JP5293143B2 - Colored resin composition for color filter, color filter, liquid crystal display device and organic EL display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored resin composition in which a highly microparticulated pigment is efficiently and stably dispersed, so that the composition achieves a high transmittance, high contrast and superior color characteristic, suppresses developer stain, and has developability suitable for a plate making process; to manufacture a color filter of a small film thickness by using such a colored resin composition; and to provide a liquid crystal display and an organic EL display of high quality using an obtained color filter base. <P>SOLUTION: The colored resin composition comprises (A) a pigment, (B) a polymer, (C) a solvent and (F) a polymerizable monomer, wherein, in a chromatograph obtained by gel permeation chromatography (GPC) of (B) the polymer, an area of a component having a weight average molecular weight (Mw) in terms of polystyrene of &le;5,000 is &le;20% relative to the total area except peak areas of the unreacted polymerizable monomer and polymerization solvent. The use of the composition is also provided. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a colored resin composition (hereinafter sometimes referred to as a resist), a color filter, a liquid crystal display device, and an organic EL display. More specifically, by controlling the weight average molecular weight of the polymer used in the colored resin composition, it has become possible to disperse highly finely divided pigments efficiently and stably, resulting in excellent color characteristics. And a color resin composition having improved developer stains and having developability suitable for a plate making process, a color filter having a pixel produced using the color resin composition, and the color filter The present invention relates to a liquid crystal display device and an organic EL display.

Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.
In recent years, the trend of technological innovation has been rapid, and higher transmittance and high contrast have been required for color filters. In order to form a high-contrast color filter, it is necessary to disperse a pigment that is highly atomized and whose particle size distribution is narrowly controlled, and the technology for controlling the pigment particle size is rapidly developing. Naturally, the surface area of the pigment tends to increase, and the amount of the dispersant added tends to increase.

  On the other hand, it is necessary to limit components other than the pigment so as to obtain a constant color density and pixel film thickness. If the color density is to be increased, components that contribute to image forming properties such as photosensitivity, solubility, and curability are relatively decreased, and a problem that originally necessary image forming performance is lost tends to occur. That is, for example, when trying to reduce the pixel thickness (reducing the film thickness) by increasing the concentration of the pigment, the surface smoothness of the pixel is decreased due to the decrease in the curability of the composition, and the liquid crystal tends to be poorly aligned. There is. In addition, due to the increase in the amount of the dispersant and the solubility in the developer depending on the type of the dispersant, when development is not possible within a predetermined time, or coloring is possible on the non-image area after development even if development is possible In some cases, the undissolved resin composition tends to remain. Furthermore, when the undissolved material of the colored resin composition remains in the non-pixel portion on the substrate, the obtained color filter causes a decrease in transmittance and contrast, and in the case where it remains on the pattern edge portion, the ITO film This causes a situation that affects the subsequent process such as peeling of the film and deterioration of the sealing property in the liquid crystal cell forming process.

In recent years, electrical reliability is also very important. The charge charged between the electrodes of the liquid crystal display element may decay with time due to various factors, and a problem may occur that a predetermined charge is not applied to the liquid crystal layer (decrease in voltage holding ratio). Many known dispersants cause this and have low electrical reliability.
Furthermore, recent colored resin compositions are mainly those in which organic pigments are dispersed in organic solvents, but they contain water due to problems in product management and manufacturing processes from pigment production to color filter production. there is a possibility. As a result, the dispersion system is destroyed, causing thickening. In extreme cases, the pigment may aggregate and cause sedimentation. In the development process, when a color filter pixel is formed using a colored resin composition by a photolithography method, the color of the pixel changes locally due to moisture contained in the developer and a stain appears. Sometimes. As a result of intensive studies, it has been found that such problems vary depending on several factors. The structure of the polymer, the molecular weight distribution of the polymer, etc. not only affect the color characteristics such as the contrast ratio and coloring power, but also the developer. It was found that it has a great influence on the occurrence of spots.

  In order to solve such a series of problems, a pigment dispersant made of an acrylic block copolymer with an improved structure and acid value is used, or a pigment dispersion treatment is performed using a polymer having a specific structure in combination with this. Attempts have been made to improve dispersibility by adding a small amount (see Patent Documents 1 and 2). However, these methods have insufficient dispersibility in order to efficiently disperse recent highly atomized pigments with a small addition amount.

On the other hand, it has also been proposed to use a copolymer having a controlled molecular weight distribution as the polymer in the color filter composition (see Patent Documents 3 and 4). However, in the methods disclosed in these documents, it is not possible to improve the dispersibility of the pigment in the composition, and the specific molecular weight component contained in them rather lowers the dispersibility and reduces the coloring power. Met.
JP 2004-287298 A JP 2004-287366 A JP 2006-259680 A JP 2003-295432 A

The present invention has been made in view of the above-mentioned problems, and its object is as follows.
(A) A problem in preparing a colored resin composition that reduces the amount of the pigment dispersant that may adversely affect the electrical characteristics of the display device and that contains a high concentration of highly atomized pigment. Had become,
(1) increase in viscosity over time,
(2) decrease in contrast,
(3) To provide a colored resin composition for a color filter having improved initial viscosity and the like, high contrast, excellent dispersion stability, improved developer stain, and good developability and image formability.

(B) To provide a high-quality color filter using the colored resin composition for a color filter.
(C) To provide a high-quality liquid crystal display device and organic EL display using the color filter substrate.

  As a result of intensive studies to solve the above problems, the present inventors have used a polymer having a specific molecular weight distribution, so that a small amount of dispersant or the like is sufficient for a highly atomized pigment in recent years. It is possible to obtain a colored resin composition capable of ensuring excellent pigment dispersibility. Furthermore, when producing a pixel for a color filter using this colored resin composition, not only development is possible in a predetermined development time, but also the stain in the development process is improved, and the alkaline developer in the development process is improved. The pattern shape after firing is ensured, ensuring good adhesion to the substrate without reducing the undissolved matter in the non-image area on the substrate, reducing the image forming ability such as curability, etc. Has been found to be capable of uniformly forming high-density color pixels, and the present invention has been completed.

That is, the gist of the present invention is as follows.
1) In a chromatograph containing (A) a pigment, (B) a polymer, (C) a solvent, and (F) a polymerizable monomer, and obtained by gel permeation chromatography (GPC) of the polymer, polystyrene A colored resin composition, wherein an area of a component having a converted weight average molecular weight (Mw) of 5000 or less is 20% or less with respect to the total area excluding the peak areas of unreacted polymerizable monomer and polymerization solvent.
2) (B) In the chromatograph obtained by gel permeation chromatography (GPC) of the polymer, the area of the component having a polystyrene-equivalent weight average molecular weight (Mw) of 8000 or less is the peak area of the unreacted polymerizable monomer and the polymerization solvent. The colored resin composition as described in 1) above, which is 35% or less based on the total area excluding.
3) The colored resin composition as described in 1) or 2) above, which contains (D) a dispersant.
4) The colored resin composition as described in 3) above, wherein the weight ratio of the pigment (A) to the dispersant (D) is 4 or more.
5) The above (1) to (4), wherein the polymer (B) is a polymer of at least one or more hydrophobic group-containing vinyl monomers and at least one or more hydrophilic group-containing vinyl monomers. The colored resin composition according to any one of the above.
6) The colored resin composition as described in 5) above, wherein the polymer (B) has a carboxyl group as at least one hydrophilic group.
7) The colored resin composition as described in 5) or 6) above, wherein the hydrophilic group-containing vinyl monomer contains (meth) acrylic acid.
8) The colored resin composition according to any one of 5) to 7) above, wherein the acid value of the polymer (B) is 1 to 500 mgKOH / g.
9) The colored resin composition according to any one of 1) to 8) above, which comprises (E) a photopolymerization initiator and / or a thermal polymerization initiator.
10) Colored resin composition prepared using (A) pigment, (B) polymer, (C) pigment dispersion containing solvent, (F) polymerizable monomer, and other optional components In the chromatograph obtained by gel permeation chromatography (GPC) of polymer (B), the area of the component having a polystyrene equivalent weight average molecular weight (Mw) of 5000 or less is the peak area of the unreacted monomer and polymerization solvent A colored resin composition characterized by being 20% or less based on the total area excluding.
11) The pigment dispersion comprising (A) a pigment, (B) a polymer, and (C) a solvent further contains (D) a dispersant, and (D) the weight of (A) pigment relative to the dispersant. The colored resin composition according to 10), wherein the ratio is 4 or more.
12) The colored resin composition according to any one of 1) to 11), which is for a color filter.
13) A color filter comprising a pixel produced using the colored resin composition according to any one of 1) to 12).
14) A liquid crystal display device comprising the color filter according to 13).
15) An organic EL display comprising the color filter described in 13).

The present invention has the following effects.
(1) Highly atomized pigments that are being used in recent years for color filter applications can be efficiently dispersed in the composition, resulting in the production of color filters with high transmittance, high contrast, and low film thickness. The obtained colored resin composition can be provided.
In addition, (2) the solubility in the developer is good, development is possible within a predetermined time in the development process, the occurrence of developer stains is suppressed, and the colored resin composition is not applied to the non-image area on the substrate. No melt remains, excellent adhesion to the substrate, no deterioration of image forming ability such as curability, good pattern shape after firing, high transmittance, high contrast, low film thickness A colored resin composition capable of producing a color filter can be provided.

  Furthermore, (3) a high quality display device using such a color filter can be provided.

The constituent requirements and embodiments of the present invention will be described in detail below, but these are examples of the embodiments of the present invention, and the present invention is not limited to these contents.
Note that “(meth) acryl” and the like are “at least one of acrylic and methacrylic”, “
“(Meth) acrylate” or the like means “at least one of acrylate and methacrylate” or the like, for example, “(meth) acrylic acid” means “at least one of acrylic acid or methacrylic acid”. And

Further, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored resin composition.
In the present invention, unless otherwise specified, the weight average molecular weight refers to a polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).

Furthermore, in the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
<(A) Pigment>
The colored resin composition of the present invention comprises (A) a pigment as an essential component. For example, when forming a color filter pixel or the like, a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, brown Various color pigments such as pigments can be used. Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, although the specific example of the pigment which can be used is shown by a pigment number, the pigment which can be used is not limited to these illustrations.

