molecular chain. Thereby, the influence with respect to PPS resin can be made smaller, and discharge stability can be made excellent. Moreover, the solubility in the ink for color filters of the curable resin material which is explained in full detail later can be made excellent. In particular, even when an environmental change such as a temperature change occurs, the solubility of the curable resin material can be made excellent, and an unintentional curable resin material of the color filter ink can be stored during storage. Precipitation and hardening of the curable resin material can be reliably prevented. As a result, deterioration and clogging of the droplet discharge head (inkjet head) that discharges the color filter ink can be effectively prevented, and the manufactured color filter has higher quality and individual characteristics. It can be made excellent in uniformity. In addition, it can stably discharge liquid droplets for a longer period of time, and has particularly excellent adhesion (color filter durability) to the substrate of the colored portion formed using the color filter ink. can do.

  Examples of the compound having the above properties and usable as a liquid medium include 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate, tripropylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether, 1,3-butylene glycol diacetate, triethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, diethylene glycol diacetate, polyethylene glycol monomethyl ether, 1-butoxy-2-propanol, 2-butoxy-1 -Propanol, ethylene carbonate, butylene carbonate, propylene carbonate, 3,5,5-trimethyl-2-cyclohexen-1-one, ethyl octoate, butyl lactate, dipropylene glycol Dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, 3-ethoxypropionic acid Examples thereof include dicarboxylic acid diesters such as ethyl, 3-methoxy-n-butyl acetate, dimethyl succinate, dimethyl glutarate, and dimethyl adipate. These can be used alone or in combination of two or more. .

  The liquid medium may have an acetyl group at both ends of the molecular chain. As a result, the influence of the liquid medium on the vibration plate can be reduced, and deterioration or clogging of the droplet discharge head (inkjet head) that discharges the color filter ink can be effectively prevented. Can do. As a result, the manufactured color filter can be made higher in quality and excellent in uniformity of characteristics among individuals. Examples of the compound having an acetyl group at both ends of the molecular chain (liquid medium) include 1,3-butylene glycol diacetate, triethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate, diethylene glycol diacetate and the like. Is mentioned.

  Further, the liquid medium may include an ether oxygen atom bonded to the second carbon atom (a carbon atom bonded to two carbon atoms) in the molecule. As a result, the influence of the liquid medium on the vibration plate can be reduced, and deterioration or clogging of the droplet discharge head (inkjet head) that discharges the color filter ink can be effectively prevented. Can do. As a result, the manufactured color filter can be made higher in quality and excellent in uniformity of characteristics among individuals. Examples of the compound (liquid medium) containing an ether oxygen atom bonded to the second carbon atom in the molecule include 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate, 3-methoxy- Examples include n-butyl acetate, 1-butoxy-2-propanol, and 2-butoxy-1-propanol.

Moreover, it is good also as a liquid medium using multiple types of compounds as mentioned above.
For example, the liquid medium may include a first liquid medium as a liquid medium as a main component and a second liquid medium as a subcomponent.
In such a case, the second liquid medium is preferably a glycol condensate monoalkyl ether having an average degree of polymerization of 4 to 10. The glycol condensate monoalkyl ether is a compound in which the terminal hydroxyl group of the glycol condensate is substituted with an alkyl group.

  The glycol condensate monoalkyl ether having the average polymerization degree as described above is a compound having a relatively high boiling point and capable of reducing the thixotropic property of the ink. By including the glycol condensate monoalkyl ether, the color filter ink is thixotropic due to the glycol condensate monoalkyl ether remaining in the ink even when a certain amount of the liquid medium is volatilized from the color filter ink. As a result, it is possible to maintain the high fluidity for a relatively long time. For this reason, even when the liquid medium is volatilized from a specific portion at the time of forming the colored portion, the color filter ink can be more uniformly mixed, and the solid content of the ink is concentrated on the portion. Is prevented. As a result, the color filter ink in the cell has a uniform solid content concentration in each portion, and can lose its fluidity and solidify when the surface is flat. As a result, the colored portions to be formed have a particularly high flatness, and the resulting color filter has particularly excellent uniformity in characteristics among individuals, with suppressed color unevenness and density unevenness in each part. It becomes. In addition, the brightness and contrast ratio are particularly excellent.

  Glycols constituting the glycol condensate monoalkyl ether are not particularly limited. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol and other propanediols, various butanediols, various pentanediols, various types A hexanediol etc. are mentioned, Among these, it can use 1 type or in combination of 2 or more types. Of these, ethylene glycol, 1,2-propanediol, and 1,3-propanediol are preferably used. Thereby, it is possible to sufficiently suppress an increase in the thixotropic property of the ink when forming the colored portion while sufficiently reducing the ink viscosity for the color filter. As a result, the colored portions to be formed have a particularly high flatness, and the resulting color filter has particularly excellent uniformity in characteristics among individuals, with suppressed color unevenness and density unevenness in each part. It becomes. In addition, the brightness and contrast ratio are particularly excellent.

  The average degree of polymerization of the glycol condensate monoalkyl ether may be within the above-mentioned range, but is preferably 4-8. Thereby, it is possible to sufficiently suppress an increase in the thixotropic property of the ink when forming the colored portion while sufficiently reducing the ink viscosity for the color filter. As a result, the colored portions to be formed have a particularly high flatness, and the resulting color filter has particularly excellent uniformity in characteristics among individuals, with suppressed color unevenness and density unevenness in each part. It becomes. In addition, the brightness and contrast ratio are particularly excellent.

  Moreover, it is preferable that it is 210-500, and, as for the weight average molecular weight of glycol condensate monoalkyl ether, it is more preferable that it is 210-400. Thereby, it is possible to sufficiently suppress an increase in the thixotropic property of the ink when forming the colored portion while sufficiently reducing the ink viscosity for the color filter. As a result, the colored portions to be formed have a particularly high flatness, and the resulting color filter has particularly excellent uniformity in characteristics among individuals, with suppressed color unevenness and density unevenness in each part. It becomes. In addition, the brightness and contrast ratio are particularly excellent.

Further, the terminal alkyl group of the glycol condensate monoalkyl ether may be linear or may have a branched chain.
The number of carbon atoms of the terminal alkyl group of the glycol condensate monoalkyl ether is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. Thereby, the said effect can be made more remarkable.

Further, for example, the first liquid medium can have a relatively low boiling point, and the second liquid medium can have a higher boiling point than the first liquid medium. Thereby, at the time of removal of the liquid medium as described later, the first liquid medium volatilizes first with priority. The second liquid medium is retained in the color filter ink for a relatively long period of time. For this reason, the color filter ink in the cell can maintain fluidity for a relatively long time.
In such a case, the boiling point of the second liquid medium is preferably 5 to 80 ° C., more preferably 10 to 70 ° C. higher than the boiling point of the first liquid medium. Thereby, the color filter ink can maintain fluidity for a longer period when the colored portion is formed.

  In addition, when the color filter ink includes the first liquid medium and the second liquid medium as the liquid medium, the content of the first liquid medium in the color filter ink is the second liquid. When the content of the sex medium is 100 parts by weight, it is preferably 100 to 2000 parts by weight, and more preferably 150 to 1000 parts by weight. Thereby, the color filter ink can maintain fluidity for a longer period when the colored portion is formed. In addition, productivity when manufacturing a color filter is improved.

  Moreover, it is preferable that it is 0.5-20 mPa * s, and, as for the viscosity in 25 degreeC of a liquid medium, it is more preferable that it is 1-18 mPa * s. As described above, since the liquid medium has a sufficiently low viscosity, the viscosity of the color filter ink can be made sufficiently low, and the uniformity of the droplets of the color filter ink and the stability of the discharge amount can be achieved. Can be made particularly excellent. The viscosity of the liquid medium can be measured using, for example, an E-type viscometer (for example, RE-01 manufactured by Toki Sangyo Co., Ltd.), and in particular, can be performed according to JIS Z8803.

  The boiling point of the liquid medium under atmospheric pressure (1 atm) is preferably 160 to 330 ° C, more preferably 180 to 320 ° C, and further preferably 200 to 310 ° C. When the boiling point of the liquid medium under atmospheric pressure is a value within the above range, clogging or the like in the droplet discharge head that discharges the color filter ink can be more effectively prevented, and the productivity of the color filter is improved. Can be made particularly excellent.

  The vapor pressure at 25 ° C. of the liquid medium is preferably 0.7 mmHg or less, and more preferably 0.1 mmHg or less. When the vapor pressure of the liquid medium is within the above range, it is possible to more effectively prevent clogging and the like in the droplet discharge head that discharges the color filter ink, and the color filter productivity is particularly excellent. Can be.

  The content of the liquid medium in the color filter ink is preferably 50 to 98 wt%, more preferably 55 to 95 wt%, and even more preferably 65 to 93 wt%. When the content of the liquid medium is a value within the above range, the color filter ink is excellent in the discharge property from the droplet discharge head, and the manufactured color filter has excellent durability. can do. In addition, a sufficient color density can be ensured in the manufactured color filter.

<Polyhydric alcohol>
The color filter ink may contain a polyhydric alcohol. The polyhydric alcohol is a compound containing a plurality of unsubstituted hydroxyl groups. By including the polyhydric alcohol, the viscosity of the color filter ink can be in a suitable range, and the ink ejection stability can be further improved.
Further, the polyhydric alcohol has a function of flattening the colored portion by reducing the thixotropic property of the color filter ink at the time of forming the colored portion.

  In general, the colored portion is formed by applying a color filter ink to a cell formed by partition walls, removing a liquid medium from the applied color filter ink, and further solidifying the color filter ink. . In such a case, the solid content concentration of the colorant or the resin material as described later in the color filter ink in the cell is increased, and the thixotropic property and viscosity of the color filter ink are removed as the liquid medium is removed. Rises. In particular, when a pigment is used as the colorant, such an increase in thixotropic property becomes remarkable. As described above, since the thixotropic property is high, the color filter ink loses fluidity and easily solidifies even when the viscosity is relatively low.

  In addition, when the ink is dried by heating or vacuum drying, a phenomenon in which the ink is thermally convected (benard cell phenomenon) occurs in the cell due to volatilization of the liquid medium from the outer surface of the ink. In addition, due to heat distribution in the ink in the cell, volatilization of the liquid medium in the ink tends to occur from a specific portion of the cell. For this reason, the color filter ink in the cell does not have a uniform thickness and is easily uneven.

  As described above, when the convection of the ink in the cell and the volatilization of the liquid medium from a specific portion occur while the viscosity and thixotropic property of the color filter ink are increased, the color filter ink In a relatively early stage of removal, the shape having irregularities may lose fluidity and solidify. In such a case, the surface of the colored part to be formed tends to have many irregularities.

On the other hand, since the color filter ink contains a polyhydric alcohol, the polyhydric alcohol remains even when the majority of the liquid medium is removed from the color filter ink. An increase in thixotropic property can be suppressed, and the presence of a polyhydric alcohol whose viscosity has been reduced by heating makes it possible to maintain fluidity without solidifying for a relatively long time. At this time, even though the viscosity decreased, the color filter ink had a relatively high viscosity when a certain amount of the liquid medium was removed, and the rapid convection due to the temperature difference was suppressed. It has become. As described above, in the later stage of forming the colored portion, the color filter ink has fluidity while suppressing the convection of the color filter ink for a relatively long time. It loses fluidity and solidifies in a flat surface. For this reason, when such a color filter ink is used, the formed colored portion has a uniform thickness. As a result, the produced color filter is suppressed in color unevenness and density unevenness in each part, and is particularly excellent in the uniformity of characteristics among individuals. In addition, unintentional light scattering in the colored portion is suppressed, and the brightness and contrast ratio are particularly high.
Such polyhydric alcohol is decomposed or volatilized and removed from the color filter ink by heating when forming the colored portion. For this reason, polyhydric alcohol hardly remains in the formed colored portion, and changes in chromaticity, brightness, etc. of the colored portion due to the polyhydric alcohol contained in the ink are extremely small.

  In addition, by using the above-described glycol condensate monoalkyl ether in combination with a polyhydric alcohol in the ink, the glycol condensate monoalkyl ether is used in the ink when the liquid medium is volatilized when forming the colored portion. High fluidity can be maintained, and the solid content concentration of the ink in the cell can be made uniform. In addition, after most of the liquid medium is removed, the polyhydric alcohol maintains its fluidity while preventing rapid convection of the ink in the cell, so that the thickness is particularly uniform and the surface is particularly smooth. A colored portion is formed. As a result, the obtained color filter has suppressed color unevenness and density unevenness in each part, and is particularly excellent in the uniformity of characteristics among individuals. In addition, the brightness and contrast ratio are particularly excellent.

  The polyhydric alcohol that can be used in the color filter ink is not particularly limited as long as it reduces the thixotropic property of the color filter ink as described above. For example, an oligomer of a diol compound can be used. May be an oligomer of glycols. Such a compound can easily reduce the thixotropic property of the color filter ink, and can suppress convection in the cell of the color filter ink during the formation of the colored portion. In particular, when the polyhydric alcohol is an oligomer of glycols, the above-described effect becomes more remarkable.

Examples of glycols constituting the oligomer of glycols include the glycols described above, and one or more of these can be used in combination. Among these, it is preferable to use ethylene glycol or 1,3-propanediol as glycols.
As the polyhydric alcohol, an oligomer of glycols obtained by mixing and condensing ethylene glycol and 1,2-propylene glycol may be used, or an oligomer of ethylene glycol and an oligomer of 1,2-propylene glycol may be used. You may mix and use.

Moreover, when using the oligomer of glycols as a polyhydric alcohol, it is preferable that the terminal hydroxyl group is not substituted. Thus, when the polyhydric alcohol has a hydroxyl group, the polyhydric alcohol has a relatively high polarity, and the viscosity of the polyhydric alcohol easily falls within the range described later. In addition, the affinity for the color filter ink to a substrate (particularly a glass substrate) described later is excellent, and the color filter ink can spread more suitably in the cell. As a result, the obtained color filter has suppressed color unevenness and density unevenness in each part, and is particularly excellent in the uniformity of characteristics among individuals. In addition, the brightness and contrast ratio are particularly excellent.
When the polyhydric alcohol is an oligomer, the degree of polymerization of the polyhydric alcohol is preferably 3 to 40, and more preferably 3 to 20. Thereby, the thixotropic property of the color filter ink can be sufficiently lowered, and the convection of the color filter ink in the cell can be suppressed when the colored portion is formed.

  Moreover, it is preferable that the molecular weight of a polyhydric alcohol is 150-2000, It is more preferable that it is 180-1000, It is further more preferable that it is 180-500. Thereby, the thixotropic property of the color filter ink can be sufficiently lowered, and convection of the color filter ink in the cell can be suppressed during the formation of the colored portion. In addition, when a polyhydric alcohol is an oligomer, molecular weight can be made into a weight average molecular weight.

  The polyhydric alcohol is preferably a liquid in an atmosphere of 25 ° C. and 1 atm. As described above, since the polyhydric alcohol is a liquid, it can be uniformly mixed in the color filter ink, and the solid content of the color filter ink at the time of forming the colored portion should be relatively small. Can do. For this reason, it is possible to more reliably suppress an increase in the thixotropic property of the ink when forming the colored portion.

Further, when the polyhydric alcohol is a liquid in the atmosphere as described above, the viscosity η ₆₀ [mPa · s] measured using a rotary viscometer under the conditions of 25 ° C. and 60 rpm is 40 to 400 mPa · s. It is preferable and it is more preferable that it is 50-300 mPa * s. By using a liquid having a relatively high viscosity in this manner, the color filter ink in the cell has a relatively high viscosity when the colored portion is formed, and convection in the cell is suppressed.

  The content of the polyhydric alcohol in the color filter ink is preferably 0.3 to 15.0 wt%, more preferably 0.4 to 13.0 wt%, and 0.5 to 6 More preferably, it is 0.0 wt%. Thereby, the discharge stability of the color filter ink droplets can be made particularly excellent while sufficiently reducing the thixotropic property of the color filter ink.