  First, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 1 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 254 and the like.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc., more preferably C.I. I. Pigment Blue 15: 6 or the like.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Of these, C.I. I. Pigment green 7, 36, 58, and the like.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208 and the like. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, etc., more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180, and the like.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, pigment blue 80, and the like. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C.I. I. Pigment violet 23 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and the like.
The above various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (A) pigment, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

When forming the resin black matrix of a color filter using the colored resin composition of this invention, a black pigment can be used. Black pigments may be used alone, or pigments such as red, green, and blue may be mixed and used. Further, it may be an inorganic pigment or an organic pigment.
Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.

  Examples of carbon black include, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32 as products manufactured by Mitsubishi Chemical Corporation. , # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Etc. are products made by Degussa, such as Printex3, Printex3OP, Printex30, P intex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5 , Special Black4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc. are products manufactured by Cabot Corporation, such as Monarch120, MonLach280, MonLh300, MonL800, MonLh100, MonLH100 REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN XC72 , ELFTEX-8, etc. are the products manufactured by Colombian Carbon Co., Ltd. RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, etc. .

  For the production of a resin black matrix having a high optical density and a high surface resistivity, it is particularly preferable to use resin-coated carbon black. The resin-coated carbon black is disclosed in, for example, JP-A-9-26571, JP-A-9-71733, JP-A-9-95625, JP-A-9-238863, or JP-A-11-60989. It can be obtained by treating the known carbon black by the method.

  Further, as a method for producing titanium black, a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), and obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069). And a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not limited. Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

As another example of the black pigment, red, green and blue pigments can be mixed and used as a black pigment. Examples of pigments that can be mixed for preparing a black pigment include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. Is mentioned. Furthermore, other pigments that can be mixed are described in C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

The inorganic pigment and organic pigment used in the present invention have an average primary particle size of usually 100 nm or less, preferably 50 nm or less, more preferably 10 nm or more and 30 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 10 nm to 30 nm is particularly preferable.
If the average primary particle size is too large, the depolarization characteristics will deteriorate and the contrast will be insufficient, and if it is severe, the transmittance will be lowered. In some cases, production problems may occur, such as generation of protruding foreign matter, decreasing the yield of the color filter, or causing the process filter to be blocked. On the other hand, if it is too small, problems such as a decrease in dispersion stability due to an increase in the specific surface area of the pigment and a deterioration in heat resistance and light resistance due to the pigment approaching the molecular state may occur.

  The primary particle size of the pigment can be determined by the following method. First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). In the case of organic pigments and titanium black pigments, a plurality of (usually about 200 to 300) pigment particles having a diameter equivalent to an area circle converted to the diameter of a circle having the same area as the particle diameter of each pigment particle. The particle diameter is determined for each of.

Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.
The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m
Average particle size = ΣX _i / m
(A) When carbon black is used as the pigment, the average primary particle size determined by the same method as the inorganic pigment and organic pigment described above is preferably 10 to 80 nm, and more preferably 20 to 50 nm from the viewpoint of developability. is there. The DBP oil absorption (JIS K6221) is preferably 40 to 100 cc / 100 g, and more preferably 50 to 80 cc / 100 g from the viewpoint of dispersibility and developability. Nitrogen adsorption specific surface area (JIS K6217) is preferably 50~120m ² / g, more preferably from the viewpoint of dispersion stability is 60~95m ² / g.

  In the case of carbon black, the particle shape is different from organic pigments, etc., primary particles exist in a state called a fused structure like a skewer, and fine pores may be formed on the particle surface by post treatment. is there. Therefore, in order to represent the particle shape of carbon black, generally, in addition to the average particle diameter of primary particles obtained by the same method as the organic pigment, DBP absorption (JIS K6221) and nitrogen adsorption specific surface area (JIS K6217) Is used as an index of structure and pore volume.

In the colored resin composition of the present invention, the content ratio of the pigment (A) is usually 1% by weight or more, preferably 5% by weight or more, and usually 80% by weight or less, preferably 70% by weight in the total solid content. It is as follows.
(A) If the ratio of the pigment is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control and the like when forming a liquid crystal cell. On the other hand, if the proportion of the (A) pigment is too large, sufficient image formability may not be obtained.

In addition, it is also preferable to prepare (A) pigment content in the colored resin composition which forms this for every pixel of the color filter mentioned later in the optimal range. For example, when forming red, green, and blue pixels generally provided in a color filter, those containing 5 to 60% by weight, more preferably 10 to 50% by weight of the total solid content are preferable.
In the case of the resin black matrix, the black colored resin composition preferably includes a pigment containing 20 to 80% by weight, more preferably 30 to 70% by weight of the total solid content.

<(B) polymer>
In the chromatograph obtained by gel permeation chromatography (GPC) of the polymer (B) used in the colored resin composition of the present invention, the area of the component having a polystyrene-reduced weight average molecular weight (Mw) of 5000 or less is included. The total area excluding the peak areas of the unreacted monomer and the polymerization solvent is 20% or less, and the others are not particularly limited.

  The total area excluding the peak area of the unreacted monomer and the polymerization solvent referred to here is specifically the chromatograph obtained by the GPC measured with the apparatus being completely stable before the rise of the high molecular weight. From the area enclosed by the line (straight line) and the graph (curve) drawn by connecting the point where the base line of the low molecular weight side was returned to the original baseline, It means the area excluding the area of the polystyrene equivalent weight average molecular weight (Mw) of 300 or less.

  It is preferable that the area of the component having an Mw of 5000 or less is 20% or less because the dispersion stability of the pigment is improved, the solubility in an alkali developer is excellent, and the pattern shape after firing becomes a forward taper. Further, when the color filter pixel is formed by photolithography using the colored resin composition, the problem of local discoloration of the pixel due to moisture contained in the developer, that is, the developer stain Can also be suppressed. The area of the component having Mw of 5000 or less is preferably 15% or less, more preferably 10% or less. In order to improve pigment dispersion stability, the area of the component having Mw of 8000 or less is more preferably 35% or less, and particularly preferably 30% or less.

  (B) The acid value of the polymer varies depending on the type of the polymer (B), but is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, most preferably 300 mgKOH / g or less, and preferably 1 mgKOH / g or more, 5 mgKOH / g or more is more preferable. If the acid value is too high, the viscosity tends to be high and the synthesis tends to be difficult. If it is too low, for example, the adhesion to the substrate may be lowered or it may be difficult to apply to alkali development.

As described later, the colored resin composition of the present invention is prepared in advance using a polymer (B) as described above, and the pigment dispersion is mixed with other components as necessary. The preparation is preferable because a large amount of the pigment (A) can be efficiently dispersed with a relatively small amount of the (D) dispersant described later. In addition, the further description regarding the weight ratio of the (A) pigment with respect to (D) a dispersing agent is mentioned later.

  The polymer (B) used in the colored resin composition of the present invention may be a synthetic polymer or a natural polymer, or a derivative or modified product thereof. For example, synthetic polymers such as polyolefins, vinyl polymers, diene polymers, polyamides, polyesters, polyurethanes, polyethers, polysulfides, polyimides, phenol resins, amino resins, unsaturated polyester resins, epoxy resins, silicone resins, etc. Examples of the natural polymer include cellulose resins and polypeptides.

  More specifically, as synthetic polymers, for example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000- A polymer compound having a structure described in JP-A-56118, JP-A-2003-233179, or the like can be used, and among them, a polymer containing at least one kind of vinyl monomer is preferable.

  Examples of the vinyl monomers include (meth) acrylic monomers, (meth) acrylamide and its derivative monomers, vinyl ether monomers, nitrile monomers such as (meth) acrylonitrile, vinyl halides such as vinyl chloride, acetic acid Allyl monomers such as allyl; dicarboxylic acids such as maleic acid and its esters, itaconic acid and its salts and esters and their ester derivatives, vinyl silyl monomers, vinyl monomers such as isopropenyl acetate, etc. are limited thereto. However, other known vinyl monomers may be used.

Further, the polymer is preferably a polymer of at least one or more types of hydrophobic group-containing vinyl monomers and at least one or more types of hydrophilic group-containing vinyl monomers.
<Monomer having a hydrophobic group>
Examples of the hydrophobic group include a group derived from an aliphatic hydrocarbon and a group derived from an aromatic hydrocarbon. Here, the aliphatic hydrocarbon is saturated or unsaturated, and may be linear, branched or cyclic. In these aliphatic hydrocarbons and aromatic hydrocarbons, one or more hydrogen atoms may be substituted with halogen atoms such as fluorine, bromine, iodine and chlorine. Furthermore, in the aromatic hydrocarbon, one or more hydrogen atoms may be substituted with an aliphatic hydrocarbon group.

Examples of such a monomer containing a hydrophobic group include, but are not limited to, the monomer structural unit having a conventionally known hydrophobic group. Specifically, olefins such as ethylene, propylene, 1-butene, isobutene; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate Acrylic acid esters such as t-butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacryl I-propyl acid, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, Methacrylic acid esters such as tricyclodecanyl crylate; styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, ot-butoxystyrene, mt-butoxystyrene, pt-butoxystyrene Styrenes such as o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether,
i-propyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether,
Examples include, but are not limited to, vinyl ethers such as benzyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride;

Among them, the hydrophobic group-containing vinyl monomer is preferably a monomer having a cyclic structure in its structure, and more preferably benzyl methacrylate or cyclohexyl methacrylate.
<Monomer having hydrophilic group>
Examples of the hydrophilic group include a nonionic hydrophilic group, a cationic hydrophilic group, and an anionic hydrophilic group. As described later, when used in the production of a color filter, developability and adhesion to a substrate. From the viewpoints of properties (affinity), nonionic hydrophilic monomers or anionic hydrophilic monomers are preferable, and anionic hydrophilic monomers are more preferable. Examples of such a monomer containing a hydrophilic group include the following, but are not limited thereto, and any monomer having a conventionally known hydrophilic group may be used.

<Nonionic hydrophilic monomer>
N-vinyl-2-pyrrolidone, N-vinyloxazolidone, N-vinyl-5-methyloxazolidone, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate , 2-N-pyrrolidoneethyl (meth) acrylate, N- (meth) acryloylpiperidine, N-
(Meth) acryloylpyrrolidine N-vinyl lactam containing a cyclic group having 4 to 9 carbon atoms, vinyl alcohol, caprolactone-modified hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, methallyl alcohol Cole, glycerol monoallyl ether, (meth) acrylamide, C1-6N-alkyl or C1-3N, N-dialkyl (meth) acrylamide, diacetone (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) ) Acrylamide, N-2-hydroxyethylacrylamide, N, N-diethanolacrylamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N -Methyl-N-vinylformamide, p-hydroxymethylstyrene, p- (2-hydroxyethyl) styrene, p- (2-hydroxyethyloxycarbonyl) styrene, a ring-opening structure of alkylene oxide having 2 to 5 carbon atoms, etc. Can be mentioned.

<Anionic hydrophilic monomer>
Examples of the anionic monomer structure include the following monomer structures, but are not limited to these and may be conventionally known anionic monomer structures.
(Meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl maleic acid 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- ( (Meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyl Adipic acid, 2- (meta Vinyl monomers such as acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; ε-caprolactone, β-propiolactone, γ-butyrolactone in acrylic acid Monomers obtained by adding lactones such as δ-valerolactone; monomers obtained by adding acid or anhydride such as succinic acid, maleic acid, phthalic acid, or anhydride thereof to hydroxyalkyl (meth) acrylate Carboxyl group-containing monomers such as vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, styrene sulfonic acid, 2-acrylamide ethane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide ethane sulfonic acid , 2-metac Luamido-2-methylpropanesulfonic acid, 2-acryloyloxyethanesulfonic acid, 3-acryloyloxypropanesulfonic acid, 4-acryloyloxybutanesulfonic acid, 2-methacryloyloxyethanesulfonic acid, 3-methacryloyloxypropanesulfonic acid, 4 -Sulphonic acid monomers such as methacryloyloxybutanesulfonic acid, vinylphosphonic acid, methacryloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxy Phosphoric monomer types such as ethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate, etc. Examples of such a structure include metal salts such as alkali metals and alkaline earth metals, and ammonium salts.

Among these, as the monomer having a hydrophilic group, a carboxyl group-containing monomer is preferable, and (meth) acrylic acid is particularly preferable.
<Polymer structure>
(B) The primary structure of the polymer is not limited, and specific examples include random polymer, diblock polymer, triblock or higher multiblock polymer, gradient polymer, graft polymer, star polymer, etc. It is not limited to the structure.

<Specific examples of polymer>
(B) Particularly preferred as the polymer is, for example,
(B-1) An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer with respect to the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer. Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction,
(B-2) a linear alkali-soluble resin containing a carboxyl group in the main chain,
(B-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin of (B-2) above,
(B-4) (meth) acrylic resin,
(B-5) An epoxy (meth) acrylate resin having a carboxyl group can be used. Hereinafter, these resins will be described.

In the following description, the method for producing each resin is described by taking an example of general radical polymerization. However, as the polymer (B) of the present invention, the low molecular weight component of the resin thus obtained is used. It may be removed by various methods described below, and a copolymer having a low low molecular weight component may be produced by a living radical polymerization method described later.
<(B-1) An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer with respect to the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer. Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction (hereinafter sometimes referred to as (B-1) resin)>
In the colored resin composition of the present invention, as one of the preferred (B) polymers, “the epoxy contained in the copolymer with respect to the copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer” Examples thereof include a resin obtained by adding an unsaturated monobasic acid to at least a part of a group, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group generated by the addition reaction. Among these, as a particularly preferred (B-1) resin, “the copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer is used. Obtained by adding a polybasic acid anhydride to a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of an epoxy group of a polymer, or to 10 to 100 mol% of a hydroxyl group generated by the addition reaction. Alkali-soluble resin ”.

  Examples of the “epoxy group-containing (meth) acrylate” constituting the (B-1) resin include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl. Examples thereof include (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  As the “other radical polymerizable monomer” to be copolymerized with the epoxy group-containing (meth) acrylate, mono (meth) acrylate having a structure represented by the following general formula (1) is preferable.

In formula (1), R ^{1 to} R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R ⁷ and R ⁸ may be linked to each other to form a ring.
In the formula (1), when R ⁷ and R ⁸ are connected to each other to form a ring structure, the formed ring structure is preferably an aliphatic ring, which may be saturated or unsaturated, The carbon number is preferably 5-6.

Especially, as a structure represented by General formula (1), the structure represented by following formula (1a), (1b), or (1c) is preferable.
(B) By introducing these structures into the polymer, when the colored resin composition of the present invention is used in a color filter or a liquid crystal display device, the heat resistance of the colored resin composition is improved, and the colored resin composition It is possible to increase the intensity of the pixels formed using the object.

  In addition, the mono (meth) acrylate which has a structure represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (1), various known ones can be used as long as the structure has the structure, and those represented by the following general formula (2) are particularly preferable. .

In the formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents the structure of the general formula (1).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (1) is “others”. Among the repeating units derived from the "radically polymerizable monomer", those containing 5 to 90 mol% are preferred, those containing 10 to 70 mol% are more preferred, and those containing 15 to 50 mol% are particularly preferred.

  The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (1) is not particularly limited. Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (meth) acrylic acid furyl, (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid-1 , 1,1-trifluoroe Chill, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as cumyl, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic acid amides such as N-di-iso-propylamide and (meth) acrylic acid anthracenylamide; Vinyl compounds such as anilic rilates, (meth) acryloylnitriles, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

  Among these “other radical polymerizable monomers”, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used to impart excellent heat resistance and strength to the colored resin composition. It is effective to do. In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol%. Some are preferred, and more preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Propylene glycol monoalkyl ether acetates; Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvent agents may be used alone or in combination of two or more.

The amount of these solvents used is usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

  Specific examples thereof include, for example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2. -Ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5 -Bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) ) Peroxydicarbonate, diiso Propyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like.

Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.
Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or the monomer added with the radical polymerization initiator is heated, You may carry out by dripping in the stirred solvent. Alternatively, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

  In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer includes 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and other radicals. What consists of 10-95 mol% of repeating units derived from a polymerizable monomer is preferable, what consists of the former 20-80 mol% and the latter 80-20 mol% is still more preferable, The former 30-70 mol% The latter is particularly preferably composed of 70 to 30 mol%.

If the amount of the epoxy group-containing (meth) acrylate is too small, the addition amount of the polymerizable component and the alkali-soluble component described later may be insufficient, while the amount of the epoxy group-containing (meth) acrylate is too large and other radicals. When there are too few polymerizable monomers, heat resistance and intensity | strength may become inadequate.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer. ).

As the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together. By adding such a component, it is possible to impart polymerizability to the polymer (B) used in the colored resin composition of the present invention.

  These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of unsaturated monobasic acid is too small, there is a concern about the adverse effects of the remaining epoxy groups on the temporal stability of the colored resin composition. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the polymer used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. If the addition ratio is too large, the remaining film ratio during development may decrease, and if it is too small, the solubility may be insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be.
Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups.

Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries Denacol EX-171 "," Denacol EX-192 "and the like.

As for the structure of such a resin, for example, JP-A-8-297366 and JP-A-2
001-89533.
The acid value of (B-1) resin in this invention is 10-200 mgKOH / g normally, Preferably it is 15-150 mgKOH / g, More preferably, it is 25-100 mgKOH / g. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.

<(B-2) Linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as (B-2) resin)>
(B-2) The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and is usually obtained by polymerizing a polymerizable monomer containing a carboxyl group. It is done.

  Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl adipic acid. 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- ( (Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutyl Succinic acid, 2- (me ) Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; -Monomers obtained by adding lactones such as caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or anhydrides thereof And monomers added with acids or anhydrides. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
Moreover, (B-2) resin may copolymerize the other polymerizable monomer which does not have a carboxyl group with said carboxyl group-containing polymerizable monomer.
Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (Meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobonyl (meth) acrylate (Meth) acrylic acid esters such as adamantyl (meth) acrylate; vinyl aromatics such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylmaleimide, N-phenylmaleimide, N-benzyl N-substituted maleimides such as maleimide; macros such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer And monomers. These may be used in combination.

Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth)
Acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecanyl ( (Meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide.

  The (B-2) resin used in the present invention may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. It is done. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

  Specific examples of the (B-2) resin that can be used in the colored resin composition of the present invention include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, Polymeric monomers not containing hydroxyl groups such as isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Of (meth) acrylic acid and methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. )acrylic Copolymer of ester; Copolymer of (meth) acrylic acid and styrene; Copolymer of (meth) acrylic acid, styrene and α-methylstyrene; Copolymerization of (meth) acrylic acid and cyclohexylmaleimide Examples include coalescence. From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.

The acid value of (B-2) resin in this invention is 30-500 mgKOH / g normally, Preferably it is 40-350 mgKOH / g, More preferably, it is 50-300 mgKOH / g.
<A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (B-3) (B-2) (hereinafter sometimes referred to as (B-3) resin)>
A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the (B-2) linear alkali-soluble resin containing a carboxyl group in the main chain is also particularly preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.

  For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- An acyclic epoxy group-containing unsaturated compound such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoint of heat resistance and the dispersibility of the pigment (A) described later, an alicyclic epoxy group-containing unsaturated compound. Saturated compounds are preferred.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and suitable alicyclic epoxy group-containing unsaturated compounds are represented by the following general formulas (3a) to (3m). And the compounds represented.

In formulas (3a) to (3m), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n is an integer of 1 to 10.
In general formulas (3a) to (3m), the alkylene group for R ¹² preferably has 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable. As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
A known technique can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (B-2). For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride. A quaternary ammonium salt such as pyridine, triphenylphosphine, etc., in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours to react with the carboxyl group of the resin. Saturated compounds can be introduced.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g.
<(B-4) (Meth) acrylic resin (hereinafter may be referred to as (B-4) resin)>
The (meth) acrylic resin refers to a polymer (B-4) obtained by polymerizing (meth) acrylic acid and / or (meth) acrylic ester as monomer components. As a preferable (meth) acrylic resin, for example, a polymer (B-4a) obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate, and the following general formula (4) and / or ( And a polymer (B-4b) obtained by polymerizing a monomer component essentially comprising the compound represented by 5).

In formula (4), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (5), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (6). Or an adamantyl group which may be substituted. L ³ may be bonded to R ^3b or R ^4b in the following formula (6) to form a ring.