In addition, as an index of thixotropic property of the color filter ink, for example, the ratio of the obtained viscosity (thixotropic index) when the viscosity at two different rotational speeds is measured using a rotary E-type viscometer. ). Specifically, the viscosity measured with a color filter ink at 25 ° C. under the condition of 6 rpm is η ₆ [mPa · s], and the viscosity measured with the color filter ink at 25 ° C. under the condition of 60 rpm is η _{When it is 60} [mPa · s], the thixo index of the color filter ink can be η ₆ / η ₆₀ . In addition, thixotropic property is so high that (eta) ₆ / (eta) ₆₀ is large.
The thixo index (η ₆ / η ₆₀ ) of the color filter ink is specifically preferably 1.06 or less, more preferably 1.05 or less, and 1.03 or less. It is more preferable that the above-described effects can be obtained more remarkably.

<Resin material>
The color filter ink usually contains a binder resin (resin material) for the purpose of improving the adhesion of the formed colored portion to the substrate. In addition, the binder resin is required to have solvent resistance in order to prevent adverse effects due to chemical application and washing in the subsequent process of the ink application process by the inkjet method. In the present invention, it is preferable to use a curable resin material as the binder resin.

[Curable resin material]
The curable resin material is generally excellent in adhesion to the substrate after curing. Therefore, the durability of the color filter can be improved by using a curable resin material as the binder resin.
The curable resin is not particularly limited. For example, various thermal chemical resins, energy ray curable resins such as a photocurable resin, and the like can be used, and the following curable resin materials are included. preferable. In general, when a large amount of a curable resin material is included in the ink, the viscosity tends to be high and the droplet ejection stability is not easily improved. However, when the following curable resin material is used as the curable resin material, the ink is prevented from increasing in viscosity even when a relatively large amount of the curable resin material is included, and discharge stability is particularly high. It will be excellent. In addition, when the colored portion is formed, the thixotropic property of the color filter ink is prevented from increasing. Further, the obtained color filter is particularly excellent in durability.

Hereinafter, a curable resin material (curable resin composition) that can be suitably used for the color filter ink will be described in detail.
[Polymer A]
The polymer A contains at least an epoxy group-containing vinyl monomer a1 as a monomer component. The polymer A may consist essentially of a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer A is a mixture of a plurality of types of compounds, each compound contains at least an epoxy group-containing vinyl monomer a1 as a monomer component.

(Epoxy group-containing vinyl monomer a1)
The polymer A contains at least an epoxy group-containing vinyl monomer a1 as a monomer component. By containing such an epoxy group-containing vinyl monomer a1 as a monomer component, an epoxy group can be easily and reliably introduced into the polymer A. Further, by using such a curable resin containing the epoxy group-containing vinyl monomer a1 together with the polyhydric alcohol as described above, it is easier to increase the thixotropic property of the ink when forming the colored portion. Can be suppressed. Further, by containing the epoxy group-containing vinyl monomer a1 as a monomer component, the polymer A is prevented from being unintentionally cured during storage of the color filter ink and when ink is applied to the cells. The Further, the long-term storage stability and ejection stability of the color filter ink can be made particularly excellent. Moreover, the colored part formed using the ink for color filters can be made especially excellent in solvent resistance by containing the epoxy group containing vinyl monomer a1 as a monomer component. Further, by containing the epoxy group-containing vinyl monomer a1 as a monomer component, the curable resin material is cured under relatively mild conditions when forming the colored portion using the color filter ink. It is useful for improving the hardness and the like of the colored portion to be formed. In addition, when the polymer A contains a vinyl monomer a2, a vinyl monomer a3, and the like as described later, the polymer can be suitably synthesized, and the polymer A having desired characteristics can be easily obtained. And it can be obtained reliably.

  As the epoxy group-containing vinyl monomer a1, for example, one having a structure represented by the following formula (5) can be used. When the epoxy group-containing vinyl monomer a1 has such a structure, the polymer A is more reliably cured unintentionally when storing the color filter ink or when applying ink to the cell. Is prevented. Further, the long-term storage stability and ejection stability of the color filter ink can be made particularly excellent. In particular, when a pigment is contained in the color filter ink, the dispersion stability of the pigment can be made particularly excellent, and the long-term storage stability and ejection stability of the color filter ink can be made particularly excellent. it can.

  Moreover, when the epoxy group-containing vinyl monomer a1 has a structure represented by the following formula (5), the solvent resistance of the colored portion formed using the color filter ink is more excellent. can do. In addition, when the epoxy group-containing vinyl monomer a1 has a structure represented by the following formula (5), it is cured under relatively mild conditions when forming a colored portion using the color filter ink. This is advantageous in that the resin material can be cured and the hardness of the colored portion to be formed is particularly excellent. In addition, when the epoxy group-containing vinyl monomer a1 has such a structure, the compatibility between the polymer A and the polymer B described later can be made particularly excellent, and an ink for a color filter. The transparency of the colored part formed using can be made particularly high.

In formula (5), examples of the alkyl group having 1 to 7 carbon atoms represented by R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl group An alkyl group such as a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. As a result, the polymer A is more reliably prevented from unintentionally curing when the color filter ink is stored and when ink is applied to the cells. Further, the long-term storage stability and ejection stability of the color filter ink can be made particularly excellent. Further, in the manufactured color filter, the contrast of the displayed image can be made particularly excellent. Moreover, the hardness etc. of the coloring part formed using the ink for color filters can be made excellent. Further, the compatibility between the polymer A and the polymer B described later can be made particularly excellent, and the transparency of the colored portion formed using the color filter ink can be made extremely high. it can.
In formula (5), a divalent hetero atom represented by G may be contained. As typical examples of the hydrocarbon group, a linear or branched alkylene group, more specifically, for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, oxymethylene, Examples include oxyethylene and oxypropylene.

  Specific examples of the epoxy group-containing vinyl monomer a1 include, for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, ethyl glycidyl (meth) acrylate, glycidyl vinyl benzyl ether (manufactured by Seimi Chemical Co., Ltd., (Trade name VBGE), alicyclic epoxy group-containing unsaturated compounds represented by the following formulas (5-1) to (5-31), and the like, and one or more selected from these are combined As the epoxy group-containing vinyl monomer a1, (3,4-epoxycyclohexyl) methyl (meth) acrylate is particularly preferable. As a result, the polymer A is more reliably prevented from unintentionally curing when the color filter ink is stored and when ink is applied to the cells. Further, the long-term storage stability and ejection stability of the color filter ink can be made particularly excellent. In addition, the hardness and solvent resistance of the colored portion formed using the color filter ink can be made particularly excellent. Further, the compatibility between the polymer A and the polymer B described later can be made particularly excellent, and the transparency of the colored portion formed using the color filter ink can be made extremely high. it can.

In formulas (5-1) to (5-31), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁹ represents And a C1-C20 divalent hydrocarbon group. R ⁷ , R ⁸ and R ⁹ may be the same or different from each other. Moreover, w shows 0-10.
The content of the epoxy group-containing vinyl monomer a1 in the polymer A (value obtained by conversion in terms of the weight of the monomer used for the synthesis of the polymer) is preferably 50 to 99 wt%, and preferably 70 to More preferably, it is 94 wt%. When the content of the epoxy group-containing vinyl monomer a1 in the polymer A is a value within the above range, the polymer A cures unintentionally when storing the color filter ink or applying ink to the cells. Is more reliably prevented. Further, the long-term storage stability and ejection stability of the color filter ink can be made particularly excellent. Further, when the content of the epoxy group-containing vinyl monomer a1 in the polymer A is a value within the above range, it is cured under relatively mild conditions when forming the colored portion using the color filter ink. The resin material can be cured and the hardness, solvent resistance, and the like of the colored portion to be formed can be made particularly excellent.

  In addition, when the polymer A is a mixture of a plurality of types of compounds, the content of the epoxy group-containing vinyl monomer a1 is a weighted average value (weighted average value based on a weight ratio) for these compounds. ) Can be adopted. Moreover, when the polymer A is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the epoxy group-containing vinyl monomer a1 with the content as described above.

(Vinyl monomer a2)
The polymer A only needs to contain at least an epoxy group-containing vinyl monomer a1 as a monomer component. In addition to the epoxy group-containing vinyl monomer a1, the polymer A further has an isocyanate group or a protective group. It is preferably a copolymer (copolymer) containing a vinyl monomer a2 having a blocked isocyanate group protected with a group as a monomer component. As a result, the gas content in the color filter ink (dissolved gas, bubbles present as microbubbles, etc.) can be lowered more effectively, and the droplet discharge stability by the ink jet method is particularly excellent. It will be a thing. Further, since there are few air bubbles contained in the color filter ink, it is possible to prevent bursting of the air bubbles in the color filter ink when forming the colored portion, and to make the colored portion particularly flat. As a result, in the manufactured color filter, it is possible to more effectively prevent color unevenness, density unevenness, and characteristic variation among individuals from occurring in each part.

Examples of the polymerizable vinyl monomer a2 include 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name “Karenz MOI”), 2-methacryloyloxyethyl isocyanate, etc., (meth) acryloyl groups having a carbon number. (Meth) acryloyl isocyanate etc. which couple | bonded with the isocyanate group through 2-6 alkylene groups are mentioned.
The isocyanate group of the (meth) acryloyl isocyanate is preferably a blocked isocyanate group. The blocked isocyanate group here refers to an isocyanate group whose end is masked with a blocking agent. Examples of the monomer having a blocked isocyanate group include 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate and the like, and “Karenz MOI-BM” manufactured by Showa Denko KK It is marketed with the brand name. These polymerizable vinyl monomers can be used alone or in combination of two or more.

  The content of the vinyl monomer a2 in the polymer A (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is 2 with respect to 100 parts by weight of the epoxy group-containing vinyl monomer a1. It is preferably ˜20 parts by weight, more preferably 3 to 15 parts by weight. When the content of the vinyl monomer a2 in the polymer A is a value within the above range, the gas content in the color filter ink while sufficiently improving the long-term storage stability of the color filter ink and the like. (Dissolved gas, bubbles present as microbubbles, etc.) can be reduced more effectively, and the stability of droplet ejection by the ink jet method is particularly excellent. Moreover, the transparency of the colored part formed using the color filter ink can be made sufficiently high.

  In addition, when the polymer A is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the vinyl monomer a2. can do. Moreover, when the polymer A is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the vinyl monomer a2 with the content as described above.

(Vinyl monomer a3)
The polymer A only needs to contain at least an epoxy group-containing vinyl monomer a1 as a monomer component. In addition to the epoxy group-containing vinyl monomer a1, the polymer A further includes a vinyl monomer having a hydroxyl group. It is preferable that the monomer a3 is contained as a monomer component (copolymer). As a result, the adhesion of the colored portion formed using the color filter ink to the substrate, particularly the adhesion when repeatedly exposed to a rapid temperature change accompanying image display, is particularly excellent. it can. As a result, for example, even when the color filter is used for a long period of time, it is possible to more reliably prevent problems such as light leakage (white spots, bright spots). That is, the durability of the color filter can be made particularly excellent. Further, if the polymer A contains the vinyl monomer a3 as a monomer component, the compatibility between the polymer A and the polymer B described later can be made particularly excellent. The transparency of the colored portion formed using the color filter ink can be made extremely high. Further, when the polymer A contains the vinyl monomer a3 as a monomer component, the discharge stability of the ink droplets is particularly excellent.

  Examples of the vinyl monomer a3 include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl. Monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid, such as (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, Compounds obtained by ring-opening polymerization of ε-caprolactone to the monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid (Dacel Chemical Industries, Ltd. Plaxel FA series, Plaxel FM series, etc.) or ethylene Kisaido compound was ring-opening polymerization of propylene oxide and the like, may be used alone or in combination of two or more selected from these.

  The content of the vinyl monomer a3 in the polymer A (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is 2 with respect to 100 parts by weight of the epoxy group-containing vinyl monomer a1. It is preferably ˜20 parts by weight, more preferably 3 to 15 parts by weight. When the content of the vinyl monomer a3 in the polymer A is a value within the above range, the color filter ink is manufactured using the color filter ink while sufficiently improving the long-term storage stability of the color filter ink. The durability of the color filter can be made particularly excellent. Moreover, the transparency of the colored part formed using the color filter ink can be increased. In addition, the ejection stability of ink droplets is particularly excellent.

  In addition, when the polymer A is a mixture of a plurality of types of compounds, the weighted average value (weighted average value based on the weight ratio) for these compounds is adopted as the content value of the vinyl monomer a3. can do. Moreover, when the polymer A is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the vinyl monomer a3 with the content as described above.

(Other polymerizable vinyl monomer a4)
The polymer A contains the above-mentioned epoxy group-containing vinyl monomer a1, vinyl monomer a2, and polymerizable vinyl monomer a4 other than the vinyl monomer a3 as monomer components. Also good. As such a polymerizable vinyl monomer a4, a vinyl monomer copolymerizable with the epoxy group-containing vinyl monomer a1 can be used, and specifically, for example, methyl (meth) acrylate, ethyl (Meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate Alkyl having 1 to 12 carbon atoms such as isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenylethyl (meth) acrylate, aralkyl (meth) acrylate; vinyl aromatic compounds such as styrene and α-methylstyrene; CF ₃ (CF ₂ ) ₃ CH ₂ CH═C H ₂ , CF ₃ (CF ₂ ) ₃ CH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH═ CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH═CH ₂ , F ₅ C ₆ CH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , H (CF ₂ ) ₆ CH ₂ OCH _{2 CH = CH 2, H (CF} 2) 8 CH 2 OCH 2 CH = CH 2, (CF 3) 2 CF (CF 2) 2 CH 2 CH 2 OCOCH = CH 2, (CF 3) 2 CF (CF 2) ₂ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ C H ₂ OCOC (CH ₃ ) ═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) _{9 CH 2 CH 2 OCOC (CH 3} ) = CH 2, H (CF 2) 6 CH 2 CH 2 OCOCH = CH 2, H (CF 2) 8 CH 2 CH 2 OCOC (CH 3) = _{H 2, F (CF 2)} 8 CH 2 CH 2 OCOCH = CH 2, F (CF 2) 8 CH 2 CH 2 OCOC (CH 3) = CH 2, H (CF 2) 4 CH 2 OCOC (CH 3) Fluoroalkyl groups or fluoroaryl group-containing vinyl compounds such as ═CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOCH═CH _{2 and the} like, and one or more selected from these may be used in combination. it can. However, the polymer A does not contain an alkoxysilyl group-containing vinyl monomer b1 as described later as a monomer component.

  The content of the polymerizable vinyl monomer a4 in the polymer A (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is 100 parts by weight of the epoxy group-containing vinyl monomer a1. , Preferably 20 parts by weight or less, and more preferably 10 parts by weight or less. In addition, when the polymer A is a mixture of a plurality of types of compounds, the value of the content of the polymerizable vinyl monomer a4 is a weighted average value (weighted average value based on weight ratio) for these compounds. Can be adopted. Moreover, when the polymer A is a mixture of a plurality of types of compounds, it is preferable that the content of the polymerizable vinyl monomer a4 satisfies the above conditions for each compound.

  As described above, the polymer A only needs to contain at least an epoxy group-containing vinyl monomer a1 as a monomer component, but in addition to the epoxy group-containing vinyl monomer a1, It is preferable to contain the body a2 and the vinyl monomer a3. Thereby, the effect by including the vinyl monomer a2 as described above and the effect by including the vinyl monomer a3 as described above can be compatible.

Although the ratio (content rate) of the polymer A in the curable resin material is not particularly limited, it is preferably 25 to 80 wt%, and more preferably 33 to 70 wt%. In addition, when the polymer A is a mixture of a plurality of types of compounds, the total content of these compounds is adopted as the content of the polymer A.
The weight average molecular weight of the polymer A is preferably 1000 to 50000, more preferably 1200 to 10000, and further preferably 1500 to 5000.

[Polymer B]
In the color filter ink, the curable resin material may include a polymer B containing at least an alkoxysilyl group-containing vinyl monomer b1 represented by the following formula (1) as a monomer component. preferable.