In formula (6), R ^2b , R ^3b and R ^4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group or an organic group, and L ¹ and L ² represent a divalent linking group. , L ¹ , L ² and L ³ in the above formula (5) may be bonded to each other to form a ring.
<(B-4a) A polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate (hereinafter sometimes referred to as (B-4a) resin)>
A polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate is preferably used in terms of high affinity with the pigment.

  The proportion of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (meth) acrylic acid in the total monomer component is usually 10 to 90% by weight, preferably 15 to 80% by weight. More preferably, it is 20 to 70% by weight. Moreover, benzyl (meth) acrylate is 5 to 90 weight% normally in all the monomer components, Preferably it is 15 to 80 weight%, More preferably, it is 20 to 70 weight%. If the amount of (meth) acrylic acid is too large, the surface of the coating film tends to be roughened during development, and if it is too small, development may be impossible. Further, if the amount of benzyl (meth) acrylate is too much or too little, dispersion tends to be difficult.

<(B-4b) A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (4) and / or (5) (hereinafter sometimes referred to as (B-4b) resin)>
First, the compound of General formula (4) is demonstrated.
In the ether dimer represented by the general formula (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like.

  Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.

These ether dimers may be used alone or in combination of two or more.
The proportion of the ether dimer in the monomer component when obtaining the (B-4) acrylic resin is not particularly limited, but is generally 2 to 60% by weight, preferably 5 to 55% by weight, in all monomer components. More preferably, it is 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, transparency, heat resistance, etc. The coating film performance may be insufficient.

Then, the compound of General formula (5) is demonstrated.
In general formula (5), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
In the general formula (6), the organic groups represented by R ^2b , R ^3b , and R ^4b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, or an acyl group. Carboxyl group or acyloxy group, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkenyl group having 3 to 18 carbon atoms. Group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, and more preferably. Is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents among R ^2b , R ^3b , and R ^4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
L ¹ and L ² are not particularly limited as long as they are divalent linking groups and L ³ is a divalent linking group or a direct bond, but at least either L ¹ or L ² is a linking group having 1 or more carbon atoms. Is preferred. L ¹ , L ² , and L ³ are each independently a direct bond, alkylene having 1 to 15 carbons, —O—, —S—, —C (═O) —, or alkenylene having 1 to 15 carbons. , Phenylene, or combinations thereof are preferred.

As a preferable combination of L ¹ , L ² and L ³ , L ³ is a direct bond, alkylene having 1 to 5 carbon atoms, or a ring formed by combining with R ^3b or R ^4b, and L ¹ and L ² are C1-C5 alkylene.
Moreover, as a preferable thing of General formula (6), the compound represented by following General formula (7) can be mentioned.

In the formula (7), R ^2b , R ^3b , R ^4b , L ¹ and L ² have the same meaning as in the formula (6), and R ^5b and R ^6b each independently represent a hydrogen atom, a hydroxyl group, or a halogen atom. Represents an amino group or an organic group.
In the general formula (7), the organic groups represented by R ^5b and R ^6b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, or An acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and 1 carbon atom. -15 alkoxy group, C1-C15 alkylthio group, C1-C15 acyl group, C1-carboxyl group, or C1-C15 acyloxy group, more preferably C1-C15. Or an alkyl group having 10 to 10 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents among R ^5b and R ^6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, the alkyl group of R ^1b , each organic group of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ , and the adamantyl group of X are each independently substituted with a substituent. You may have, specifically,
For example, the following substituents can be mentioned.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group and t-octyl group; carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as a xyl group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms such as t-octylthio group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; carbon such as benzyl group and phenethyl group Aralkyl group having 7 to 18 carbon atoms; straight chain or branched chain having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group Alkenyloxy group; represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group An acyloxy group represented by —NR ¹⁹ R ²⁰ ; an acylamino group represented by —NHCOR ²¹ ; a carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; Carboxylic acid ester group represented by ²⁵ ; sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group , Oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide A saturated or unsaturated heterocyclic group such as a side group; a trialkylsilyl group such as a trimethylsilyl group;

R ^{17 to} R ²⁸ are each independently a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl that may have a substituent. Or an aralkyl group which may have a substituent.
Moreover, the positional relationship of the said substituent is not specifically limited, When it has a some substituent, it may be same or different.

  Specific examples of the compound represented by the general formula (5) include the following.

  In the monomer component constituting the polymer of (B-4b) according to the present invention, the ratio of the general formula (5) is not particularly limited, but is usually 0.5 to 60% by weight, preferably 1 in the total monomer components. It is -55 weight%, More preferably, it is 5-50 weight%. If the amount is too large, the dispersion stability of the pigment dispersion may be lowered when used as a dispersant. On the other hand, if the amount is too small, the stain resistance may be lowered.

The (B-4) (meth) acrylic resin in the present invention preferably has an acid group, including the polymers (B-4a) and (B-4b). By having an acid group, the resulting colored resin composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter sometimes abbreviated as acid-epoxy curing). A colored resin composition, or a composition in which an uncured portion can be visualized with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups contained in one molecule of resin may be only one kind or two or more kinds.

  (B-4) In order to introduce an acid group into a (meth) acrylic resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter “to introduce an acid group”) May be used as a monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

Only one type of monomer for introducing these acid groups may be used, or two or more types may be used.
(B-4) When the monomer component for obtaining the (meth) acrylic resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but usually 5 to 5 in all the monomer components. 70% by weight, preferably 10 to 60% by weight. By adjusting the amount of the monomer for introducing the acid group within this range, good electrical characteristics and developability can be obtained.

Moreover, (B-4) (meth) acrylic-type resin may have a radically polymerizable double bond.
In order to introduce a radical polymerizable double bond into the (B-4) (meth) acrylic resin, for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “radical polymerizable double bond”). May be referred to as a “monomer for introducing a radical.”) After polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

  When the monomer component in obtaining the (meth) acrylic resin of (B-4) also contains a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, but usually all It is 5-70 weight% in a monomer component, Preferably it is 10-60 weight%. By adjusting the amount of the monomer for introducing the radical polymerizable double bond within this range, good plate making characteristics can be obtained, and a pixel having a desired taper angle with little chipping can be obtained.

When the (B-4) (meth) acrylic resin according to the present invention is a polymer having the compound of the general formula (4) described in (B-4a) as an essential monomer component, it has an epoxy group. It is preferable.
In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types.
In the case where the monomer component for obtaining the (meth) acrylic resin of (B-4) also contains the monomer for introducing the epoxy group, the content ratio is not particularly limited. It should be ˜70% by weight, preferably 10 to 60% by weight. By adjusting the amount of the monomer for introducing the epoxy group within this range, the heat resistance and the like can be improved without deteriorating exposure sensitivity and color characteristics.

The monomer component for obtaining the (meth) acrylic resin (B-4) may contain other copolymerizable monomers, if necessary, in addition to the essential monomer component.
Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.

  Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more. When the monomer component for obtaining the (B-4) (meth) acrylic resin also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, 85 More preferably, it is less than wt%. When there is too much content rate, developability may deteriorate.

Next, the manufacturing method (polymerization method) of (B-4) (meth) acrylic resin is demonstrated.
There is no particular limitation on the method for polymerizing the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used and the target polymer. Varies with molecular weight. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. Regarding the polymerization concentration, the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.

  Moreover, what is necessary is just to use the solvent used by normal radical polymerization reaction when using a solvent at the time of superposition | polymerization. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide and the like Is mentioned. These solvents may be used alone or in combination of two or more.

  When the monomer component is polymerized, a polymerization initiator may be used as necessary. Although there is no restriction | limiting in particular in a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.

The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand without gelation. It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on all monomer components, in that tens of thousands of polymers can be obtained.
Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but it is a weight average without gelation. It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on all monomer components, in that a polymer having a molecular weight of several thousand to several tens of thousands can be obtained.

In addition, when using the compound of General formula (4) as an essential monomer component, in the said polymerization reaction, it is thought that the cyclization reaction of an ether dimer advances simultaneously, The cyclization rate of the ether dimer at this time Is not necessarily 100 mol%.
When obtaining the acrylic resin, when an acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component, it is necessary to perform a treatment for imparting the acid group after polymerization. The treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An acid anhydride such as a product may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When the radical polymerizable double bond is introduced by using the monomer capable of imparting the radical polymerizable double bond described above as the monomer component when the (meth) acrylic resin of (B-4) is obtained, It is necessary to perform a treatment for imparting a radically polymerizable double bond after the polymerization.
The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, ) A compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.

When the said (meth) acrylic-type resin has an acid group, a preferable acid value is 30-500 mgKOH / g, More preferably, it is 50-400 mgKOH / g. When the acid value is less than 30 mgKOH / g, it may be difficult to apply to alkali development, and when it exceeds 500 mgKOH / g, the viscosity tends to be too high to form a coating film.
Among the (meth) acrylic resin components, polymers having a compound represented by the general formula (4) as an essential monomer component are disclosed in, for example, JP-A-2004-300203 and JP-A-2004-300204. The compounds described can be mentioned.

<(B-5) Epoxy Acrylate Resin Having Carboxyl Group (hereinafter, may be referred to as (B-5) resin)>
(B-5) The epoxy acrylate resin is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester portion to the epoxy resin, and further adding a polybasic acid anhydride. It is synthesized by reacting the product. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Japan Epoxy Resin Co., Ltd.), Epoxy resin obtained by reaction of alcoholic hydroxyl group and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, manufactured by Japan Epoxy Resin Co., Ltd.) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc."), epoxy resins obtained by reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example, Nippon Kayaku) “NE” -7406 "(epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Japan Epoxy Resin), phenol novolac type epoxy resin (for example, Nippon Kayaku) “EPPN-201” manufactured by Yakuhin, “EP-152”, “EP-154” manufactured by Japan Epoxy Resin, “DEN-438” manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolak Type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), trisphenol Methane type epoxy resin (for example, “EPPN-501”, “EP” manufactured by Nippon Kayaku Co., Ltd.) -502 "," EPPN-503 "), fluorene epoxy resin (for example, cardo epoxy resin" ESF-300 "manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (" Celoxide 2021P "manufactured by Daicel Chemical Industries, Ltd.) , “Celoxide EHPE”), dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA” manufactured by Dainippon Ink & Chemicals, Inc. -7200 "," NC-3000 "," NC-7300 "manufactured by Nippon Kayaku Co., Ltd.), and an epoxy resin represented by the following structural formula (see JP-A-4-355450), etc. are preferably used. it can.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymer type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and one other than these. Functional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerol mono (meth) acrylate, the following general formula (8 From the compound represented by One or more barrels are reacted city include a copolymer obtained by.

In formula (8), R ⁶¹ represents hydrogen or an ethyl group, R ⁶² represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10.
Examples of the compound of the general formula (8) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; methoxydiethylene glycol mono ( Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight based on the second component of the copolymerization type epoxy resin. % By weight or less, particularly preferably 50% by weight or less.
As such a copolymerization type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.
The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  The addition reaction of an α, β-unsaturated monocarboxylic acid or ester thereof with an epoxy resin can be carried out by using a known method, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. can do. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and the reaction can be carried out by continuing the reaction under the same conditions as in the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably in the range of 20 to 140 mgKOH / g. If the acid value of the resin is too small, the alkali developability is poor, and if the acid value of the resin is too large, the curing performance tends to be inferior.

In addition, as the (B-5) epoxy acrylate resin having a carboxyl group, for example, a naphthalene-containing resin described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331, Examples include fluorene-containing resins described in JP-A-2001-354735; resins described in JP-A-2005-126684, JP-A-2005-55814, JP-A-2004-295084, and the like.

Moreover, (B-5) epoxy acrylate resin which has a commercially available carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item.
As the polymer, for example, an acrylic polymer described in JP-A-2005-154708 can also be used.

  As the polymer (B) in the colored resin composition of the present invention, more preferably (B-2) a linear alkali-soluble resin containing a carboxyl group in the main chain, and (B-4) a (meth) acrylic resin Yes, among (B-4) (meth) acrylic resins, a polymer obtained by polymerizing a monomer component essentially containing the compound represented by the general formula (4) is preferable. Particularly preferred is (B-2) a linear alkali-soluble resin containing a carboxyl group in the main chain.

<(B) Polymer Synthesis Method>
As a method for synthesizing the polymer of the vinyl monomer as described above, for example, a known polymerization method such as radical polymerization, living radical polymerization, anion polymerization, living anion polymerization, living cation polymerization, group transfer polymerization method, etc. can be selected. Moreover, the derivative | guide_body and modified body of the polymer synthesize | combined with these well-known polymerization methods may be sufficient. Among these, the radical polymerization method and the living radical polymerization method are preferable because the synthesis method is simple. Among the living radical polymerization methods, the atom transfer radical polymerization method (ATRP method) is preferable because the molecular weight can be easily controlled.

<Synthesis of (B) polymer by radical polymerization method>
The polymer can be synthesized by radical polymerization without solvent or in the presence of a solvent, but a known solution polymerization method is preferred. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.

  Specific examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, butyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyls such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate. Ether acetates; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether; acetates such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, butyl carbitol, etc. Diethylene glycol dialkyl ethers; triethylene glycol Dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane, tetrahydrofuran, propylene glycol monomethyl ether, diethyl ether, diphenyl ether, anisole, dimethoxybenzene; acetonitrile, propionitrile, Nitriles such as benzonitrile; Carbonyl compounds such as ethylene carbonate and propylene carbonate; Alcohols such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol and isoamyl alcohol; Chlorobenzene, methylene chloride, chloroform and chlorobenzene , Halogenated hydrocarbons such as carbon tetrachloride; acetone, methyl ethyl keto , Ketones such as methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; methyl lactate and ethyl lactate And lactic acid esters such as butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more. The amount of these solvents used is usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, relative to 100 parts by weight of the copolymer obtained. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.

  The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxide Oxydicarbonate, diisopropyl -Oxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned. Examples of the azo compound catalyst include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobiscyclohexane 1-carbonitrile, 2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobis (2-methylpropionate), 1 , 1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride Salt, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2- Imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamide], 2,2′-azobis {2- [1 -(2-hydroxyethyl) -2-imidazolin-2-yl) propane} dihydrochloride, 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'- Azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}, 2,2′-azobis [2- (5-methyl-imidazolin-2-yl) propane] dihydrochloride, 2, 2'-azobis [2- (3,4,5,6, -tetrahydropyrimidin-2-yl) propane] dihydrochloride and the like. Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

<Additives such as chain transfer agents>
In the radical polymerization reaction, in addition to the above polymerization initiator, known materials such as a chain transfer agent, a chain terminator, and a polymerization accelerator can be added and used in order to adjust the resulting polymer to a preferred molecular weight.
As the chain transfer agent, mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercapto Nicotinic acid, 3- [N (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol-2-mercaptoethylamine, 2-mercaptoimidazole, -Mercapto-3-pyridinol, 4- (2-mercaptoethyloxycarbonyl) phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2-mercaptoethylphosphonoic acid monomethyl ester, etc.), or the above polar group or substituent Examples thereof include iodinated alkyl compounds (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

<Polymer synthesis by living radical polymerization method>
The atom transfer type radical polymerization method is one of the living radical polymerization methods, and is a particularly preferable polymerization method as the (B) polymer production method of the present invention. Generally, it is represented by the following diagram.

(In the above diagram, P is a polymer or initiator, M is a transition metal, Q ¹ and Q ² are halogen atoms, L is a ligand capable of coordinating to M, and s and s + 1 are valences of the transition metal. The low valence complex [1] and the high valence complex [2] constitute a redox conjugated system.)
First, the low-valence complex [1] radically extracts the halogen atom Q ¹ from the halogen-containing polymerization initiator PQ ¹ to form the high-valence complex [2] and the carbon-centered radical P. . The rate of this reaction is expressed as Kact. This radical P • reacts with the monomer as shown to form the same kind of intermediate radical species P •. In addition, this reaction rate is represented by Kpropagion.

The reaction between the high valence complex [2] and the radical P • produces the product PQ ¹ and at the same time regenerates the low valence complex [1]. The rate of this reaction is expressed as Kdeact. Then, low valent complex [1] to advance a new reaction further reacts with P-Q ^1. In this reaction, it is most important in controlling the polymerization to suppress the concentration of the growing radical species P · to be low.

The transition metal M used in the atom transfer radical polymerization method is not particularly limited, but at least one transition metal selected from Groups 7 to 11 of the periodic table is preferable.
In the redox catalyst (redox conjugated complex), the low valence complex [1] and the high valence complex [2] reversibly change as shown in the above-described diagram. Specific examples of the low-valent metal (M) ^s include Cu ⁺ , Ni ⁹ , Ni ⁺ , Ni ²⁺ , Pd ⁹ , Pd ⁺ , Pt ⁹ , Pt ⁺ , Pt ²⁺ , Rh ⁺ , Rh ²⁺ , ^{Rh 3+, Co +, Co 2+} , Ir 9, Ir +, Ir 2+, Ir 3+, Fe 2+, Ru 2+, Ru 3+, Ru 4+, Ru 5+, Os 2+, Os 3+, Re 2+, Re 3+, Re 4+ , Re ⁶⁺ , Mn ²⁺ , Mn ³⁺ , among which Cu ⁺ , Ru ²⁺ , Fe ²⁺ and Ni ²⁺ are preferable, and Cu ⁺ is particularly preferable. Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide and the like.

As the ligand L, an organic ligand is generally used. Specific examples include 2,2′-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, triphenylphosphine, and tributylphosphine. In particular, aliphatic polyamines such as pentamethyldiethylenetriamine and tris (dimethylaminoethyl) amine are preferred.

<Initiator of ATRP method>
The polymerization initiator is an organic halide or sulfonyl halide compound containing a bromine atom or an iodine atom. The compound is not particularly limited as long as it is a compound having at least one bromine atom or iodine atom that serves as a polymerization initiation point (also referred to as polymerization initiation terminal or initiation terminal), but usually serves as the initiation point. Compounds having one or two bromine atoms or iodine atoms, and compounds represented by the following general formulas (V1) to (V19) are preferable. However, in the general formulas (V1) to (V19), C ₆ H ₅ is a phenyl group, C ₆ H ₄ is a phenylene group, R ⁹¹ and R ⁹² are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group. Or it is an aralkyl group, and may have a functional group such as an alcoholic hydroxyl group, an amino group, a carboxyl group, or an alkylthio group on each carbon atom, and may be the same or different. Y represents chlorine, bromine or iodine, and J represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group. The alkyl group, alkenyl group, aryl group or aralkyl group in J preferably has 1 to 20 carbon atoms, and may be linear, branched or cyclic, and the carbon atom has a substituent. Also good. i is an integer of 0-20.