The polymer B may consist essentially of a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer B is a mixture of a plurality of types of compounds, each compound contains at least an alkoxysilyl group-containing vinyl monomer b1 as a monomer component.
Since such a polymer B contains an alkoxysilyl group, it has a high affinity with a substrate (particularly a glass substrate) that supports the colored portion of the color filter. For this reason, when the ink contains the polymer B as the curable resin material, the ink ejected onto the substrate can suitably spread on the substrate, and the resulting colored portion has a particularly uniform thickness. It can be. For this reason, the obtained color filter has particularly little color unevenness and density unevenness in each part. Moreover, since the polymer B has high affinity with respect to a board | substrate, the coloring part of the color filter obtained can make the adhesiveness with respect to a board | substrate especially excellent. Moreover, by having such a polymer B, the hardening of the polymer A can be supplemented, and the colored portion can be formed under relatively mild conditions, and the hardness and light resistance of the formed colored portion can be formed. The heat resistance and the like can be made sufficiently excellent. In addition, by having such a polymer B, the ink applied in the cell can more effectively maintain the flatness of the surface in the process of removing the liquid medium.

(Alkoxysilyl group-containing vinyl monomer b1)
The polymer B contains at least the alkoxysilyl group-containing vinyl monomer b1 represented by the formula (1) as a monomer component. By containing such an alkoxysilyl group-containing vinyl monomer b1 as a monomer component, an alkoxysilyl group can be easily and reliably introduced into the polymer B. Further, by containing the alkoxysilyl group-containing vinyl monomer b1 as a monomer component, the curing of the polymer A is performed when the curable resin material (curable resin composition) is cured to form a colored portion. The colored portion can be formed under relatively mild conditions, and the formed colored portion has sufficient hardness, adhesion to the substrate, light resistance, heat resistance, etc. Can be. Further, when the polymer B contains a vinyl monomer b2 or the like as will be described later, the synthesis of the polymer can be suitably performed, and the polymer B having desired characteristics can be obtained easily and reliably. it can.

In the formula (1), examples of the alkyl group having 1 to 7 carbon atoms represented by R ¹ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl group An alkyl group such as a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. Thereby, the discharge stability of the ink droplets can be made particularly excellent. Moreover, the hardness of the colored part to be formed, adhesion to the substrate, light resistance, heat resistance and the like can be made particularly excellent. Further, the compatibility between the polymer A and the polymer B can be made particularly excellent, and the transparency of the colored portion formed using the color filter ink can be made particularly high.

  In the formula (1), as a representative example of the divalent hydrocarbon group represented by E, a linear or branched alkylene group, more specifically, for example, methylene, ethylene, propylene, tetramethylene, Examples include ethylethylene, pentamethylene, hexamethylene and the like. Among these, a C1-C3 linear alkylene group (for example, a methylene, ethylene, a propylene group) is especially preferable.

In formula (1), the alkyl group having 1 to 6 carbon atoms represented by R ² , R ³ and R ⁴ is a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, Examples include isobutyl, s-butyl, t-butyl, pentyl, hexyl group and the like. Examples of the alkoxyl group having 1 to 6 carbon atoms represented by R ² and R ³ include linear or branched alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t- Examples include butoxy, pentoxy, hexyloxy groups and the like.

  Specific examples of the monomer represented by the formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and γ- (meth) acryloyloxypropyltrimethoxy. Silane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane And alkoxysilyl group-containing polymerizable unsaturated compounds such as γ- (meth) acryloyloxybutylphenyldimethoxysilane, and the like, and one or more selected from these can be used in combination.

  The content of the alkoxysilyl group-containing vinyl monomer b1 in the polymer B (value obtained by conversion in terms of the weight of the monomer used for the synthesis of the polymer) is preferably 70 to 100 wt%, and 80 More preferably, it is -100 wt%. When the content of the alkoxysilyl group-containing vinyl monomer b1 in the polymer B is a value within the above range, the ejection stability of the ink droplets can be made particularly excellent. Moreover, when hardening a curable resin material (curable resin composition) and forming a colored part, hardening of the polymer A can be supplemented effectively and a colored part is formed on milder conditions. Can do. Moreover, the uniformity of the shape of the colored part to be formed, hardness, adhesion to the substrate, light resistance, heat resistance and the like can be made particularly excellent. In addition, when the polymer B is a mixture of a plurality of types of compounds, the value of the content of the alkoxysilyl group-containing vinyl monomer b1 is a weighted average value (weighted average based on weight ratio) for these compounds. Value). Moreover, when the polymer B is a mixture of a plurality of types of compounds, it is preferable that all of these compounds contain the alkoxysilyl group-containing vinyl monomer b1 at the content described above.

(Other polymerizable vinyl monomer b2)
The polymer B only needs to contain at least an alkoxysilyl group-containing vinyl monomer b1 as a monomer component. In addition to the alkoxysilyl group-containing vinyl monomer b1, the polymer B further contains an alkoxysilyl group. A polymerizable vinyl monomer b2 other than the vinyl monomer b1 may be contained as a monomer component. As such a polymerizable vinyl monomer b2, a vinyl monomer copolymerizable with the alkoxysilyl group-containing vinyl monomer b1 can be used. Specifically, for example, 2-hydroxyethyl (meta ) Acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 4- For monoesterified products of polyhydric alcohol and acrylic acid or methacrylic acid, such as hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, and monoesterified products of polyhydric alcohol and acrylic acid or methacrylic acid ε-Caprolak A polymerizable vinyl monomer having a hydroxyl group, such as a compound obtained by ring-opening polymerization of ethylene (Placcel FA series, Plaxel FM series, etc. manufactured by Daicel Chemical Industries, Ltd.) or a compound obtained by ring-opening polymerization of ethylene oxide or propylene oxide; (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxy C1-C12 alkyl such as ethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, aralkyl (meth) acrylate; styrene, α-methylstyrene Vinyl aromatic compounds such _{as; CF 3 (CF 2) 3} CH 2 CH = CH 2, CF 3 (CF 2) 3 CH = CH 2, CF 3 (CF 2) 5 CH 2 CH = CH 2, CF 3 ( CF ₂ ) ₅ CH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH═CH ₂ , ( _{CF 3) 2 CF (CF 2} ) 4 CH = CH 2, (CF 3) 2 CF (CF 2) 6 CH 2 CH = CH 2, (CF 3) 2 CF (CF 2) 6 CH = CH 2, F _{5 C 6 CH = CH 2,} CF 3 (CF 2 _{5 CH 2 CH 2 OCH 2 CH} = CH 2, CF 3 (CF 2) 5 CH 2 CH 2 CH 2 OCH 2 CH = CH 2, CF 3 (CF 2) 7 CH 2 CH 2 OCH 2 CH = CH 2, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , H (CF ₂ ) ₆ CH ₂ OCH ₂ CH═CH ₂ , H (CF ₂ ) ₈ CH ₂ OCH ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH _{2 CH 2 OCOCH = CH 2,} (CF 3) 2 CF (CF 2) 2 CH 2 CH 2 OCOC (CH 3) = CH 2, (CF 3) 2 CF (CF 2) 4 CH 2 CH 2 _{COCH = CH 2, (CF 3} ) 2 CF (CF 2) 4 CH 2 CH 2 OCOC (CH 3) = CH 2, (CF 3) 2 CF (CF 2) 6 CH 2 CH 2 OCOCH = CH 2, ( _{CF 3) 2 CF (CF 2} ) 6 CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 5 CH 2 CH 2 OCOCH = CH 2, CF 3 (CF 2) 5 CH 2 CH 2 OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF _{2 ) 9 CH 2 CH 2 OCOCH =} CH 2, CF 3 (CF 2) 9 CH 2 CH 2 OCOC (CH 3) = CH 2, H (CF 2) 6 CH 2 CH 2 OCOCH = _{H 2, H (CF 2)} 8 CH 2 CH 2 OCOC (CH 3) = CH 2, F (CF 2) 8 CH 2 CH 2 OCOCH = CH 2, F (CF 2) 8 CH 2 CH 2 OCOC (CH _{3) = CH 2, H (} CF 2) 4 CH 2 OCOC (CH 3) = CH 2, H (CF 2) 4 CH 2 OCOCH = CH 2 , etc. fluoroalkyl or fluoroaryl-containing vinyl monomers and the like of 1 type or 2 types or more selected from these can be used in combination. However, the polymer B does not contain the epoxy group-containing vinyl monomer a1 as described above as a monomer component. Moreover, it is preferable that the polymer B does not contain the above fluoroalkyl group or fluoroaryl group containing vinyl monomer as a monomer component.

  The content of the polymerizable vinyl monomer b2 in the polymer B (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 30 wt% or less, and is 20 wt% or less. Is more preferable. In addition, when the polymer B is a mixture of a plurality of types of compounds, the content of the polymerizable vinyl monomer b2 is a weighted average value (weighted average value based on the weight ratio) for these compounds. Can be adopted. Moreover, when the polymer B is a mixture of a plurality of types of compounds, it is preferable that the content of the polymerizable vinyl monomer b2 satisfies the above-described conditions for each compound.

As described above, the polymer B only needs to contain at least the alkoxysilyl group-containing vinyl monomer b1 as a monomer component, and monomers other than the alkoxysilyl group-containing vinyl monomer b1. Although it may contain a component, it is preferably a homopolymer of an alkoxysilyl group-containing vinyl monomer b1. That is, it is preferable that the polymer B does not contain any component other than the alkoxysilyl group-containing vinyl monomer b1 as a monomer component. Thereby, the discharge stability of the color filter ink and the durability of the color filter produced using the color filter ink can be made particularly excellent.
The ratio (content ratio) of the polymer B in the curable resin material is not particularly limited, but is preferably 20 to 60 wt%, and more preferably 25 to 55 wt%. In addition, when the polymer B is a mixture of a plurality of types of compounds, the total content of these compounds is adopted as the content of the polymer B.

  The weight average molecular weight of the polymer B is preferably 1000 to 50000, more preferably 1200 to 10000, and further preferably 1500 to 5000. Thereby, in the color filter ink, the polymer B becomes relatively easy to flow. For this reason, when ink is ejected, it can move to the ink interface more quickly, and the ink can quickly and moderately spread on the nozzle plate. As a result, the ink ejection stability is improved, and the ink applied to the cell can more effectively maintain the flatness of the surface in the process of removing the liquid medium. Thereby, in the manufactured color filter, it is possible to more effectively prevent color unevenness, density unevenness, and variation in characteristics among individuals.

  Further, when the polymer A and the polymer B are included as the curable resin material, the ratio of the content ratio of the polymer A and the content ratio of the polymer B is 25:75 to 75:25 by weight ratio. It is preferable that it is 45:55 to 55:45. By satisfying such conditions, the discharge stability of the color filter ink can be made particularly excellent. In addition, color filters manufactured using color filter inks can more reliably prevent color unevenness and density unevenness at each part, and are particularly excellent in uniformity of characteristics among individuals. It can be. Further, the durability of the color filter can be made particularly excellent.

[Polymer C]
The curable resin material (curable resin composition) further includes a polymer C containing a fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 represented by the following formula (6) as a monomer component. May be included.

By including such a polymer C, the discharge stability of the color filter ink can be made particularly excellent. In particular, the liquid breakage from the nozzle of the droplet discharge head is improved. Further, the heat resistance of the colored portion formed using the color filter ink can be made particularly excellent.
The polymer C may be substantially composed of a single compound, or may be a mixture of a plurality of types of compounds. However, when the polymer C is a mixture of a plurality of types of compounds, each compound contains at least a fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 as a monomer component.

(Fluoroalkyl group or fluoroaryl group-containing vinyl monomer c1)
The polymer C contains at least a fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 represented by the formula (6) as a monomer component. By containing such a fluoroalkyl group or fluoroaryl group-containing vinyl monomer c1 as a monomer component, the fluoroalkyl group or fluoroaryl group can be easily and reliably introduced into the polymer C. Further, by containing the fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 as a monomer component, the discharge stability of the color filter ink can be made particularly excellent. In particular, the ink drainage from the nozzle can be made particularly excellent. Further, the heat resistance of the colored portion formed using the color filter ink can be made particularly excellent. Further, when the polymer C contains a vinyl monomer c2 or the like as will be described later, the polymer can be synthesized suitably, and the polymer C having desired characteristics can be obtained easily and reliably. it can.

In formula (6), examples of the alkyl group having 1 to 7 carbon atoms represented by R ⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl and heptyl groups. An alkyl group such as a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. Thereby, the discharge stability of the color filter ink and the heat resistance of the colored portion formed using the color filter ink can be made particularly excellent.

  In the formula (6), as a typical example of the divalent hydrocarbon group represented by D (hydrocarbon group which may contain a hetero atom), a linear or branched alkylene group, more specifically, Examples include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, oxymethylene, oxyethylene, and oxypropylene.

Specific examples of the monomer represented by the formula (6) include, for example, CF ₃ (CF ₂ ) ₃ CH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₃ CH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₅ CH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH═CH ₂ , CF ₃ ( CF ₂ ) ₉ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH═CH ₂ , (CF ₃ ) ₂ CF ( _{CF 2) 4 CH 2 CH =} CH 2, (CF 3) 2 CF (CF 2) 4 CH = CH 2, (CF 3) 2 CF (CF 2) 6 CH 2 CH = CH 2, (CF 3) 2 _{CF (CF 2) 6 CH =} CH 2, F 5 C 6 CH = C _{2, CF 3 (CF 2)} 5 CH 2 CH 2 OCH 2 CH = CH 2, CF 3 (CF 2) 5 CH 2 CH 2 CH 2 OCH 2 CH = CH 2, CF 3 (CF 2) 7 CH 2 CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCH ₂ CH═CH ₂ , CF ₃ (CF _{2) 9 CH 2 CH 2 CH} 2 OCH 2 CH = CH 2, H (CF 2) 6 CH 2 OCH 2 CH = CH 2, H (CF 2) 8 CH 2 OCH 2 CH = CH 2, (CF 3) ₂ CF (CF ₂ ) ₂ CH ₂ CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , (CF ₃ ) ₂ CF (CF _{2) 4 CH 2 CH 2 OCOCH} = CH 2, (CF 3) 2 CF (CF 2) 4 CH 2 CH 2 OCOC (CH 3) = CH 2, (CF 3) 2 CF (CF 2) 6 CH 2 CH ₂ OCOCH═CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ (CF _{2) 5 CH 2 CH 2 OCOC} (CH 3) = CH 2, CF 3 (CF 2) 7 CH 2 CH 2 OCOCH = CH 2, CF 3 (CF 2) 7 CH 2 CH 2 OCOC (CH 3) = CH _{2, CF 3 (CF 2)} 9 CH 2 CH 2 OCOCH = CH 2, CF 3 (CF 2) 9 CH 2 CH 2 OCOC (CH 3) = CH 2, H (CF 2) 6 C _{2 CH 2 OCOCH = CH 2,} H (CF 2) 8 CH 2 CH 2 OCOC (CH 3) = CH 2, F (CF 2) 8 CH 2 CH 2 OCOCH = CH 2, F (CF 2) 8 CH 2 CH ₂ OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) ═CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOCH═CH _{2 and the} like are selected from these One kind or a combination of two or more kinds can be used.

  The content of the fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 in the polymer C (value obtained by conversion based on the weight of the monomer used for the synthesis of the polymer) is 15 to 100 wt%. Is preferable, and it is more preferable that it is 18-100 wt%. When the content of the fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 in the polymer C is a value within the above range, the ejection stability of the color filter ink can be made particularly excellent. In particular, the ink drainage from the nozzle can be made particularly excellent. The heat resistance of the colored portion formed using the color filter ink can be made particularly excellent. Further, the compatibility of the polymer C with the polymer A or the polymer B can be made particularly excellent, and the transparency of the colored part formed using the color filter ink is made particularly high. Can do.

  When the polymer C is a mixture of a plurality of types of compounds, the value of the content of the fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 is a weighted average value (weight ratio) for these compounds. Based weighted average). Further, when the polymer C is a mixture of a plurality of types of compounds, these compounds all contain the fluoroalkyl group- or fluoroaryl group-containing vinyl monomer c1 at the content as described above. Is preferred.