(One polymerization initiator starting _{point) :( V1) C 6 H 5} -CH 2 Y (V2) C 6 H 5 C (H) (
_{Y) CH 3 (V3) C} 6 H 5 -C (Y) (CH 3) 2 (V4) R 91 -C (H) (Y) -CO 2 R 92 (V5) R 91 -C (CH 3) (Y) -CO ₂ R ⁹² (V6) R ⁹¹ —C (H) (Y) —C (O) R ⁹² (V7) R ⁹¹ —C (CH ₃ ) (Y) —C (O) R ⁹² ( V8) ^{R 9
1} -C ₆ H ₄ -SO ₂ Y
(Starting point two polymerization initiators) :( V9) o-, m-, p-YCH 2 -C 6 H 4 -CH 2 Y (V10) o-, m-, p-CH 3 C (H) _{(Y) -C 6 H 4 -C} (H) (Y) CH 3 (V11) o-, m-, p- (CH 3) 2 C (Y) -C 6 H 4 -C (Y) (CH _{3) 2 (V12) JO 2} C-C (H) (Y) - (CH 2) i -C (H) (Y) -CO 2 J (V13) JO 2 C-C (CH 3) (Y) _{- (CH 2) i -C (} CH 3) (Y) -CO 2 J (V14) JC (O) -C (H) (Y) - (CH 2) i -C (H) (Y) -C (O) J (V15) JC (O) -C (CH 3) (Y) - (CH 2) i -C (CH 3) (Y) -C (O) J (V16) YCH 2 CO 2 - ( _{CH 2) i -OCOCH 2 Y (} V17) CH 3 C (H) (Y) CO 2 - (CH 2) _i- OC
OC (H) (Y) CH 3 (V18) (CH 3) 2 C (Y) CO 2 - (CH 2) i -OCOC (
Y) (CH ₃ ) ₂ (V19) JC (O) CH (Y) ₂
Examples of the polymerization initiator represented by the general formula (V1) include phenylmethyl bromide and phenylmethyl iodide. Examples of the polymerization initiator represented by the general formula (V2) include 1-phenylethyl bromide and 1-phenylethyl. Examples of the polymerization initiator represented by the general formula (V3) such as iodide include 1-phenylisopropyl bromide and 1-phenylisopropyl iodide, and the polymerization initiator represented by the general formula (V4) includes 2- Bromopropionic acid, 2-iodopropionic acid, 2-bromobutanoic acid, 2-iodobutanoic acid, methyl-2-bromopropionate, ethyl-2-bromopropionate, methyl-2-iodopropionate, etc. Examples of the polymerization initiator represented by (V5) include 2-bromoisobutanoic acid, 2-iodoisobutanoic acid, and methyl-2-bromide. Examples of the initiator represented by the general formula (V6) such as isobutyrate, ethyl-2-bromoisobutyrate (Synthesis Example 1), methyl-2-iodoisobutyrate, ethyl-2-iodoisobutyrate, and the like include α Examples of the initiator represented by the general formula (V7) such as -bromoacetophenone and α-bromoacetone include α-bromoisopropylphenyl ketone, and the initiator represented by the general formula (V8) include p-toluenesulfonyl. Examples of the initiator represented by the general formula (V9) such as bromide include α, α′-dibromoxylene, α, α′-diiodoxylene and the like, and the initiator represented by the general formula (V10) includes bis ( Examples of the initiator represented by the general formula (V11) such as 1-bromoethyl) benzene include the initiator represented by the general formula (V12) such as bis (1-bromo-1-ethyl) benzene. Are dimethyl 2,5-dibromoadipate, dimethyl 2,5-diiododipinate, diethyl 2,5-dibromoadipate, diethyl 2,5-diiododipinate, 2,6-dibromo-1,7- Dimethyl heptanedioate, dimethyl 2,6-diiodo-1,7-heptanedioate, diethyl 2,6-dibromo-1,7-heptanedioate, diethyl 2,6-diiodo-1,7-heptanedioate, etc. As the initiator represented by the general formula (V13), as the initiator represented by the general formula (V14) such as dimethyl 2,6-dibromo-2,6-dimethyl-1,7-heptanedioate, etc. Initiators represented by the general formula (V15) such as 3,5-dibromo-2,6-heptanedione and the like include 3,5-dibromo-3,5-dimethyl-2,6-heptanedione and the like. Expressed by formula (V16) Examples of the initiator include an ethylene glycol bis (2-bromoacetic acid) ester and the like represented by the general formula (V17). Examples of the initiator include an ethylene glycol bis (2-bromopropionic acid) ester and the general formula (V18). Examples of the initiator represented include ethylene glycol bis (2-bromoisobutyric acid) ester, and examples of the initiator represented by the general formula (V19) include α, α-dibromoacetophenone.

As a solvent, the solvent quoted as the polymerization solvent used for the above-mentioned radical polymerization can be used similarly.
The amount of the solvent used is not particularly limited, but is usually 1 part by weight or more, preferably 100 parts by weight or more with respect to 100 parts by weight of the monomer, and the upper limit is usually 2000 parts by weight or less, preferably 1000 parts by weight or less. .

The amount of the low-valent metal (M) ^s used is not particularly limited, but the concentration in the polymerization reaction system is usually 10 ⁻⁶ mol / liter or more, preferably 10 ⁻⁵ mol / liter or more, and its upper limit is Usually, it is 10 ⁻¹ mol / liter or less. And it is 0.001 mol or more with respect to 1 mol of initiators, Preferably it is 0.005 mol or more, The upper limit is 100 mol or less normally, Preferably it is 50 mol or less.

The polymerization temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and the upper limit is 200 ° C. or lower, preferably 150 ° C. In the present invention, the polymerization proceeds in a living manner.
In the chromatograph obtained by gel permeation chromatography (GPC), the polymer thus obtained preferably has a polystyrene equivalent weight average molecular weight (Mw) of 7000 or more, more preferably 9000 or more. . Further, it is preferably 60000 or less, more preferably 50000 or less, and particularly preferably 40000 or less. If the molecular weight is less than 7000, the dispersibility may be inferior, and the proportion of the low molecular weight component is relatively large. Therefore, the polymer (B) is “polystyrene equivalent weight average molecular weight (Mw) of 5000 or less. It becomes difficult for the area of the component to be 20% or less with respect to the total area excluding the peak areas of the unreacted polymerizable monomer and the polymerization solvent. On the other hand, when it exceeds 60,000, the viscosity tends to be too high.

  Further, as a measure of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 or less and 1.0 or more, and 1.8 or less and 1.0 or more. Is more preferably 1.5 or less and 1.0 or more. When the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) exceeds 2, the polymer region becomes wide and the solubility in the developer tends to be lowered.

In order to control Mw within the above range, the ratio of the polymerization initiator and the monomer may be controlled as in the usual atom transfer polymerization method, and in order to make Mw / Mn within the above range, As in the atom transfer polymerization method, the amount of catalyst and reaction temperature may be controlled.
In a chromatograph obtained by gel permeation chromatography (GPC) of a polymer synthesized using the atom transfer polymerization method as described above, the area of a component having a polystyrene-equivalent weight average molecular weight (Mw) of 5000 or less is not yet determined. When the total area excluding the peak area of the reaction monomer and polymerization solvent is not less than 20%, low molecular weight components such as reprecipitation method, fractional reprecipitation method, ultrafiltration method and phase separation method are removed. Is possible.

As described above, the acid value of the polymer (B) in the present invention varies depending on the structure of each polymer, but is usually 1 mgKOH / g or more and 300 mgKOH / g or less.
<Method for removing low molecular weight components>
The polymer (B) of the present invention can be obtained by strictly controlling the molecular weight in the polymerization process as described above, but is obtained by removing the low molecular weight component from the polymer obtained by a conventional general polymerization method. You can also.

The method for removing the low molecular weight component is not particularly limited, and examples thereof include a reprecipitation method, a fractional reprecipitation method, an ultrafiltration membrane method, and a phase separation method. Among them, the reprecipitation method can remove low molecular weight components with a simple apparatus and in a short time, and since a desired polymer component can be obtained by changing the type and amount of good and poor solvents, preferable.
<Reprecipitation method and fractional reprecipitation method>
In the reprecipitation method, the polymer is dissolved in a solvent (good solvent) in which the polymer is uniformly dissolved, and the polymer solution is dropped into a solvent in which the polymer is insoluble and / or hardly soluble (poor solvent). By appropriately setting the amount of the good solvent and the poor solvent for the polymer, the low molecular weight component in the polymer is dissolved in the solvent, and the polymer component having a low content of the low molecular weight component is obtained as a precipitate.

  On the other hand, in the fractional reprecipitation method, the polymer is dissolved in a solvent (good solvent) in which the polymer is uniformly dissolved, and a solvent insoluble and / or hardly soluble in the polymer (poor solvent) is dropped into the polymer solution. By appropriately setting the amount of the good solvent and the poor solvent for the polymer, the low molecular weight component in the polymer is dissolved in the solvent, and the polymer component having a low content of the low molecular weight component is obtained as a precipitate.

  Using the reprecipitation method and the fractional reprecipitation method, the area of the component having a polystyrene equivalent weight average molecular weight (Mw) of 5000 or less is 20% or less with respect to the total area excluding the peak area of the unreacted monomer and the polymerization solvent. To obtain a polymer component precipitate using an appropriate good solvent and a poor solvent, GPC is measured. If the content of low molecular weight is large, the amount of good solvent that dissolves the polymer is determined. By increasing the amount and reducing the amount of the poor solvent, it is possible to obtain a polymer having a desired low molecular content.

<Ultrafiltration membrane method>
A polymer component having a specific molecular weight or less can be removed by dissolving the polymer in a solvent in which the polymer is uniformly dissolved and allowing the polymer to pass through the ultrafiltration membrane. As a material of the membrane module, an organic resin or an inorganic material such as ceramic can be used.
Using an ultrafiltration membrane method, the area of components having a polystyrene-equivalent weight average molecular weight (Mw) of 5000 or less is adjusted to 20% or less with respect to the total area excluding the peak areas of unreacted monomers and polymerization solvent. Therefore, depending on the polymer species and the solvent species, the dissolved state in the polymer solution, that is, the interaction between the polymer species and the solvent species results in different hydrodynamic behavior. After processing using an ultrafiltration membrane with a molecular weight, the GPC of the polymer component on the permeate side and the polymer component on the mother liquor side is measured. By selecting an ultrafiltration membrane having a fractional molecular weight, it is possible to obtain a polymer having a desired low molecular content.

<Phase separation method>
Polymer components with a specific molecular weight or less are removed by liquid-liquid phase separation of the polymer solution into a liquid phase (diluted phase) in which many low molecular weight substances are dissolved and a liquid phase (concentrated phase) in which many high molecular weight substances are dissolved. Is possible. Examples of the liquid-liquid phase separation include a method of lowering the temperature of the solution after dissolving the polymer in a θ (sheeter) solvent for the polymer, or adding a poor solvent after dissolving the polymer in a good solvent.

In order to adjust the area of the component having a polystyrene-equivalent weight average molecular weight (Mw) of 5000 or less to 20% or less with respect to the total area excluding the peak areas of the unreacted monomer and the polymerization solvent by using the phase separation method. After selecting the appropriate solvent and temperature and performing liquid-liquid phase separation, the GPC of both layers is measured, and if the polymer component on the dense phase side has a low molecular weight content, θ (sheeter) ) It is possible to obtain a polymer with a desired low molecular content by increasing the solvent, increasing the amount of good solvent, and decreasing the amount of poor solvent.

As the polymer (B) used in the colored resin composition of the present invention, one of the various resins described above may be used alone, or two or more may be used in combination.
In addition, the above-mentioned various resins are used in combination with the below-mentioned (D) dispersant and the like. The effect that a color pixel can be formed is obtained, which is preferable.