(Other polymerizable vinyl monomer c2)
The polymer C may contain a polymerizable vinyl monomer c2 other than the fluoroalkyl group or fluoroaryl group-containing vinyl monomer c1 as described above as a monomer component. As such a polymerizable vinyl monomer c2, a vinyl monomer copolymerizable with a fluoroalkyl group or fluoroaryl group-containing vinyl monomer c1 can be used. (Meth) acryloyl groups such as acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name “Karenz MOI”), 2-methacryloyloxyethyl isocyanate and the like are bonded to isocyanate groups via alkylene groups having 2 to 6 carbon atoms. Isocyanates or protective groups such as (meth) acryloyl isocyanate, 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate (manufactured by Showa Denko KK, trade name “Karenz MOI-BM”) A polymerizable vinyl monomer having a blocked isocyanate group protected with 2; -Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meta ) Monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid, such as acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, etc., the polyhydric alcohol and acrylic acid or methacrylic acid A compound obtained by ring-opening polymerization of ε-caprolactone to a monoester product of the above (such as Plaxel FA series and Plaxel FM series manufactured by Daicel Chemical Industries, Ltd.), ethylene oxide, and propylene oxide. Polymerizable vinyl monomers having hydroxyl groups such as polymerized compounds; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl ( 1 to 12 carbon atoms such as (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, etc. Examples include alkyl, aralkyl (meth) acrylate; vinyl aromatic compounds such as styrene and α-methylstyrene, and one or more selected from these can be used in combination. However, the polymer C does not contain the epoxy group-containing vinyl monomer a1 and the alkoxysilyl group-containing vinyl monomer b1 as described above as monomer components.

The content of the polymerizable vinyl monomer c2 in the polymer C (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is preferably 85 wt% or less, and is 82 wt% or less. More preferably. In addition, when the polymer C is a mixture of a plurality of kinds of compounds, the content of the polymerizable vinyl monomer c2 is a weighted average value (weighted average value based on the weight ratio) for these compounds. Can be adopted. Moreover, when the polymer C is a mixture of a plurality of types of compounds, it is preferable that the content of the polymerizable vinyl monomer c2 satisfies the above-described conditions for each compound.
When the curable resin material contains the polymer C, the ratio (content ratio) of the polymer C in the curable resin material is not particularly limited, but is preferably 1 to 20 wt%, and 2 to 15 wt%. It is more preferable that In addition, when the polymer C is a mixture of a plurality of types of compounds, the total content of these compounds is adopted as the content of the polymer C.

  The weight average molecular weight of the polymer C is preferably 1000 to 50000, more preferably 1200 to 10000, and still more preferably 1500 to 5000. Thereby, in the color filter ink, the polymer C becomes relatively easy to flow, and an increase in thixotropic property of the color filter ink at the time of forming the colored portion can be suppressed. As a result, in the manufactured color filter, it is possible to more effectively prevent color unevenness, density unevenness, and characteristic variation among individuals from occurring in each part.

  Further, when the curable resin material contains the polymer C, the ratio of the content ratio of the polymer A and the content ratio of the polymer C is preferably 50:50 to 99: 1 by weight ratio, More preferably, it is 60: 40-98: 2. By satisfying such conditions, the dispersion stability of the pigment in the color filter ink and the discharge stability of the color filter ink are particularly excellent, and the color unevenness and density unevenness in each part of the color filter are reduced. It can be more effectively prevented, the uniformity of characteristics among individuals can be made particularly excellent, and the durability of the color filter can be made particularly excellent.

  The content of the curable resin material in the color filter ink is preferably 0.5 to 10 wt%, and more preferably 1 to 5 wt%. When the content of the curable resin material is a value within the above range, the color filter manufactured has a particularly excellent discharge property from the droplet discharge head, and the manufactured color filter has a particularly excellent durability. Can be. In addition, a sufficient color density can be ensured in the manufactured color filter.

The content of the curable resin material with respect to 100 parts by weight of the pigment is preferably 15 to 50 parts by weight, and more preferably 19 to 42 parts by weight. By satisfying such conditions, the dispersion stability of the pigment in the color filter ink and the discharge stability of the color filter ink are particularly excellent, and the color filter formed using the color filter ink The color developability and contrast of the colored portion can be made particularly excellent. Further, the adhesion of the colored portion to the substrate can be made particularly excellent.
The curable resin material constituting the color filter ink may include a polymer other than the polymer A, the polymer B, and the polymer C described above.

<Thermoplastic resin>
The color filter ink may contain a thermoplastic resin. Thereby, for example, when the color filter ink contains a pigment, the dispersibility of the pigment particles in the color filter ink can be made particularly excellent. In particular, the dispersion stability of the pigment particles in the color filter ink can be made extremely excellent by using a thermoplastic resin in the preliminary dispersion step in the production method described later.

  Examples of the thermoplastic resin include alginic acids, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, styrene-acrylic acid resin, styrene-acrylic acid-acrylic ester resin, styrene-maleic acid resin, styrene- Maleic acid half ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid-acrylic acid ester resin, isobutylene-maleic acid resin, rosin-modified maleic acid resin, polyvinylpyrrolidone, gum arabic starch, polyallylamine, polyvinylamine, polyethyleneimine, etc. 1 type or 2 types or more selected from these can be used in combination.

The content of the thermoplastic resin in the color filter ink is not particularly limited, but is preferably 1.5 to 7.7 wt%, and more preferably 2.1 to 7.2 wt%.
The color filter ink may contain components other than those described above. Examples of the components other than those described above constituting the color filter ink include a dispersant.

<Dispersant>
The color filter ink may contain a dispersant. Thereby, for example, the ejection stability of ink droplets can be made particularly excellent. Further, when a pigment is contained in the color filter ink, the dispersant can contribute to improving the dispersibility of the pigment particles in the color filter ink.

  Although it does not specifically limit as a dispersing agent, For example, a polymeric dispersing agent can be used. Examples of the polymer dispersant include basic polymer dispersants, neutral polymer dispersants, acidic polymer dispersants, and the like. Examples of such polymeric dispersants include, for example, dispersants made of acrylic and modified acrylic copolymers, urethane dispersants, polyaminoamide salts, polyether esters, phosphate esters, and aliphatic polycarboxylic acids. And the like, and the like.

  More specific examples of the dispersant include, for example, Dispersic 101, Dispersic 102, Dispersic 103, Dispersic P104, Dispersic P104S, Dispersic 220S, Dispersic 106, Dispersic 108, Dispersic 109, Disperse BIC 110, DISPERBIC 111, DISPERBIC 112, DISPERBIC 116, DISPERBIC 140, DISPERBIC 142, DISPERBIC 160, DISPERBIC 161, DISPERBIC 162, DISPERBIC 163, DISPERBIC 164, DISPERBIC 166, DISPERBIC 167 Dispersic 168, Dispersic 170, Dispersic 171, Dispersic 1 4, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2050, Dispersic 2070, Dispersic 2095, Dispersic 2150, Dispersic LPN6919, Dispersic 9075, Dispersic 9077 (above, manufactured by BYK Chemie); EFKA 4008, EFKA 4009, EFKA 4010, EFKA 4015, EFKA 4020, EFKA 4046, EFKA 4047, EFKA 4050, EFKA 4055, EFKA 4055, EFKA 4055 , EFKA 4401, EFKA 4402, EF A 4403, EFKA 4406, EFKA 4408, EFKA 4300, EFKA 4330, EFKA 4340, EFKA 4015, EFKA 4800, EFKA 5010, EFKA 5065, EFKA 5066, EFKA 5070, EFKA 5070, EFKA 5070 Sol Sparse 3000, Sol Sparse 9000, Sol Sparse 13000, Sol Sparse 16000, Sol Sparse 17000, Sol Sparse 18000, Sol Sparse 20000, Sol Sparse 21000, Sol Sparse 24000, Sol Sparse 26000, Sol Sparse 27000, Sol Sparse 28000, Sol Sparse 32000, Sol Sparse 32500, Sol Sparse 32550, Sol Sparse 33500, Solsperse 35100, Solsperse 35200, Solsperse 36000, Solsperse 36600, Solsperse 38500, Solsperse 41000, Solsperse 41090, Solsperse 20000 (above, manufactured by Lubrizol); Manufactured by Ajinomoto Fine Techno Co., Ltd.); Disparon 1850, Disparon 1860, Disparon 2150, Disparon 7004, Disparon DA-100, Disparon DA-234, Disparon DA-325, Disparon DA-375, Disparon DA-705, Disparon DA-725, Disparon PW-36 (above, manufactured by Enomoto Kasei Co., Ltd.) And Florene DOPA-14, Florene DOPA-15B, Floren DOPA-17, Floren DOPA-22, Floren DOPA-44, Floren TG-710, Floren D-90 (manufactured by Kyoei Chemical Co., Ltd.), Anti-Terra-205 (Made by Big Chemie) etc. are mentioned, It can use combining 1 type (s) or 2 or more types selected from these.

  In particular, in the present invention, as the dispersant, a dispersant having a predetermined acid value (hereinafter also referred to as an acid value dispersant) and a dispersant having a predetermined amine value (hereinafter also referred to as an amine value dispersant) It is preferable to use together. As a result, the trajectory of the droplet ejected from the droplet ejection head changes (so-called flight bending occurs), and it becomes impossible to land the droplet on the target site, or the ejection amount of the droplet is inadequate. It can effectively prevent problems such as stabilization (instability of droplet discharge), and more effectively prevent color unevenness and density unevenness at each part of the manufactured color filter. The uniformity of the characteristics between them can be made particularly excellent. Further, the dispersion stability of the pigment in the color filter ink (long-term storage stability of the color filter ink) can be made particularly excellent. In particular, when a pigment is contained in the color filter ink, the pigment can be stably dispersed in a fine particle state.

  Specific examples of the acid value dispersant include Dispersic P104, Dispersic P104S, Dispersic 220S, Dispersic 110, Dispersic 111, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 2095 (above, BYC Chemie) EFKA 5010, EFKA 5065, EFKA 5066, EFKA 5070, EFKA 7500, EFKA 7554 (above, manufactured by Ciba Specialty); Solsperse 3000, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 36000, Solsperse 36000, (Above, manufactured by Lubrizol).

  Specific examples of the amine value dispersant include Dispersic 102, Dispersic 160, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 164, Dispersic 166, Dispersic 167, Dispersic 168, Dispersic 2150, Dispersic LPN6919, Dispersic 9075, Dispersic 9077 (above, manufactured by BYK Chemie); EFKA 4015, EFKA 4020, EFKA 4046, EFKA 4047, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4060, EFKA 4060, EFKA 4060, , EFKA 4340, EFKA 4400, EFKA 4401, EFKA 4402, EFK A4403, EFKA 4800 (manufactured by Ciba Specialty Company); Azisper PB711 (manufactured by Ajinomoto Fine-Techno Company); Anti-Terra-205 (manufactured by Big Chemie Company) and the like.

When an acid value dispersant and an amine value dispersant are used in combination, the acid value of the acid value dispersant (acid value when converted to solid content) is not particularly limited, but is preferably 5 to 370 KOHmg / g. It is more preferably 20 to 270 KOH mg / g, and further preferably 30 to 135 KOH mg / g. When the acid value of the acid value dispersant is within the above range, the viscosity of the color filter ink can be more significantly reduced and stabilized when used in combination with the amine value dispersant as described above. . In addition, when a pigment is contained in the color filter ink, the dispersion stability of the pigment can be made particularly excellent. The acid value of the dispersant can be determined by a method based on DIN EN ISO 2114, for example.
Moreover, it is preferable that the acid value dispersant does not have a predetermined amine value, that is, the amine value is zero.

When the amine value dispersant and the acid value dispersant are used in combination, the amine value of the amine value dispersant (amine value in terms of solid content) is not particularly limited, but is preferably 5 to 200 KOHmg / g. It is more preferably 25 to 170 KOH mg / g, and further preferably 30 to 130 KOH mg / g. When the amine value of the amine value dispersant is within the above range, the viscosity reduction and stabilization effect of the color filter ink when used in combination with the amine value dispersant as described above can be obtained more remarkably. . In addition, when a pigment is contained in the color filter ink, the dispersion stability of the pigment can be made particularly excellent. In addition, the amine value about a dispersing agent can be calculated | required by the method based on DIN 16945, for example.
Moreover, it is preferable that the amine value dispersant does not have a predetermined acid value, that is, the acid value is zero.

Further, when the acid value dispersant and the amine value dispersant are used in combination, the content of the acid value dispersant in the color filter ink is X _A [wt%], and the amine value dispersant is contained in the color filter ink When the rate is X _B [wt%], it is preferable that the relationship of 0.1 ≦ X _A / X _B ≦ 1 is satisfied, and the relationship of 0.15 ≦ X _A / X _B ≦ 0.5 is satisfied. Is more preferable. By satisfying such a relationship, the synergistic effect by using the acid value dispersant and the amine value dispersant in combination is more remarkably exhibited, and the discharge stability of the droplets can be made particularly excellent. .

The acid value of the acid value dispersant is AV [KOH mg / g], the amine value of the amine value dispersant is BV [KOH mg / g], the content of the acid value dispersant is X _A [wt%], the amine When the content of the valent dispersant is X _B [wt%], it is preferable that the relationship of 0.01 ≦ (AV × X _A ) / (BV × X _B ) ≦ 1.9 is satisfied, and 0.10 It is more preferable that the relationship of ≦ (AV × X _A ) / (BV × X _B ) ≦ 1.5 is satisfied. By satisfying such a relationship, the synergistic effect by using the acid value dispersant and the amine value dispersant in combination is more remarkably exhibited, and the discharge stability of the droplets can be made particularly excellent. .
The content of the dispersant in the color filter ink is not particularly limited, but is preferably 2.5 to 10.2 wt%, and more preferably 3.2 to 9.2 wt%.

<Other ingredients>
The color filter ink of the present invention may contain components other than those described above. Examples of such components include various crosslinking agents; thermal acid generators such as diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, onium salts such as benzothiazolium salts; Photoacid generators such as diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts; various polymerization initiators; acid crosslinking agents; surfactants; sensitizers; light stabilizers; Various polymerization accelerators; various light stabilizers; fillers such as glass and alumina; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Limethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloro Adhesion promoters such as propylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) ), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; Aggregation of sodium polyacrylate, etc. Sealing agent, and the like.

  As the crosslinking agent, for example, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid, polyfunctional epoxy monomer, polyfunctional acrylic monomer, polyfunctional vinyl ether monomer, polyfunctional oxetane monomer and the like can be used. Specific examples of the polyvalent carboxylic acid anhydride include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; Fats such as 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Polyhydric carboxylic acid dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Examples of the acid anhydrides include aromatic polycarboxylic anhydrides. Masui. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably. Specific examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid; hexahydrophthalic acid, 1,2-cyclohexane Aliphatic polycarboxylic acids such as dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5 , 8-Naphthalenetetracarboxylic acid, benzophenonetetracarboxylic acid, and other aromatic polyvalent carboxylic acids, among which aromatic polyvalent carboxylic acids are preferred. Specific examples of the polyfunctional epoxy monomer include Daicel Chemical Industries, Ltd., trade name Celoxide 2021, Daicel Chemical Industries, Ltd., trade name Epolide GT401, Daicel Chemical Industries, Ltd., trade name Epolide PB3600, and Bisphenol A. , Hydrogenated bisphenol A, triglycidyl isocyanurate, and the like. Specific examples of the polyfunctional acrylic monomer include pentaerythritol ethoxytetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxytriacrylate, dipentaerythritol. Examples include hexaacrylate trimethallyl isocyanurate and triallyl isocyanurate. Specific examples of the polyfunctional vinyl ether monomer include 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and triethylene. Examples include glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and the like. Specific examples of the polyfunctional oxetane monomer include xylylene oxetane, biphenyl type oxetane, novolak type oxetane and the like.

  The surfactant has a function of reducing the surface tension of the ink. When the ink contains a surfactant, the ink ejection stability can be made particularly excellent. In addition, the ink applied in the cell can more effectively maintain the surface flatness in the process of removing the liquid medium, and can more effectively flatten the colored portion. . As such surfactants, for example, acrylic surfactants, vinyl ether surfactants, silicone surfactants, fluorine surfactants and the like can be used, and among these, acrylic surfactants are used. It is preferable to use it. The acrylic surfactant can contribute to the flattening of the colored portion and has excellent affinity with the polymer A as described above, and can increase the brightness of the formed colored portion.

Examples of the acrylic surfactant include LF-1983, 230, LF-1982, LF-1984, LHP-95, LHP-96 (manufactured by Enomoto Kasei Co., Ltd.) and the like.
Examples of vinyl ether surfactants include UVX-188, UVX-190, LHP-90, LHP91 (above, manufactured by Enomoto Kasei Co., Ltd.) BYK-350, BYK-392 (above, manufactured by BYK Chemie) and the like.

Examples of the fluorosurfactant include Mega-Fac R-08MH, Mega-Fac F482, Mega-Fac F470, Mega-Fac F471, Mega-Fac F472SF, HAS-36 (above, Dainippon Ink Co., Ltd.), BYK-340 (above , Manufactured by Big Chemie).
Examples of the silicone surfactant include BYK-307, BYK-300, BYK-302, BYK-306, BYK-330, BYK-331, BYK-344, BYK-silclean 3700 (above, manufactured by BYK Chemie), KP -321, KP-324, DF-58 (above, manufactured by Shin-Etsu Silicone) and the like.

  The thermal acid generator is a component that generates an acid by heating, and among them, a sulfonium salt and a benzothiazolium salt are particularly preferable. As more specific examples of thermal acid generators, as trade names, Sun-Aid SI-45, Same as left SI-47, Same as left SI-60, Same as left SI-60L, Same as left SI-80, Same as left SI-80L, Same as left SI- 100, same left SI-100L, same left SI-145, same left SI-150, same left SI-160, same left SI-110L, same left SI-180L (above, Sanshin Chemical Co., Ltd., product name), CI-2921, CI -2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (Nippon Soda Co., Ltd. product, trade name), CP-66, CP-77 (Asahi Denka Kogyo Co., Ltd. products) , Product name), FC-520 (product of 3M company, product name) and the like.

  The photoacid generator is a component that generates an acid by light, and more specific examples include, as trade names, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, US Union Carbide, trade name), Irgacure 261 (Ciba Specialty Chemicals, trade name), SP-150, SP-151, SP-170, Optmer SP-171 (above, manufactured by Asahi Denka Kogyo Co., Ltd.) , Product name), CG-24-61 (product name, manufactured by Ciba Specialty Chemicals Co., Ltd.), DAICATII (product name, manufactured by Daicel Chemical Industries, Ltd.), UVAC1591 (product name, manufactured by Daicel UCB Co., Ltd.) CI-2064, CI-2639, CI-2624, CI-2481, CI-2 34, CI-2855, CI-2823, CI-2758 (Nippon Soda Co., Ltd., trade name), PI-2074 (Rhone-Poulenc, trade name, pentafluorophenylborate toluylcumyl iodonium salt), FFC509 ( 3M company product, trade name), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (Midori Chemical Co., Ltd., product) Name), CD-1012 (trade name, manufactured by Sartomer, USA) and the like.

  Further, the surface tension of the color filter ink at 25 ° C. is preferably 25 to 38 dyn / cm, more preferably 25 to 35 dyn / cm, and further preferably 25 to 32 dyn / cm. Thereby, the discharge property of the droplet can be made particularly stable. For this reason, the characteristic difference between individuals of the color filter to be manufactured can be made particularly small. As the surface tension, a value measured according to JIS K 3362 can be adopted.

  The contact angle of each color filter ink constituting the color filter ink set with respect to the surface of the color filter substrate (work) at 25 ° C. is preferably 3 to 15 °, and more preferably 5 to 10 °. It is more preferable. As a result, the color filter ink ejected and landed on the substrate can be suitably wetted and spread, and the manufactured color filter has particularly small unevenness in color density in the cell. In addition, the value measured based on JISR3257 can be employ | adopted for the contact angle with respect to the substrate surface for color filters of the ink for color filters.

  The viscosity of the color filter ink measured at 60 rpm using an E-type viscometer at 25 ° C. is preferably 13 mPa · s or less, more preferably 12 mPa · s or less, and 5 to 11 mPa · s. More preferably, it is s. Thus, when the viscosity of the color filter ink is sufficiently low, for example, the production efficiency of the color filter (formation efficiency of the colored portion) can be made particularly excellent, and the thickness of the colored portion It is possible to effectively prevent such unintentional variations.

<Ink set>
The color filter ink as described above is used for manufacturing a color filter by an ink jet method. Since the color filter usually corresponds to full color display, it has a plurality of colored portions (usually, three RGB colors corresponding to the three primary colors of light). For forming the colored portions of the plurality of colors, a plurality of types of color filter inks of corresponding colors are used. That is, an ink set including a plurality of color filter inks is used for manufacturing a color filter. In the present invention, in the production of the color filter, the color filter ink as described above may be used as long as it can be used to form at least one colored portion, but can be used to form colored portions of all colors. Is preferred.

"Color filter"
Next, an example of a color filter manufactured using the color filter ink (ink set) as described above will be described.
FIG. 1 is a cross-sectional view showing a preferred embodiment of the color filter of the present invention.
As shown in FIG. 1, the color filter 1 includes a substrate 11 and a colored portion 12 formed using the color filter ink described above. As the coloring portion 12, a first coloring portion 12A, a second coloring portion 12B, and a third coloring portion 12C having different colors are provided. A partition wall 13 is provided between the adjacent colored portions 12.

<Board>
The substrate 11 is a plate-like member having optical transparency, and has a function of holding the colored portion 12 and the partition wall 13.
The substrate 11 is preferably made of a substantially transparent material. Thereby, a clearer image can be formed by the light transmitted through the color filter 1.

  The substrate 11 is preferably excellent in heat resistance and mechanical strength. Thereby, for example, deformation due to heat applied during the manufacture of the color filter 1 can be reliably prevented. Examples of the constituent material of the substrate 11 that satisfies such conditions include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, norbornene-based ring-opening polymer, and hydrogenated products thereof.

<Coloring part>
The colored portion 12 is formed using the color filter ink (ink set) as described above.
Since the colored portion 12 is formed using the color filter ink as described above, the surface thereof is flat. For this reason, the color filter 1 is excellent in brightness and contrast ratio and has high reliability. Further, the color filter 1 is excellent in the color developability of the colored portion 12.
Each colored portion 12 is provided in a cell 14 which is a region surrounded by a partition wall 13 which will be described later.

  The first colored portion 12A, the second colored portion 12B, and the third colored portion 12C are of different colors. For example, the first colored portion 12A can be a red filter region (R), the second colored portion 12B can be a green filter region (G), and the third colored portion 12C can be a blue filter region (B). One set of colored portions 12A, 12B, and 12C of different colors constitutes one pixel. In the color filter 1, a predetermined number of colored portions 12 are arranged in the horizontal direction and the vertical direction. For example, when the color filter 1 is a high-definition color filter, 1366 × 768 pixels are arranged, and when the color filter 1 is a full high-definition color filter, 1920 × 1080 pixels are arranged. In the case of a super high vision color filter, 7680 × 4320 pixels are arranged. Note that the color filter 1 may be provided with a spare pixel outside the effective area, for example.

<Partition wall>
A partition wall (bank) 13 is provided between the adjacent colored portions 12. Thereby, it can prevent reliably that the adjacent coloring parts 12 will mix colors, As a result, a clear image can be displayed reliably.
The partition wall 13 may be made of a transparent material, but is preferably made of a light-shielding material. Thereby, an image with excellent contrast can be displayed. The color of the partition wall (light shielding part) 13 is not particularly limited, but is preferably black. Thereby, the contrast of the displayed image can be made particularly excellent.

  The height of the partition wall 13 is not particularly limited, but is preferably larger than the thickness of the colored portion 12. Thereby, the color mixture between the adjacent coloring parts 12 can be prevented reliably. The specific thickness of the partition wall 13 is preferably 0.1 to 10 μm, and more preferably 0.5 to 3.5 μm. As a result, color mixing between the adjacent colored portions 12 can be reliably prevented, and the viewing angle characteristics of the image display device and electronic apparatus including the color filter 1 can be improved.

  The partition wall 13 may be composed of any material, but is preferably composed mainly of a curable resin material, for example. Thereby, the partition wall 13 can be easily formed as having a desired shape by a method as described later. Moreover, when the partition 13 has a function as a light-shielding part, it may include a light-absorbing material such as carbon black as a constituent material.

《Color filter manufacturing method》
Next, a method for manufacturing the color filter 1 as described above will be described.
2 is a cross-sectional view showing a method for manufacturing a color filter, FIG. 3 is a perspective view showing a droplet discharge device used for manufacturing the color filter, and FIG. 4 is a droplet discharge means in the droplet discharge device shown in FIG. FIG. 5 is a diagram showing the bottom surface of the droplet ejection head in the droplet ejection device shown in FIG. 3, and FIG. 6 is a diagram showing the droplet ejection head in the droplet ejection device shown in FIG. It is a figure, (a) is a section perspective view, (b) is a sectional view.

  As shown in FIG. 2, in this embodiment, a substrate preparation step (1a) for preparing a substrate 11, a partition formation step (1b, 1c) for forming a partition 13 on the substrate 11, and a color filter by an ink jet method. An ink application step (1d) for applying the ink 2 to the region surrounded by the partition wall 13, and removing the solvent (liquid medium) from the color filter ink 2 to harden the curable resin material, thereby solid-state coloring And a colored portion forming step (1e) as a portion 12.

<Board preparation process>
First, the substrate 11 is prepared (1a). The substrate 11 prepared in this step is preferably subjected to a cleaning process. In addition, the substrate 11 prepared in this step has been subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, and the like. Also good.

<Partition forming process>
Next, the radiation-sensitive composition for forming the partition walls of the substrate 11 is applied to almost the entire one surface of the substrate 11 to form the coating film 3 (1b). In addition, after giving a radiation sensitive composition on the board | substrate 11, you may perform a prebaking process as needed. The pre-bake treatment can be performed, for example, under the conditions of heating temperature: 50 to 150 ° C. and heating time: 30 to 600 seconds.

Then, the partition 13 is formed by performing a post-exposure baking process (PEB) by irradiating with a radiation through a photomask, and further performing a developing process using an alkaline developer (1c). PEB can be performed, for example, under the conditions of heating temperature: 50 to 150 ° C., heating time: 30 to 600 seconds, and radiation irradiation intensity: 1 to 500 mJ / cm ² . The development processing can be performed by, for example, a liquid piling method, a dipping method, a vibration dipping method, or the like, and the development processing time can be set to, for example, 10 to 300 seconds. Further, after the development process, a post-bake process may be performed as necessary. The post-bake treatment can be performed, for example, under the conditions of heating temperature: 150 to 280 ° C. and heating time: 3 to 120 minutes.

<Ink application process>
Next, the color filter ink 2 is applied to the cell 14 surrounded by the partition wall 13 by an inkjet method (1d).
This step is performed using a plurality of types of color filter inks 2 corresponding to the plurality of colored portions 12 to be formed. At this time, since the partition wall 13 is provided, it is reliably prevented that two or more kinds of color filter inks 2 are mixed.
The color filter ink 2 is discharged using a droplet discharge device as shown in FIGS.

  As shown in FIG. 3, the droplet discharge device 100 used in this step is supplied with the color filter ink 2 from the tank 101 that holds the color filter ink 2, the tube 110, and the tube 110. A discharge scanning unit 102. The ejection scanning unit 102 includes a droplet ejection unit 103 having a plurality of droplet ejection heads (inkjet heads) 114 mounted on a carriage 105, and a first position control device 104 (movement) that controls the position of the droplet ejection unit 103. Means), a stage 106 for holding the substrate 11 on which the partition wall 13 is formed in the above process (hereinafter also simply referred to as "substrate 11"), and a second position control device 108 (moving means) for controlling the position of the stage 106. ) And a control means 112. The tank 101 and a plurality of droplet discharge heads 114 in the droplet discharge means 103 are connected by a tube 110, and the color filter ink 2 is compressed by compressed air from the tank 101 to each of the plurality of droplet discharge heads 114. Supplied.

The first position control device 104 moves the droplet discharge means 103 along the X-axis direction and the Z-axis direction orthogonal to the X-axis direction in response to a signal from the control means 112. Further, the first position control device 104 also has a function of rotating the droplet discharge means 103 around an axis parallel to the Z axis. In the present embodiment, the Z-axis direction is a direction parallel to the vertical direction (that is, the direction of gravitational acceleration). The second position controller 108 moves the stage 106 along the Y-axis direction orthogonal to both the X-axis direction and the Z-axis direction in response to a signal from the control unit 112. Further, the second position control device 108 also has a function of rotating the stage 106 around an axis parallel to the Z axis.
The stage 106 has a plane parallel to both the X-axis direction and the Y-axis direction. The stage 106 is configured so that the substrate 11 having the cells 14 to which the color filter ink 2 is to be applied can be fixed or held on the plane.

As described above, the droplet discharge means 103 is moved in the X-axis direction by the first position control device 104. On the other hand, the stage 106 is moved in the Y-axis direction by the second position control device 108. That is, the first position control device 104 and the second position control device 108 change the relative position of the droplet discharge head 114 with respect to the stage 106 (the substrate 11 held on the stage 106 and the liquid droplet discharge means 103 are relative to each other). Move on).
The control unit 112 is configured to receive ejection data representing a relative position at which the color filter ink 2 is to be ejected from an external information processing apparatus.

  As shown in FIG. 4, the droplet discharge means 103 has a plurality of droplet discharge heads 114 each having substantially the same structure, and a carriage 105 that holds these droplet discharge heads 114. In the present embodiment, the number of droplet discharge heads 114 held by the droplet discharge means 103 is eight. Each droplet discharge head 114 has a bottom surface provided with a plurality of nozzles 118 described later. The shape of the bottom surface of each droplet discharge head 114 is a polygon having two long sides and two short sides. The bottom surface of the droplet discharge head 114 held by the droplet discharge means 103 faces the stage 106 side, and the long side direction and the short side direction of the droplet discharge head 114 are respectively an X-axis direction and a Y-axis direction. Parallel to the direction.

  As shown in FIG. 5, the droplet discharge head 114 has a plurality of nozzles 118 arranged in the X-axis direction. The plurality of nozzles 118 are arranged such that the nozzle pitch HXP in the X-axis direction in the droplet discharge head 114 has a predetermined value. Although the specific value of nozzle pitch HXP is not specifically limited, For example, it can be set as 50-90 micrometers. Here, the “nozzle pitch HXP in the X-axis direction of the droplet discharge head 114” is a plurality of images obtained by projecting all the nozzles 118 in the droplet discharge head 114 onto the X-axis along the Y-axis direction. This corresponds to the pitch between nozzle images.

In the present embodiment, the plurality of nozzles 118 in the droplet discharge head 114 form a nozzle row 116A and a nozzle row 116B that both extend in the X-axis direction. The nozzle row 116A and the nozzle row 116B are arranged in parallel with a space therebetween. In this embodiment, 90 nozzles 118 are arranged in a line in the X-axis direction at a constant interval LNP in each of the nozzle array 116A and the nozzle array 116B. Although the specific value of LNP is not specifically limited, It can be set as 100-180 micrometers.
The position of the nozzle row 116B is shifted from the position of the nozzle row 116A by a half length of the nozzle pitch LNP in the positive direction in the X-axis direction (right direction in FIG. 5). Therefore, the nozzle pitch HXP in the X-axis direction of the droplet discharge head 114 is half the nozzle pitch LNP of the nozzle row 116A (or nozzle row 116B).