Specifically, the polymer (B) is used in the dispersion treatment step described later together with the solvent (C) and the dispersant (D) described later. At this time, the polymer (B) is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the pigment (A).
As described above, as the (B) polymer used in the dispersion treatment step, various resins described in the section of (B) polymer can be used, and in particular, (B-2) the main chain contains a carboxyl group. Linear alkali-soluble resins and (B-4) (meth) acrylic resins are preferred. (B-4) Among (meth) acrylic resins, a polymer obtained by polymerizing a monomer component essentially containing the compound represented by the general formula (4) is preferable. Most preferred as the polymer (B) used in the dispersion treatment step is (B-2) a linear alkali-soluble resin containing a carboxyl group in the main chain.

  In the colored resin composition of the present invention, the content of the (B) polymer is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably in the total solid content. 60% by weight or less. (B) When there is less content of a polymer than this range, a film | membrane becomes weak and the adhesiveness to a board | substrate may fall. On the other hand, when the amount is larger than this range, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

<(C) Solvent>
In addition to the (A) pigment and (B) polymer, the colored resin composition of the present invention dissolves or disperses the (A) pigment, (B) polymer and other components blended as necessary, and has a viscosity. In order to adjust, it is essential to contain (C) a solvent.
Specifically, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol- t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3- Methoxybutanol, triethylene Recall monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Glycerin triacetates such as triacetin;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol glycerol, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

  Examples of commercially available (C) solvents corresponding to the above include mineral spirits, Barsol # 2, Apco # 18 solvent, Apco thinner, and Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These (C) solvents may be used alone or in combination of two or more.

In the case of forming color filter pixels by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], the same applies to the boiling point hereinafter) is selected. Is preferred. More preferably, it has a boiling point of 120-170 ° C. By controlling the boiling point within this range, it can be prevented that traces of bubbles remain and become defects, or drying does not end within a predetermined time and color unevenness occurs in the pixels.
Glycol alkyl ether acetates are preferred from the viewpoints of good balance between the above-mentioned solvent (C), coating properties, surface tension and the like, and relatively high solubility of the constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5 wt% to 30 wt%, more preferably 5 wt% to 20 wt%.

  It is also preferable to use a solvent having a boiling point of 150 ° C. or higher. By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult for the pigment dispersions to break apart due to rapid drying. The content of the high boiling point solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight with respect to the solvent. If the amount of the high-boiling solvent is too small, for example, the pigment component may precipitate and solidify at the tip of the slit nozzle and cause foreign matter defects. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .
When forming a pixel of a color filter by the inkjet method, the boiling point of the solvent (C) is usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower. When the boiling point is too low, the uniformity of the resulting coating film tends to be poor. Conversely, if the boiling point is too high, as described later, the effect of inhibiting the drying of the colored resin composition is high, but there are many residual solvents in the coating film even after thermal firing, causing problems in quality, In some cases, the drying time in vacuum drying or the like becomes long, resulting in problems such as an increase in tact time.

The vapor pressure of the solvent (C) is usually 10 mmHg or less, more preferably 5 mmHg or less, and further preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.
In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by weight or more, more preferably 70% by weight or more in the total solvent contained in the pigment dispersion and / or the colored resin composition for color filters. 90% by weight or more is most preferable. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
Furthermore, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the pigment dispersion or the colored resin composition and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

On the other hand, when the (C) solvent contains alcohol, the ejection stability in the ink jet method may be deteriorated. Therefore, the alcohol is preferably 20% by weight or less in the total solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
The content of the (C) solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less. (C) When the solvent exceeds 99% by weight, the amount of (A) pigment, (D) dispersant, etc. is too small to form a coating film. On the other hand, the lower limit of the (C) solvent content is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more in consideration of viscosity suitable for coating.

<(D) Dispersant>
The colored resin composition of the present invention can contain (D) a dispersant in combination with the (B) polymer as long as the effects of the present invention are not impaired. (D) The type of the dispersant is not particularly limited as long as the effects of the present invention are not impaired. For example, (D-1) a graft copolymer containing a nitrogen atom,
(D-2) an acrylic block copolymer containing a nitrogen atom,
And (D-3) at least one dispersant selected from urethane resin dispersants.

In any of these (D-1) to (D-3), the nitrogen atom contained therein has an affinity for the pigment surface, and the portion other than the nitrogen atom increases the affinity for the medium as a whole. It is estimated that it contributes to the improvement of dispersion stability.
(D) The performance of the dispersant greatly depends on the adsorption behavior on the solid surface. Regarding the relationship between the molecular architecture and the adsorption behavior, it is known that when the same unit is used, the adsorption behavior is excellent in the order of random copolymerization <graft copolymer <block copolymer ( For example, Jones and Richards, “Polymers at Surfaces and Interfaces” p281).

Although the detailed mechanism is unknown, the following can be inferred.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically during the formation of the polymer. . The portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, and thus may be an obstacle when adsorbed to the pigment. In contrast, for resins with a controlled molecular arrangement, such as graft copolymers or block copolymers, the part that prevents the adsorption of the dispersant should be placed at a position away from the adsorption part of the pigment and the dispersant. Can do. That is, an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a portion suitable for it can be arranged in the portion requiring solvent affinity. In particular, for the dispersion of pigments containing pigments having a small crystallite size, it is presumed that this molecular arrangement affects good dispersibility.

<(D-1) Graft copolymer containing nitrogen atom>
(D-1) A graft copolymer containing a nitrogen atom (hereinafter sometimes referred to as “dispersing agent (D-1)”) is preferred in that (A) the pigment can be dispersed very efficiently. The reason is not clear, but because it has a structure that can positively eliminate the part (molecule) that hinders the adsorption of the pigment and the dispersant around the adsorption part to the pigment. As the graft copolymer containing a nitrogen atom, one having a repeating unit containing a nitrogen atom in the main chain is preferable, among which the repeating unit represented by the following general formula (I) and / or the following: It preferably has a repeating unit represented by the general formula (II).

(In formula (I), R ⁵¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following formulas (III) to (V).)
In formula (I), R ⁵¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably an ethylene group. It is.

  A represents a hydrogen atom or any one of the following general formulas (III) to (V), preferably the following formula (III).

(In the formula ^{(II), R 51,} A has the same meaning as ^{R 51,} A, respectively formula (I).)

(In Formula (III), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. Represents an integer of -20, preferably an integer of 5-10.)

(In formula (IV), Y ₁ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, or an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. preferably .W ₂ represents ethylene, propylene, a linear or branched alkylene group having 2 to 10 carbon atoms butylene, among which ethylene, an alkylene group having 2 to 3 carbon atoms such as propylene preferred .Y ₂ Represents a hydrogen atom or —CO—R ⁵² (R ⁵² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among them, C 2-5 such as ethyl, propyl, butyl, pentyl, etc. Q represents an integer of 1 to 20, and preferably an integer of 5 to 10.)

(In the above formula (V), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, among which alkyl having 10 to 20 carbon atoms such as stearyl. A hydroxyalkyl group having 10 to 20 carbon atoms having 1 to 2 hydroxyl groups such as a group and monohydroxystearyl is preferred.)
The content of the repeating unit represented by the general formula (I) or the general formula (II) in the dispersant (D-1) is preferably higher, and is usually 50 mol% or more, preferably 70 mol% or more. is there. The repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) may be both present, and the content ratio is not particularly limited, but the general formula (I) It is preferable to contain a large number of repeating units. The total number of repeating units represented by the general formula (I) or the general formula (II) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50 in one molecule.

Further, the dispersant (D-1) may contain a repeating unit other than the general formula (I) and the general formula (II), and examples of the other repeating unit include an alkylene group and an alkyleneoxy group. .
(D-1) graft copolymer, the end -NH ₂ and ^-R 51 _-NH 2 ^{(R 51} has the formula (synonymous with ^{R 51} is the I)) that are preferred.

In addition, as long as the dispersing agent (D-1) is a graft copolymer, the main chain may be linear or branched.
The amine value of a dispersing agent (D-1) is 5-100 mgKOH / g normally, Preferably it is 10-70 mgKOH / g, More preferably, it is 15-40 mgKOH / g or less. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. On the other hand, if the amine value is too high, the residue may increase or the electrical characteristics after the liquid crystal panel is formed may decrease. is there.

The amine value of the dispersant is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
The polystyrene equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) of the dispersing agent (D-1) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the weight average molecular weight (Mw) is less than 3000, the aggregation of the pigment cannot be prevented and the viscosity or gelation may occur. Conversely, if the weight average molecular weight (Mw) exceeds 100000, the viscosity itself increases. The solubility in organic solvents may be insufficient.

As a method for synthesizing the dispersant (D-1), a known method can be adopted, and for example, a method described in JP-B-63-30057 can be used.
In the present invention, as the dispersant (D-1), a commercially available graft copolymer having the same structure as that described above can also be applied.
<(D-2) Acrylic Block Copolymer>
(D-2) Acrylic block copolymer (hereinafter sometimes referred to as “dispersing agent (D-2)”) is preferred in that (A) the pigment can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed on the pigment.

As the acrylic block copolymer of the dispersant (D-2), a block copolymer composed of an A-block having solvophilicity and a B-block having a functional group containing a nitrogen atom is preferable.
Specifically, the B-block includes a B-block having a quaternary ammonium base and / or an amino group as a nitrogen atom-containing functional group in the side chain, and the solvophilic A-block includes a quaternary. A-blocks having no ammonium base and / or amino group can be mentioned. An AB block copolymer and / or an ABBA block copolymer comprising these A-block and B-block are preferred. Hereinafter, these will be described in detail with reference to examples.

The quaternary ammonium base is preferably —N ⁺ R ³¹ R ³² R ³³ · Z ⁻ (wherein R ³¹ R ³² and R ³³ are each independently a hydrogen atom, or optionally substituted cyclic or chain-like) Or two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure, Z ⁻ represents a counter anion). A quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

As the cyclic structure formed by combining two or more of R ³¹ , R ^32, and R ³³ in —N ⁺ R ³¹ R ³² R ³³ · Z ^— , for example, a 5- to 7-membered nitrogen-containing heterocyclic ring Examples thereof include a single ring or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following.

(In the above formula, R represents any group of R ³¹ , R ³² , and R ^33. These cyclic structures may further have a substituent.)
More preferred as ^{R 31,} R ^{32, R 33} in ^{-N + R 31 R 32 R 33} , each independently, optionally substituted alkyl group having 1 to 3 carbon atoms, or a substituent It is a phenyl group which may have, or a benzyl group which may have a substituent.

  As the B-block having a quaternary ammonium base, those containing a partial structure represented by the following general formula (VI) are preferable.