  Accordingly, the nozzle line density in the X-axis direction of the droplet discharge head 114 is twice the nozzle line density of the nozzle row 116A (or nozzle row 116B). In the present specification, “nozzle line density in the X-axis direction” means the number per unit length of a plurality of nozzle images obtained by projecting a plurality of nozzles on the X-axis along the Y-axis direction. It corresponds to. Of course, the number of nozzle rows included in the droplet discharge head 114 is not limited to two. The droplet discharge head 114 may include M nozzle rows. Here, M is a natural number of 1 or more. In this case, in each of the M nozzle rows, the plurality of nozzles 118 are arranged at a pitch that is M times the nozzle pitch HXP. Further, when M is a natural number of 2 or more, the other (M−1) nozzle rows are only i times as long as the nozzle pitch HXP with respect to one of the M nozzle rows. There is no overlap in the X-axis direction. Here, i is a natural number from 1 to (M−1).

  In the present embodiment, each of the nozzle row 116 </ b> A and the nozzle row 116 </ b> B includes 90 nozzles 118, and thus one droplet discharge head 114 has 180 nozzles 118. However, 5 nozzles at both ends of the nozzle row 116A are set as “pause nozzles”. Similarly, 5 nozzles at both ends of the nozzle row 116B are also set as “pause nozzles”. The color filter ink 2 is not ejected from these 20 “rest nozzles”. Therefore, 160 nozzles 118 out of 180 nozzles 118 in the droplet discharge head 114 function as nozzles that discharge the color filter ink 2.

As shown in FIG. 4, in the droplet discharge means 103, a plurality of the droplet discharge heads 114 are arranged in two rows along the X-axis direction. The droplet discharge heads 114 in one row and the droplet discharge heads 114 in the other row are arranged so as to partially overlap when viewed from the Y-axis direction in consideration of the rest nozzles. Thereby, in the droplet discharge means 103, the nozzle 118 that discharges the color filter ink 2 is continuous in the X-axis direction at the nozzle pitch HXP over the length of the dimension of the substrate 11 in the X-axis direction. It is configured.
In the droplet discharge means 103 of the present embodiment, the droplet discharge head 114 is disposed so as to cover the entire length of the substrate 11 in the X-axis direction. A part of the length of the substrate 11 corresponding to the dimension in the X-axis direction may be covered.

  As shown in the figure, each droplet discharge head 114 is an inkjet head. More specifically, each droplet discharge head 114 includes a vibration plate 126 and a nozzle plate 128. Between the diaphragm 126 and the nozzle plate 128, a liquid pool 129 in which the color filter ink 2 supplied from the tank 101 through the hole 131 is always filled is located.

  In addition, a plurality of partition walls 122 are located between the diaphragm 126 and the nozzle plate 128. A portion surrounded by the diaphragm 126, the nozzle plate 128, and the pair of partition walls 122 is a cavity 120. Since the cavities 120 are provided corresponding to the nozzles 118, the number of the cavities 120 and the number of the nozzles 118 are the same. The color filter ink 2 is supplied from the liquid pool 129 to the cavity 120 via the supply port 130 positioned between the pair of partition walls 122.

On the diaphragm 126, the vibrator 124 is positioned corresponding to each cavity 120. The vibrator 124 includes a piezoelectric element 124C and a pair of electrodes 124A and 124B that sandwich the piezoelectric element 124C. By applying a driving voltage between the pair of electrodes 124A and 124B, the vibrator 124 vibrates, and the vibration is transmitted to the color filter ink 2 through the diaphragm 126, and the corresponding nozzle 118 performs color. Filter ink 2 is ejected. The shape of the nozzle 118 is adjusted so that the color filter ink 2 is ejected from the nozzle 118 in the Z-axis direction.
By the way, the diaphragm 126 is generally chemically stable and at least a part thereof is polyphenylene sulfide resin (PPS resin) from the viewpoint of high mechanical strength such as pulling and bending and high durability against heat and solvent. It is composed of a film.

  The droplet discharge device (industrial use) used in the manufacture of color filters is completely different from that applied to printers (consumer use). Since it is used for droplet ejection, it is required to eject a large amount of droplets for a long time, and it is used under severe conditions. In addition, a droplet discharge device (for industrial use) used for manufacturing a color filter needs to have a stable droplet discharge amount with high accuracy over a long period of time.

However, since it is used under such severe conditions, conventionally, the color filter ink may swell the PPS resin film that constitutes the vibration plate, destabilizing the discharge amount of droplets, etc. Could cause problems.
On the other hand, since the influence on the PPS resin film can be made particularly small by using the color filter ink of the present invention, the color filter ink can be stably discharged over a long period of time. As a result, color unevenness, density unevenness and the like in each part are suppressed, and a color filter having excellent uniformity of characteristics among individuals can be stably manufactured.

The nozzle plate 128 is provided with a base material made of stainless steel, a silica film provided to cover the base material and mainly made of a silica compound, and provided to cover the silica film, and includes a repellent containing a fluoroalkyl compound. And a liquid film.
Further, the silica film has a function of closely attaching the liquid repellent film and the stainless steel base material, and also has a function of protecting the stainless steel base material.

The control means 112 (see FIG. 3) may be configured to give a signal to each of the plurality of vibrators 124 independently of each other. That is, the volume of the color filter ink 2 ejected from the nozzle 118 may be controlled for each nozzle 118 in accordance with a signal from the control unit 112. The control unit 112 can also set the nozzle 118 that performs the ejection operation during the application scan and the nozzle 118 that does not perform the ejection operation.
In this specification, a portion including one nozzle 118, a cavity 120 corresponding to the nozzle 118, and a vibrator 124 corresponding to the cavity 120 may be referred to as “ejection unit 127”. According to this notation, one droplet discharge head 114 has the same number of discharge units 127 as the number of nozzles 118.

Using the droplet discharge device 100 as described above, the color filter ink 2 corresponding to the colored portions 12 of the plurality of colors of the color filter 1 is applied to the cells 14. By using the apparatus as described above, the color filter ink 2 can be efficiently and selectively applied to the cells 14. In addition, as described above, the color filter ink 2 has excellent ejection stability, and even when droplets are ejected for a long period of time, the flight curve and the droplet ejection amount are low. Problems such as destabilization are extremely unlikely to occur. Accordingly, a plurality of types of inks used to form colored portions of different colors are mixed (mixed), or between a plurality of colored portions that are originally required to have the same color density. Problems such as the occurrence of variations in color density can be reliably prevented. In the illustrated configuration, the droplet discharge device 100 has only one tank 101 for holding the color filter ink 2, a tube 110, etc., but the color filter 1 has a plurality of these members. It may have a plurality of colors corresponding to the colored portion 12. In manufacturing the color filter 1, a plurality of droplet discharge devices 100 corresponding to a plurality of color filter inks 2 may be used.
In the present invention, the droplet discharge head 114 may use an electrostatic actuator as a driving element instead of a piezoelectric element. In addition, the droplet discharge head 114 may be configured to use an electrothermal conversion element as a drive element and discharge the color filter ink by utilizing the thermal expansion of the material by the electrothermal conversion element.

<Colored part forming step (curing step)>
Next, the liquid medium is removed from the color filter ink 2 in the cell 14, and the curable resin material is cured to form a solid colored portion 12 (1e). Thereby, the color filter 1 is obtained.
This step is usually performed by heating.
Moreover, in this embodiment, this process performs several heat processing from which temperature differs. Specifically, this process includes a first heat treatment for heating the substrate 11 at a relatively low temperature, and a second heat treatment for heating the substrate 11 at a temperature higher than the first heat treatment. .

  In such a case, by heating the substrate 11 at a relatively low temperature in the first heat treatment, the liquid medium is gently removed while preventing the convection of the color filter ink 2, and the color filter ink 2. Can be solidified in a state in which the surface thereof is flat. That is, in the first heat treatment, the viscosity of the color filter ink 2 rapidly increases and the fluidity decreases with the liquid medium removed to some extent. By removing the liquid medium in this state, the shape of the colored portion to be formed can be fixed with a flat surface. In particular, when polyhydric alcohol is contained in the ink 2, such an effect becomes remarkable. At this time, even if the curable resin is contained in the color filter ink 2, unintentional reaction of the curable resin can be prevented by heating at a relatively low temperature.

  In the second heat treatment, the liquid medium that could not be removed by the first heat treatment can be completely removed. Further, when the ink 2 contains a polyhydric alcohol, the polyhydric alcohol can be efficiently volatilized or decomposed and removed. Further, in this step, when the color filter ink 2 is cured by reacting the curable resin, the color filter ink 2 having a flat surface solidified in the first treatment can be efficiently cured in its shape. it can.

In the first treatment as described above, the temperature of the heated substrate 11 is not particularly limited, but is preferably 30 to 100 ° C, and more preferably 40 to 80 ° C. Accordingly, the liquid medium can be suitably removed from the color filter ink 2 while reliably preventing the convection of the substrate 11 and the color filter ink 2 and volatilization and decomposition of the flattening agent.
The time for the first heat treatment is not particularly limited, but is preferably 3 to 50 minutes, more preferably 5 to 40 minutes.

In the second treatment as described above, the temperature of the heated substrate 11 is not particularly limited, but is preferably 120 to 280 ° C, and more preferably 150 to 250 ° C. As a result, the liquid medium that could not be removed by the first heat treatment can be completely removed, and the leveling agent can be efficiently volatilized or decomposed and removed. Further, in this step, when the color filter ink 2 is cured by reacting the curable resin, the color filter ink 2 having a flat solidified surface in the first treatment can be efficiently cured in its shape. it can.
The time for the second heat treatment is not particularly limited, but is preferably 25 to 150 minutes, and more preferably 30 to 100 minutes.

  Further, in this step, for example, treatment such as irradiation with active energy rays or placing the substrate 11 to which the color filter ink 2 is applied in a reduced pressure environment may be performed. By irradiating active energy rays, the curing reaction of the curable resin material is allowed to proceed efficiently, or the curing reaction of the curable resin material is reliably advanced even when the heating temperature is relatively low. Thus, it is possible to obtain an effect that the adverse effect on the substrate 11 and the like can be prevented more reliably. As the active energy ray, light beams having various wavelengths, for example, ultraviolet rays, X-rays, g-rays, i-rays, excimer lasers and the like can be used. Further, by placing the substrate 11 provided with the color filter ink 2 in a reduced pressure environment, the liquid medium can be reliably removed even when the heating temperature is relatively low. 11. The occurrence of adverse effects on the formed colored portion 12 and the like is more reliably prevented.

<Image display device>
Next, a preferred embodiment of a liquid crystal display device that is an image display device (electro-optical device) having the color filter 1 will be described.
FIG. 7 is a cross-sectional view showing a preferred embodiment of the liquid crystal display device. As shown in the figure, the liquid crystal display device 60 includes a color filter 1, a substrate (opposite substrate) 66 disposed on the side of the color filter 1 on which the colored portion 12 is provided, a color filter 1 and a substrate 66. And a polarizing plate 67 provided on the surface side opposite to the surface of the substrate 11 of the color filter 1 opposite to the liquid crystal layer 62 (lower side in FIG. 7). And a polarizing plate 68 provided on the surface side opposite to the surface facing the liquid crystal layer 62 of the substrate 66 (upper side in FIG. 7). A common electrode 61 is provided on the surface of the color filter 1 on which the colored portion 12 and the partition wall 13 are provided (the surface opposite to the surface of the colored portion 12 and the partition wall 13 facing the substrate 11). On the surface of the (opposite substrate) 66 facing the liquid crystal layer 62 and the color filter 1, pixel electrodes 65 are arranged in a matrix at positions corresponding to the colored portions 12 of the color filter 1. Further, an alignment film 64 is provided between the common electrode 61 and the liquid crystal layer 62, and an alignment film 63 is provided between the substrate 66 (pixel electrode 65) and the liquid crystal layer 62.

The substrate 66 is a substrate having optical transparency with respect to visible light, and is, for example, a glass substrate.
The common electrode 61 and the pixel electrode 65 are made of a material having optical transparency to visible light, and are made of, for example, ITO.
Although not shown in the drawing, a plurality of switching elements (for example, TFT: thin film transistor) are provided so as to correspond to each pixel electrode 65. For each pixel electrode 65 corresponding to each coloring portion 12, by controlling the voltage application state between the common electrode 61, in the region corresponding to each coloring portion 12 (each pixel electrode 65), Light transmittance can be controlled.

  In the liquid crystal display device 60, light emitted from a backlight (not shown) enters from the polarizing plate 68 side (upper side in FIG. 7). And the light which permeate | transmitted the liquid crystal layer 62 and entered into each coloring part 12 (12A, 12B, 12C) of the color filter 1 is polarized as light of the color corresponding to each coloring part 12 (12A, 12B, 12C). The light is emitted from the plate 67 (lower side in FIG. 7).

"Electronics"
An image display device (electro-optical device) 1000 such as a liquid crystal display device having the color filter 1 as described above can be used for display portions of various electronic devices.
FIG. 8 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.
In this figure, a personal computer 1100 includes a main body 1104 having a keyboard 1102 and a display unit 1106. The display unit 1106 is supported by the main body 1104 via a hinge structure so as to be rotatable. Yes.
In the personal computer 1100, the display unit 1106 includes an image display device 1000.
FIG. 9 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 is provided with an image display device 1000 in a display unit, together with a plurality of operation buttons 1202, an earpiece 1204, and a mouthpiece 1206.

FIG. 10 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

On the back of a case (body) 1302 in the digital still camera 1300, an image display device 1000 is provided in the display unit, and is configured to display based on an imaging signal from the CCD, and a finder that displays a subject as an electronic image. Function as.
A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the input / output terminal 1314 for data communication as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

  The electronic device of the present invention includes, for example, a television (for example, a liquid crystal television), a video camera, a viewfinder type, a monitor in addition to the above-described personal computer (mobile personal computer), mobile phone, and digital still camera. Direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, videophone, security TV monitor , Electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographic display devices, ultrasonic diagnostic devices, endoscopy) Mirror display device), fish finder, each Measuring instruments, gauges (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors, and a projection display such as a projector. In particular, televisions have a remarkable tendency to increase the size of display portions in recent years. However, in electronic devices having such a large display portion (for example, a display portion having a diagonal length of 80 cm or more), conventional color filter inks are used. When the color filter manufactured using the above is applied, problems such as uneven color and uneven density are particularly likely to occur. However, if the present invention is applied, such problems can be reliably prevented. That is, the effect of the present invention is more remarkably exhibited when applied to an electronic apparatus having a large display unit as described above.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, in the above-described embodiment, after the color filter ink corresponding to the colored portion of each color is applied to the cell, the liquid medium is removed from the color filter ink of each color in the cell and cured. In the above description, the resin material is cured, that is, the colored portion forming step is performed only once. However, the ink application step and the colored portion forming step may be repeatedly performed corresponding to each color.

  In addition, each unit constituting the color filter, the image display device, and the electronic device can be replaced with an arbitrary one that exhibits the same function, or another configuration can be added. For example, in the color filter of the present invention, a protective film that covers the colored portion may be provided on the surface of the colored portion opposite to the surface facing the substrate. Thereby, damage, deterioration, etc. of a coloring part can be prevented more effectively.

In the embodiment described above, the case where the color filter ink set includes three (three colors) color filter inks corresponding to the three primary colors of light has been mainly described. The number and type (color) of the color filter ink to be configured are not limited to those described above. For example, the color filter ink set may include four or more color filter inks.
In the above-described embodiment, the colored portion forming process has been described as performing two-step heat treatment. However, the colored portion may be formed by one heat treatment, or in one heat treatment. The heating temperature may be changed.

Next, specific examples of the present invention will be described.
[1] Polymer synthesis (preparation of polymer solution)
(Synthesis Example 1)
Into a 1 L reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen introduction tube and a thermometer, 37.6 parts by weight of 1,3-butylene glycol diacetate as a solvent (solvent) was placed at 90 ° C. Heated. Subsequently, 2,2′-azobis (isobutyronitrile) (AIBN): 2 parts by weight and 1,3-butylene glycol diacetate (solvent): 3 parts by weight were added to the flask. (3,4-epoxycyclohexyl) methyl methacrylate (manufactured by Daicel Chemical Industries, trade name Cyclomer M100): 27 parts by weight, 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate ( Showa Denko Co., Ltd., trade name MOI-BM): 1.5 parts by weight, 2-hydroxyethyl methacrylate (HEMA): 1.5 parts by weight was added dropwise over about 4 hours using a dropping pump. did. On the other hand, 2,2'-azobis (isobutyric acid) dimethyl (trade name V-601, manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 5 parts by weight of 1,3-butylene glycol diacetate (solvent): A solution (polymerization initiator solution) dissolved in 20 parts by weight was dropped over about 4 hours using another dropping pump. After completion of the dropwise addition of the polymerization initiator solution, AIBN: 0.2 part by weight and 1,3-butylene glycol diacetate (solvent): 1 part by weight were added and kept at the same temperature for about 2 hours. AIBN: 0.2 part by weight and 1,3-butylene glycol diacetate (solvent): 1 part by weight was added and kept at about the same temperature for about 2 hours, and then cooled to about room temperature to give polymer A A polymer solution A1 having a solid content of 30 wt% was obtained.

(Synthesis Examples 2 to 8)
Except for changing the type of monomer component used in the synthesis of the polymer (preparation of polymer solution), the amount used, and the type of solvent (solvent) as shown in Table 1, the same operation as in Synthesis Example 1 was performed. went. As a result, seven polymer solutions (polymer solutions A2 to A8) containing the polymer A and having a solid content of 30 wt% were obtained.

(Synthesis Example 9)
(3,4-epoxycyclohexyl) methyl methacrylate (manufactured by Daicel Chemical Industries, trade name Cyclomer M100), 2- (0- [1 ′ methylpropylideneamino] carboxyamino) ethyl methacrylate (Showa Denko K.K. Manufactured, trade name MOI-BM), and γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray, trade name SZ6030): 30 parts by weight instead of 2-hydroxyethyl methacrylate (HEMA) Except for the above, the same operation as in Synthesis Example 1 was performed. As a result, a polymer solution B1 (homopolymer solution) containing the polymer B and having a solid content of 30 wt% was obtained.

(Synthesis Examples 10-14)
The same operation as in Synthesis Example 9 was performed except that the types of monomer components used in the synthesis of the polymer (preparation of the polymer solution), the amount used, and the type of the solvent (solvent) were changed as shown in Table 1. went. As a result, five types of polymer solutions (polymer solutions B2 to B6) containing polymer B and having a solid content of 30 wt% were obtained.

(Synthesis Example 15)
(3,4-epoxycyclohexyl) methyl methacrylate (manufactured by Daicel Chemical Industries, trade name Cyclomer M100), 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate (Showa Denko Co., Ltd.) Manufactured, trade name MOI-BM), and 1H, 1H, 5H-octafluoropentyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name Biscote 8FM): 30 weight instead of 2-hydroxyethyl methacrylate (HEMA) The same operations as in Synthesis Example 1 were performed except that the parts were used. As a result, a polymer solution C1 (homopolymer solution) containing the polymer C and having a solid content of 30 wt% was obtained.

(Synthesis Examples 16 to 19)
The same operation as in Synthesis Example 15 was performed except that the types of monomer components used in polymer synthesis (preparation of polymer solution), the amounts used, and the types of solvents (solvents) were changed as shown in Table 1. went. As a result, four types of polymer solutions (polymer solutions C2 to C5) containing polymer C and having a solid content of 30 wt% were obtained.

(Synthesis Example 20)
As the monomer component, (3,4-epoxycyclohexyl) methyl methacrylate (manufactured by Daicel Chemical Industries, Ltd., trade name Cyclomer M100): 13.5 parts by weight, 2- (0- [1 ′ methylpropiyl methacrylate) Ridenamino] carboxyamino) ethyl (manufactured by Showa Denko KK, trade name MOI-BM): 0.75 parts by weight, 2-hydroxyethyl methacrylate (HEMA): 0.75 parts by weight, and γ-methacryloxypropyltri Methoxysilane (trade name SZ6030, manufactured by Toray Dow Corning Co., Ltd.): The same operation as in Synthesis Example 1 was performed, except that 15 parts by weight was used and diethylene glycol ethyl ether acetate was used as a solvent (solvent). As a result, a polymer solution X1 containing polymer X and having a solid content of 30 wt% was obtained.

  Table 1 summarizes the types of materials used in the synthesis of the polymers in Synthesis Examples 1 to 20 (preparation of polymer solutions) and the amounts used (compositions of the polymers synthesized in Synthesis Examples 1 to 20). In the table, “S” means a solvent (solvent), in particular, “S1” indicates 1,3-butylene glycol diacetate (boiling point: 232 ° C.), and “S2” indicates 2- (2-methoxy-1-methylethoxy) -1-methylethyl acetate (boiling point: 213 ° C.), “S3” indicates diethylene glycol monobutyl ether acetate (boiling point: 246 ° C.), “S4” This indicates propylene glycol diacetate (boiling point: 190 ° C.), and “S5” indicates diethylene glycol ethyl ether acetate (boiling point: 217 ° C.). “V-601” indicates 2,2′-azobis (isobutyric acid) dimethyl, “AIBN” indicates 2,2′-azobis (isobutyronitrile), and “a1-1”. Indicates (3,4-epoxycyclohexyl) methyl methacrylate (cyclomer M100), “a1-2” indicates (3,4-epoxycyclohexyl) methyl acrylate, and “a2-1” indicates methacrylic acid. Acid 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl (MOI-BM), “a2-2” is 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name “ Karenz MOI ")," a3-1 "indicates 2-hydroxyethyl methacrylate (HEMA), and" a3-2 "indicates 4-hydride. “A4-1” indicates 1H, 1H, 5H-octafluoropentyl methacrylate (Biscoat 8FM), “a4-2” indicates 2-ethylhexyl methacrylate, “b1-1” represents γ-methacryloxypropyltrimethoxysilane (SZ6030), “b1-2” represents γ-methacryloxypropyltriethoxysilane, and “b2-1” represents ethyl methacrylate. “C1-1” indicates 1H, 1H, 5H-octafluoropentyl methacrylate (Biscoat 8FM), and “c1-2” indicates 2,2,3,3-tetrafluoropropyl acrylate (Biscoat 4F). "C2-1" is 2,3-dihydroxybutyl methacrylate It is shown, "c2-2" refers to cyclohexyl methacrylate. In the table, the weight average molecular weight Mw of the polymer constituting the polymer solution is also shown.

[2] Preparation of color filter ink (ink set) (Example 1)
Dispersic 111: 5.04 g (14 parts by weight) as a dispersant, Dispersic 166: 28.07 g (78 parts by weight) as a dispersant, and SPCN-17X (made by Showa Polymer Co., Ltd.) as a thermoplastic resin ): 19.43 g (54 parts by weight) and 1,3-butylene glycol diacetate as a liquid medium: 91.05 g (253 parts by weight) were charged into a stirrer (uniaxial mixer) having an internal capacity of 400 cc. Dispersant dispersion was obtained by stirring for 10 minutes with a disper mill and predispersion (preliminary dispersion step). At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm.

Next, as described below, a fine dispersion step was performed in which a pigment was added to the dispersant dispersion obtained in the preliminary dispersion step, and inorganic beads were added in multiple stages for fine dispersion treatment.
First, 355.99 g (100 parts by weight) of pigment was added to the obtained dispersant dispersion and stirred for 10 minutes. At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm. Examples of the pigment include C.I. I. A mixture of Pigment Red 254 and a pigment derivative represented by the formula (3): 25.85 g; I. A mixture of Pigment Red 177 and the pigment derivative represented by the formula (2): 7.60 g, and a sulfonated pigment derivative powder having a chemical structure represented by the formula (4): 3.55 g were used. At this time, the mixture was diluted with 1,3-butylene glycol diacetate as a liquid medium so that the pigment content in the mixture of the dispersant dispersion and the pigment was 16 wt%.

Next, inorganic beads having an average particle size of 0.8 mm (first inorganic beads, manufactured by Zirconia, “Toray ceramic pulverized ball” (trade name), manufactured by Toray Industries, Inc.) are added and stirred at room temperature for 30 minutes. First-stage distributed processing (first processing) was performed. At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm.
Next, the inorganic beads (first inorganic beads) are removed by filtration using a filter (“PALL HDCII Membrane Filter”, manufactured by PALL), and then inorganic beads having a mean particle diameter of 0.1 mm (second Inorganic beads, made of zirconia, “Toray ceramic pulverized ball” (trade name), manufactured by Toray Industries, Inc.) were added, and the mixture was further stirred for 30 minutes to perform the second stage dispersion treatment (second treatment). At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm. At this time, the pigment dispersion was diluted with 1,3-butylene glycol diacetate as a liquid medium so that the pigment content in the obtained pigment dispersion was 13 wt%.
Thereafter, the inorganic beads (second inorganic beads) were removed by filtration using a filter (“PALL HDCII Membrane Filter” (trade name), manufactured by PALL) to obtain a pigment dispersion.

  Next, the pigment dispersion obtained as described above, the polymer solution A1, the polymer solution B1, and the polymer solution C1 were mixed. In this step, the pigment dispersion, polymer solution A1, polymer solution B1, polymer solution C1, 1,3-butylene glycol diacetate and polyethylene glycol monomethyl ether (trade name, manufactured by Toho Chemical Industry Co., Ltd.) : "Hi-Mole PM", weight average molecular weight: 220, average degree of polymerization: 4, boiling point: 290-310), polyethylene glycol # 300 (weight average molecular weight: 300) as a polyhydric alcohol, and vinyl surfactant LHP-90 (manufactured by Enomoto Kasei Co., Ltd.) was placed in a stirrer (uniaxial mixer) with a content of 400 cc and stirred for 10 minutes with a disper mill. At this time, the rotation speed of the stirring blade of the stirrer was set to 2000 rpm. As a result, the intended red color filter ink (R ink) was obtained. The pigment content of the R ink at this time was 7.3 wt%.

  In addition, the color filter ink (G ink) and the blue color filter ink (B ink) are the same as the red color filter ink except that the type of pigment and the amount of each component used are changed. Was prepared. As a result, an ink set composed of three colors of R, G, and B was obtained. The average particle diameter of the pigment constituting the R ink, the average particle diameter of the pigment constituting the G ink, and the average particle diameter of the pigment constituting the B ink were 70 nm, 70 nm, and 70 nm, respectively. Examples of the G ink pigment include C.I. I. Pigment Green 58 and a sulfonated pigment derivative powder having the chemical structure represented by the above formula (4) were used, and the pigment content in the final G ink was 10.1 wt%. Examples of the B ink pigment include C.I. I. Pigment Blue 15: 6 was used, and the pigment content in the final B ink was 4.9 wt%.

(Examples 2 to 8)
A color filter ink (ink set) was prepared in the same manner as in Example 1 except that the type and content of the color filter ink were changed as shown in Tables 2 and 3.
(Comparative Examples 1 and 2)
A color filter ink (ink set) was prepared in the same manner as in Example 1 except that the type and content of the color filter ink material were changed as shown in Table 3.

  Tables 2 and 3 collectively show the types and contents of the components of the color filter ink in each of the above Examples and Comparative Examples. In the table, C.I. I. Pigment Red 254 is "PR254", C.I. I. Pigment Red 177 is “PR177”, C.I. I. Pigment Red 254 and a pigment derivative represented by the formula (3) “PR254D”, C.I. I. Pigment Red 177 and a pigment derivative represented by the formula (2) “PR177D”, a powder composed of the pigment derivative represented by the formula (4) “SPD”, C.I. I. Pigment Green 58 is changed to “PG58”, C.I. I. Pigment Green 36 is “PG36”, C.I. I. Pigment Blue 15: 6 is changed to “PB15: 6”, C.I. I. Pigment Yellow 150 is “PY150”, Dispersic 111 (acid value: 50 KOHmg / g) is “DA1”, Dispersic 2095 (acid value: 13 KOHmg / g) is “DA2”, Dispersic P104 (acid value: 360 KOHmg / g) ) “DA3”, Dispersic 166 (amine number: 115 KOHmg / g) “DA4”, Dispersic 9075 (amine number: 12 KOHmg / g) “DA5”, SPCN-17X “DR1”, polyethylene glycol # 300 (Average weight molecular weight: 300, viscosity: 70 mPa · s) is “PEG1”, polyethylene glycol # 200 (average weight molecular weight: 200, viscosity: 50 mPa · s) is “PEG2”, polyethylene glycol # 400 (average weight molecular weight: 400 Viscosity: 90m a · s) is “PEG3”, polyethylene glycol # 600 (average weight molecular weight: 600, viscosity: 135 mPa · s) is “PEG4”, polypropylene glycol # 400 (molecular weight: 400, viscosity: 70 mPa · s), monomer component : 1,2-propylene glycol) to “PPG1”, polypropylene glycol # 1000 (average weight molecular weight: 1000, viscosity: 150 mPa · s, monomer component: 1,2-propylene glycol) to “PPG2”, polypropylene glycol # 2000 (average weight molecular weight: 2000, viscosity: 310 mPa · s, monomer component: 1,2-propylene glycol) is “PPG3”, and acrylic surfactant (LHP-95, manufactured by Enomoto Kasei Co., Ltd.) is “ LHP95 ", vinyl surfactant (LHP-90, manufactured by Enomoto Kasei Co., Ltd.) LHP90 ”, fluorosurfactant (Megafac F482, manufactured by Dainippon Ink & Chemicals, Inc.) was“ MF482 ”, and silicone surfactant (BYK-307, manufactured by Big Chemie) was“ BYK307 ”. . The acid value of the dispersant was determined by a method based on DIN EN ISO 2114, and the amine value was determined by a method based on DIN 16945.

In the table, the type of solvent (liquid medium) indicates various solvents (liquid medium) in the same manner as in Table 1. Furthermore, polyethylene glycol monomethyl ether (manufactured by Toho Chemical Industry Co., Ltd., trade name: “HIGH” Mole PM ”, weight average molecular weight: 220, average degree of polymerization: 4, boiling point: 290 to 310) are indicated by“ S6 ”. In the column of the curable resin material in the table, the polymer contained in the polymer solution A1 is indicated by A1. Similarly, the polymer contained in polymer solution A2-A8, B1-B6, C1-C5 was shown by A2-A8, B1-B6, C1-C5, respectively.
In the column of “swelling ratio of PPS resin film”, a film (diameter: 3 mm × diameter) of PPS resin (manufactured by Toray Industries, trade name “Torelina”, weight average molecular weight: 50000) in a sealed liquid medium. The swelling rate of the PPS resin film was shown when a 2 mm-thick disc-shaped test piece) was allowed to stand for 10 days in an environment of 40 ° C. under atmospheric pressure.

[3] Droplet discharge stability evaluation (discharge stability evaluation)
Using the color filter inks (ink sets) obtained in the respective Examples and Comparative Examples, evaluations were performed by the following tests.
[3.1] Evaluation of landing position accuracy Prepared are a liquid droplet ejection device as shown in FIGS. With the piezo element drive waveform optimized, 150,000 (150,000 drops) of droplets were continuously discharged from each nozzle of the droplet discharge head for each ink. For the 150,000 droplets ejected from the designated nozzle near the center of the droplet ejection head, the average value of the deviation amount d from the center aiming position of the center position of each landed droplet is obtained, and the following four steps Evaluation was performed according to the criteria of It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented. In addition, as the liquid droplet ejection head, a nozzle plate joined with an epoxy adhesive (AE-40 manufactured by Ajinomoto Fine Techno Co., Ltd.) was used.
A: The average value of the shift amounts d is less than 0.04 μm.
B: The average value of the shift amount d is 0.04 μm or more and less than 0.10 μm.
C: The average value of the shift amounts d is 0.10 μm or more and less than 0.15 μm.
D: The average value of the shift amounts d is 0.15 μm or more.

[3.2] Stability evaluation of droplet discharge amount Droplet discharge device as shown in FIGS. 3 to 6 installed in a chamber (thermal chamber), and ink sets for color filters of the above-described embodiments and comparative examples Were prepared, and 150,000 droplets (150,000 droplets) were continuously discharged from each nozzle of the droplet discharge head for each ink in a state where the drive waveform of the piezo element was optimized. For the two specified nozzles on the left and right ends of the droplet discharge head, the total weight of the discharged droplets is obtained, and the absolute value ΔW [ng] of the difference between the average discharge amounts of the droplets discharged from the two nozzles is calculated. Asked. The ratio (ΔW / W _T ) of this ΔW to the target discharge amount W _T [ng] of the droplet was determined and evaluated according to the following four criteria. As the value of [Delta] W / W _T is small, it can be said that the greater the stability of the droplet discharge amount. In addition, as the liquid droplet ejection head, a nozzle plate joined with an epoxy adhesive (AE-40 manufactured by Ajinomoto Fine Techno Co., Ltd.) was used.
A: The value of ΔW / _{W T} is less than 0.050.
B: The value of ΔW / _{W T} is less than 0.050 than 0.420.
C: The value of ΔW / _{W T} is less than 0.420 than 0.750.
D: The value of ΔW / _{W T} is 0.750 or more.

[3.3] Evaluation of intermittent printing performance Prepared are a droplet discharge device as shown in FIG. 3 to FIG. 6 installed in a chamber (thermal chamber) and an ink set for a color filter of each of the above examples and comparative examples, With the driving waveform of the piezo element optimized, 15000 droplets (15000 droplets) are continuously discharged from each nozzle of the droplet discharge head for each ink, and then the droplets are discharged for 60 seconds. Interrupted (first sequence). Thereafter, similarly, the operation of continuously discharging the droplets and interrupting the discharge of the droplets were repeated. For the designated nozzle near the center of the droplet discharge head, the average weight W ₁ [ng] of the droplets discharged in the first sequence and the average weight W ₂₀ [ng] of the droplets discharged in the 20th sequence And asked. Then, the ratio (| W ₁ −W ₂₀ | / W _T ) of the absolute value of the difference between W ₁ and W ₂₀ to the target discharge amount W _T [ng] of the droplet is obtained, and the following three criteria are used. ,evaluated. | _W 1 _-W 20 | as the value of / _{W T} is small, it can be said to be excellent in intermittent printing performance (stability of the droplet discharge quantity). In addition, as the liquid droplet ejection head, a nozzle plate joined with an epoxy adhesive (AE-40 manufactured by Ajinomoto Fine Techno Co., Ltd.) was used.
_A: | _{W 1} -W 20 | value of / _{W T} is less than 0.060.
_B: | _{W 1} -W 20 | values of / _{W T} is less than 0.060 or 0.700.
_C: | _{W 1} -W 20 | value of / _{W T} is 0.700 or more.

[3.4] Continuous Discharge Test Using a droplet discharge device as shown in FIGS. 3 to 6 installed in a chamber (thermal chamber), the color filter ink set of each of the examples and comparative examples, 40 Each ink constituting the color filter ink set was ejected by continuously operating the droplet ejection apparatus for 108 hours under the environment of% RH. In addition, as the liquid droplet ejection head, a nozzle plate joined with an epoxy adhesive (AE-40 manufactured by Ajinomoto Fine Techno Co., Ltd.) was used.
The nozzle clogging rate ([(number of clogged nozzles) / (total number of nozzles)] × 100) obtained after continuous operation is found and the nozzles are clogged. With respect to the above, it was examined whether or not clogging can be eliminated by a cleaning member made of a plastic material. The results were evaluated according to the following four criteria.

A: No nozzle clogging occurs.
B: The occurrence rate of nozzle clogging is less than 0.8% (excluding zero), and clogging can be eliminated by cleaning.
C: The occurrence rate of nozzle clogging is 0.8% or more and less than 1.0%, and clogging can be eliminated by cleaning.
D: The occurrence rate of nozzle clogging is 1.0% or more, or clogging cannot be eliminated by cleaning.
In addition, said evaluation was performed on the same conditions about each Example and each comparative example.

[4] Production of color filter A color filter was produced in the following manner using the color filter ink sets obtained in the above Examples and Comparative Examples.
First, a soda glass substrate (G5 size: 1100 × 1300 mm) on which a silica (SiO ₂ ) film for preventing elution of sodium ions was formed on both surfaces was prepared and subjected to a cleaning treatment.

Next, the radiation-sensitive composition for forming partition walls containing carbon black was applied to the entire surface of one of the cleaned substrates to form a coating film.
Next, prebaking was performed under the conditions of heating temperature: 110 ° C. and heating time: 120 seconds.
Thereafter, irradiation with radiation is performed through a photomask to perform post-exposure baking (PEB), followed by development using an alkaline developer, and further by performing post-baking, thereby separating the partition walls. Formed. PEB was performed under the conditions of heating temperature: 110 ° C., heating time: 120 seconds, and radiation irradiation intensity: 150 mJ / cm ² . The development process was performed by, for example, a vibration dipping method. The development processing time was 60 seconds. The post-bake treatment was performed under the conditions of heating temperature: 150 ° C. and heating time: 5 minutes. The formed partition wall had a thickness of 2.1 μm.

Next, using a droplet discharge device as shown in FIGS. 3 to 6, color filter ink was discharged into a cell as a region surrounded by a partition wall. At this time, three color filter inks were used so that the color filter inks of the respective colors were not mixed. In each cell, the color filter ink was applied in such an amount that the average thickness of the colored portion to be formed was 2.0 μm.
Thereafter, heat treatment was performed on a hot plate at 60 ° C. for 30 minutes, and further, heat treatment was performed in an oven at 200 ° C. for 1 hour, whereby three colored portions were formed. Thereby, a color filter as shown in FIG. 1 was obtained.
Using the method as described above, 8,000 color filters were produced using the color filter inks (ink sets) of each Example and each Comparative Example.

[5] Evaluation of color filter The following evaluation was performed using each color filter obtained as described above.
[5.1] Color unevenness and density unevenness Among the color filters manufactured using the color filter inks (ink sets) of the respective examples and comparative examples, the color filters manufactured for the 8000th sheet are respectively used. Then, a liquid crystal display device as shown in FIG. 7 was manufactured under the same conditions.
Using these liquid crystal display devices, visual observation is performed in a dark room with red single color display, green single color display, blue single color display, and white single color display, and color unevenness and density at each part. The occurrence of unevenness was evaluated according to the following five-stage criteria.

A: Color unevenness and density unevenness are not recognized at all.
B: Color unevenness and density unevenness are hardly recognized.
C: Color unevenness and density unevenness are slightly recognized.
D: Color unevenness and density unevenness are clearly recognized.
E: Color unevenness and density unevenness are remarkably recognized.

[5.2] Characteristic difference between individuals Among the color filters manufactured using the color filter inks (ink sets) of the respective Examples and Comparative Examples, the 1st to 10th sheets, and 7990, respectively. A color filter manufactured on the seventh to seventh sheets was prepared, and 100 pixels were randomly extracted from each of these color filters. For the extracted 100 pixels, in a dark room, red single color display, green single color display, blue single color display, white single color display are performed, and color measurement is performed using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.) The chromaticity was determined. For each color filter, the average value of the chromaticity obtained for the 100 pixels was defined as the chromaticity of the color filter. From the results, for each example and each comparative example, the maximum color difference (Lab display) among the color filters manufactured in the 1st to 10th sheets and 7990 to 7999th sheets (total 20 color filters), respectively. The color difference ΔE) in the system was determined and evaluated according to the following five criteria.

A: Color difference (ΔE) is less than 0.6.
B: Color difference (ΔE) is 0.6 or more and less than 1.3.
C: Color difference (ΔE) is 1.3 or more and less than 1.8.
D: Color difference (ΔE) is 1.8 or more and less than 2.3.
E: Color difference (ΔE) is 2.3 or more.

[5.3] Durability Among the color filters manufactured using the color filter inks (ink sets) of the respective Examples and Comparative Examples, the color filters manufactured for the 5001st to 5010th sheets are used. A liquid crystal display device as shown in FIG. 7 was manufactured under the same conditions.
Using these liquid crystal display devices, light leakage (white spots, bright spots) occurs when visual observation is performed in a dark room with red single color display, green single color display, and blue single color display. Confirmed that there is no.

Next, the color filter was removed from the liquid crystal display device.
Each removed color filter is placed in a 20 ° C. environment for 1.5 hours, then in a 50 ° C. environment for 2 hours, then in a 20 ° C. environment for 1.5 hours, and then in a −10 ° C. environment. For 3 hours. Thereafter, the environmental temperature was returned again to 20 ° C., which was set as one cycle (8 hours), and this cycle was repeated 30 times in total (total 240 hours).
Thereafter, using these color filters, a liquid crystal display device as shown in FIG. 7 was assembled again.
Using these liquid crystal display devices, visual observation is performed in a dark room with red single color display, green single color display, and blue single color display, and the occurrence of light leakage (white spots, bright spots) is observed. The evaluation was made according to the following five-stage criteria.

A: There is no color filter in which light leakage (white spots, bright spots) occurs.
B: Light leakage (white spots, bright spots) is observed in one or two color filters.
C: Light leakage (white spots, bright spots) is observed in 3 to 5 color filters.
D: Light leakage (white spots, bright spots) is observed in 6 to 9 color filters.
E: Light leakage (white spots, bright spots) is observed in 10 color filters.

[6] Evaluation of Contrast Using the color filter ink (ink set) obtained in each of the above Examples and Comparative Examples, evaluation by the following test was performed.
A red colored film was formed on each of different glass plates (diameter: 10 cm) by the ink jet method using the R inks constituting the ink sets of the respective Examples and Comparative Examples.
The colored film was formed by performing heat treatment at 110 ° C. for 8 minutes on a hot plate after droplet discharge onto the glass plate, and further performing heat treatment in an oven at 220 ° C. for 45 minutes. The discharge amount of the color filter ink was adjusted so that the thickness of the formed colored film was 1.5 μm.

Thus, about the glass substrate in which the colored film was formed, contrast (CR) was calculated | required using the contrast tester (the Kasaka Electric Co., Ltd. make, CT-1), and it evaluated in accordance with the following three steps | paragraphs.
A: CR is 3300 or more.
B: CR is 2200 or more and less than 3300.
C: CR is less than 2200.

For the G ink and B ink constituting the ink set of each of the examples and comparative examples, a colored film is formed on a glass plate (diameter: 10 cm) by the inkjet method in the same manner as described above. Contrast was calculated | required about the made glass substrate.
The glass substrate on which the green colored film was formed was evaluated according to the following three-stage criteria.
A: CR is 12000 or more.
B: CR is 5800 or more and less than 12000.
C: CR is less than 5800.

The glass substrate on which the blue colored film was formed was evaluated according to the following three-stage criteria.
A: CR is 3000 or more.
B: CR is 2500 or more and less than 3000.
C: CR is less than 2500.
In the above evaluation, each color filter and each glass plate were observed and measured under the same conditions.
These results are shown in Tables 4 and 5.

As is apparent from the table, the present invention has excellent droplet ejection stability, and the produced color filter has suppressed color unevenness, density unevenness, and light leakage, and has characteristics among individuals. The variation of was also small. In the present invention, the durability of the color filter was also excellent. In the present invention, the contrast was also excellent. In the present invention, an excellent quality color filter could be stably produced. On the other hand, in each comparative example, a satisfactory result was not obtained.
Further, when a commercially available liquid crystal television was disassembled and the liquid crystal display device part was replaced with one manufactured as described above, and the same evaluation as described above was performed, the same result as above was obtained.

It is sectional drawing which shows suitable embodiment of the color filter of this invention. It is sectional drawing which shows the manufacturing method of a color filter. It is a perspective view which shows the droplet discharge apparatus used for manufacture of a color filter. It is the figure which observed the droplet discharge means in the droplet discharge apparatus shown in FIG. 3 from the stage side. It is a figure which shows the bottom face of the droplet discharge head in the droplet discharge apparatus shown in FIG. It is a figure which shows the droplet discharge head in the droplet discharge apparatus shown in FIG. 3, (a) is a cross-sectional perspective view, (b) is sectional drawing. It is sectional drawing which shows embodiment of a liquid crystal display device. 1 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Color filter 11 ... Board | substrate 12 ... Colored part 12A ... 1st colored part 12B ... 2nd colored part 12C ... 3rd colored part 13 ... Partition 14 ... Cell 2 ... Color filter ink 3 ... Coating film 60 ... Liquid crystal display device 61 ... Common electrode 62 ... Liquid crystal layer 63, 64 ... Alignment film 65 ... Pixel electrode 66 ... Substrate (counter substrate) 67, 68 ... Polarizing plate 100 ... Droplet discharge device 101 ... Tank 102 ... Discharge scanning unit 103 ... Droplet discharge means 104 ... first position control device 105 ... carriage 106 ... stage 108 ... second position control device 110 ... tube 112 ... control means 114 ... droplet discharge head (inkjet head) 116A, 116B ... nozzle array 118 ... nozzle 120 ... cavity 122 ... partition wall 124 ... vibrator 124A, 124B ... electrode 12 C ... Piezo element 126 ... Diaphragm 127 ... Discharge unit 128 ... Nozzle plate 129 ... Liquid pool 130 ... Supply port 131 ... Hole 1000 ... Image display device 1100 ... Personal computer 1102 ... Keyboard 1104 ... Main body 1106 ... Display unit 1200 ... Mobile Telephone 1202 ... Operation buttons 1204 ... Earpiece 1206 ... Mouthpiece 1300 ... Digital still camera 1302 ... Case (body) 1304 ... Light receiving unit 1306 ... Shutter button 1308 ... Circuit board 1312 ... Video signal output terminal 1314 ... Input for data communication Output terminal 1430 ... TV monitor 1440 ... Personal computer

Claims (14)

An ink for a color filter used for manufacturing a color filter that forms a colored portion on a substrate by an ink jet type droplet discharge device,
A colorant and a liquid medium in which the colorant is dissolved and / or dispersed,
When the film composed of polyphenylene sulfide resin is allowed to stand in an atmosphere of 40 ° C. for 10 days in the sealed liquid medium, the weight increase rate of the film is 7.0% or less. An ink for a color filter, characterized in that there is.   The color filter ink according to claim 1, wherein the polyphenylene sulfide resin has a weight average molecular weight of 5,000 to 100,000.   The color filter ink according to claim 1, wherein the liquid medium includes one having an alkoxyl group and / or an acetyl group at the end of a molecular chain.   4. The color filter ink according to claim 1, wherein the liquid medium has an acetyl group at both ends of a molecular chain.   5. The color filter ink according to claim 1, wherein the liquid medium contains an ether oxygen atom bonded to a second carbon atom in the molecule.   6. The color filter ink is used for manufacturing a color filter by being discharged from a droplet discharge head in which at least a part of a diaphragm is made of the polyphenylene sulfide resin. The color filter ink described in 1.   The color filter ink according to claim 1, wherein the color filter ink contains a polyhydric alcohol. The color filter ink includes a resin material,
The color filter ink according to any one of claims 1 to 7, wherein the resin material contains a polymer A containing at least an epoxy group-containing vinyl monomer a1 as a monomer component.   The polymer A contains, as a monomer component, a vinyl monomer a2 having an isocyanate group or a blocked isocyanate group in which it is protected with a protective group, in addition to the epoxy group-containing vinyl monomer a1. The color filter ink according to claim 8, wherein the color filter ink is a copolymer. The color filter ink includes a resin material,
10. The resin material according to claim 1, wherein the resin material includes a polymer B containing at least an alkoxysilyl group-containing vinyl monomer represented by the following formula (1) as a monomer component. Color filter ink.

A pigment as the colorant,
The pigment is C.I. I. The color filter ink according to any one of claims 1 to 10, comprising Pigment Green 58 and a sulfonated pigment derivative as an auxiliary pigment.   A color filter manufactured using the color filter ink according to claim 1.   An image display device comprising the color filter according to claim 12.   An electronic apparatus comprising the image display device according to claim 13.

Images