(In the general formula (VI), R ³¹ , R ³² , and R ³³ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ³¹ , R ³² And two or more of R ³³ may be bonded to each other to form a cyclic structure, R ³⁴ represents a hydrogen atom or a methyl group, X ¹ represents a divalent linking group, Z ^- represents a counter anion).
In the general formula (VI), the hydrocarbon groups of R ³¹ , R ³² and R ³³ are each independently preferably a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. . Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.

In the general formula (VI), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ³⁵ —, —COO—R ³⁶ — (provided that R ³⁵ and R ³⁶ is each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ³⁷ —O—R ³⁸ —: R ³⁷ and R ³⁸ are each independently Represents an alkylene group), and the like, and is preferably —COO—R ³⁶ —.

Further, Z ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.
As the nitrogen atom-containing functional group of the B block, a primary to tertiary amino group is also preferable. The content ratio of the primary to tertiary amino groups is preferably 20 mol% or more, more preferably 50 mol% or more of the entire nitrogen atom-containing functional group. Of the primary to tertiary amino groups, tertiary amino groups are particularly preferred. As the tertiary amino group, specifically, —NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represents a cyclic or chain-like alkyl group which may have a substituent, or a substituent. And an allyl group which may have or an aralkyl group which may have a substituent. Examples of the repeating unit having such a structure include structures represented by the following general formula.

(However, R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, and R ⁴³ is preferably a methylene group or an ethylene group. R ⁴⁴ is preferably a hydrogen atom or a methyl group, more preferably a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following formula is particularly preferably used.

(Wherein R ⁴⁴ has the same meaning as described above.)
Moreover, the structure represented by a following formula can also be mentioned as a preferable structural formula.

Two or more kinds of partial structures containing the specific quaternary ammonium base and / or amino group as described above may be contained in one B-block. In that case, two or more quaternary ammonium bases and / or amino group-containing partial structures may be contained in the B-block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base and / or amino group may be contained in the B-block, and examples of the partial structure are derived from the (meth) acrylic acid ester monomer described later. And the like. The content of the partial structure containing no quaternary ammonium base and / or amino group in the B-block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the base and / or amino group-free partial structure is not contained in the B-block.

On the other hand, the solvophilic A-block constituting the acrylic block copolymer of the dispersant (D-2) does not have a nitrogen atom-containing functional group such as the amino group described above, and the B block described above. If it consists of a monomer which can be copolymerized with the monomer which comprises, there will be no restriction | limiting in particular.
Examples of the solvophilic A-block constituting the acrylic block copolymer of the dispersant (D-2) include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, (meta ) Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl ( (Meth) acrylate monomers such as (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; (meth) acrylic acid chloride (meth) ) Acrylate Monomers; vinyl acetate monomers; allyl glycidyl ether, polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers such as crotonic acid glycidyl ether.

  Among them, as the A block, polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate is included as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate is included. ) Are preferable, and an A block having a partial structure represented by the following formula (VII) is particularly preferable.

(In the formula, g represents an integer of 1 to 5, and R ⁶⁰ represents a hydrogen atom or a methyl group.)
The partial structure represented by the above formula (VII) is particularly preferably contained in the A-block in an amount of 5 to 40 mol%.
The details of the mechanism of action are unknown, but by having a partial structure derived from polyalkylene glycol (meth) acrylate, particularly the partial structure represented by the above formula, it is possible to increase the hydrogen bonding properties of the dispersant molecule. It is considered that the affinity with the dispersion solvent is improved and the stability of the dispersion system is increased.

In addition, the A-block is a (meth) acrylic acid ester-based compound represented by the following general formula (VIII), particularly in terms of improving the familiarity with the nonpolar portion of the solvent by imparting appropriate hydrophobicity. It preferably contains a partial structure derived from a monomer.

(In Formula (VIII), R ³⁹ represents a hydrogen atom or a methyl group. R ⁴⁰ represents a cyclic or chain alkyl group which may have a substituent, or an allyl which may have a substituent. Represents an aralkyl group which may have a group or a substituent.)
R ⁴⁰ is preferably a cyclic group from the viewpoint of high affinity with the pigment and good compatibility.

  Two or more types of partial structures derived from the (meth) acrylic acid ester monomer may be contained in one A-block. Of course, the A-block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in an A-block that does not contain a quaternary ammonium base, each partial structure is contained in the A-block in any form of random copolymerization or block copolymerization. May be. When the A-block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the A-block of the partial structure other than the (meth) acrylate monomer is , Preferably 0 to 99% by weight, more preferably 0 to 85% by weight.

When the colored resin composition of the present invention contains a dispersant (D-2), it is a copolymer comprising an A block and a B block as described above, preferably an AB block or an ABA block. Contains a copolymer. Among these, an AB block copolymer is preferable. Such a block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

The amine value of 1 g of the dispersant (D-2) is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the B-block has a quaternary ammonium base and when it does not have. And different.
That is, when the B block of the AB block copolymer and the ABA block copolymer of the dispersant (D-2) has a quaternary ammonium base, the quaternary in 1 g of the copolymer. The amount of ammonium base is preferably 0.1 to 10 mmol. Outside this range, it may not be possible to combine good heat resistance and dispersibility. In such a block copolymer, an amino group generated in the production process may be contained, and its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 50 mgKOH per 1 g of the copolymer. / G, more preferably 1 to 30 mg KOH / g.

  When the B-block does not contain a quaternary ammonium base, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more. It is 150 mgKOH / g or less, More preferably, it is 90-150 mgKOH / g, Most preferably, it is 100-140 mgKOH / g.

If there are too few nitrogen atom-containing functional groups, the adsorptive power of the dispersant molecules on the pigment surface will be insufficient, and it will be difficult to obtain sufficient dispersion stability. On the other hand, if the amine value is too high, the molecular weight of the A block becomes relatively small, and the dispersion stability may be insufficient.
In other words, the amine value is in the above range in order to develop the optimum dispersibility. The method for measuring the amine value is as described above.

  Moreover, although the acid value of this block copolymer is based on the presence and kind of the acidic group which becomes the origin of this acid value, generally the lower one is preferable. The molecular weight is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by GPC. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

  When the colored resin composition of the present invention further contains a dispersant, a commercially available acrylic block copolymer having the same structure as that described above can also be applied as the dispersant (D-2). In particular, 20% by mole or more of the repeating unit having a functional group containing a nitrogen atom in the B block is a repeating unit having a nitrogen atom-containing functional group, so that a sufficient adsorptive power can be obtained and high dispersion can be obtained. Since stability is obtained, it is preferable.

<(D-3) Urethane resin dispersant>
(D-3) As a urethane resin dispersant (hereinafter sometimes referred to as “dispersant (D-3)”), a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule, A urethane resin obtained by reacting an active hydrogen with a compound having a tertiary amino group in the same molecule is particularly preferred.

  Examples of the polyisocyanate compound include aroma such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane; xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate And triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane) and tris (isocyanatephenyl) thiophosphate; and their trimers, water adducts, and polyol adducts thereof.

Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination of two or more. .
As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. For example, after the trimerization is stopped by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, or one terminal hydroxyl group of these compounds is an alkyl group having 1 to 25 carbon atoms and alkoxy. Or a mixture of two or more of these.
Examples of the polyether glycol include polyether diol, polyether ester diol, or a mixture of two or more of these.

  As the polyether diol, those obtained by homopolymerizing or copolymerizing alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, Or the mixture of 2 or more types of those is mentioned.

Examples of the polyether ester diol include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or by reacting polyester glycol with an alkylene oxide. And oxytetramethylene) adipate.
Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Examples of the polyester glycol include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid, or anhydrides thereof, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene. Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Aliphatic glycols such as glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene Obtained by polycondensation with a diol such as N-alkyldialkanolamine such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or the like; The diols The polylactone diol or polylactone monool obtained by using a monohydric alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone, or mixture of two or more thereof. Most preferred as the polyester glycol is a polycaprolactone glycol or polycaprolactone starting from an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. is there.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like.
Of these compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.

In addition, the number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.
In the compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes a hydroxyl group, an amino group, a thiol group, etc. Among these, a hydrogen atom in the functional group is mentioned, and an amino group, particularly a primary amino group hydrogen atom is preferable. As the tertiary amino group, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like, and the dialkylamino group are linked to form a heterocyclic structure. More specifically, an imidazole ring or a triazole ring can be mentioned. Among them, a dimethylamino group and an imidazole ring are preferable because of excellent dispersion stability.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  As the tertiary amino group is a nitrogen-containing heterocycle, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include nitrogen-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring; nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. It is done.

  Further, specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H. -1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino Examples include -1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole.

Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4- Triazole and the like are preferable.
The preferred use ratio of these urethane resin dispersant raw materials is that the compound having one or two hydroxyl groups in the same molecule is usually 10 to 200 parts by weight, preferably 20 to 190 parts by weight per 100 parts by weight of the polyisocyanate compound. Parts, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

If the content of a compound having one or more hydroxyl groups in the same molecule is more than the above range, the synthesis may be difficult, such as gelation due to too many reaction points during compound synthesis, If the amount is less than the above range, the so-called tail portion of the dispersant is shortened, which may result in insufficient dispersibility.
Further, if the content of the compound having active hydrogen and amino group in the same molecule is larger than the above range, free adsorbing groups that do not adsorb to the pigment increase, and these are the reactive sites in the colored photopolymerizable composition. The storage stability may be adversely affected. When the amount is less than the above range, the dispersant is difficult to be adsorbed to the pigment and may not function sufficiently as a dispersant.

  Manufacture of a urethane resin dispersing agent (D-3) is performed according to the well-known method of urethane resin manufacture. As the solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone; esters such as ethyl acetate, butyl acetate, cellosolve acetate; benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, some alcohols such as isopropanol, sec-butanol and tert-butanol; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide An aprotic polar solvent such as N-methylpyrrolidone or dimethyl sulfoxide is used. Moreover, a normal urethanization reaction catalyst is used as a catalyst at the time of manufacture. For example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate, and the like tin; iron acetylacetonate, ferric chloride, and the like; tertiary amines such as triethylamine, triethylenediamine, etc. Can be mentioned.

  The amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g, more preferably 5 in terms of amine value of the urethane resin obtained by the reaction. It is the range of -80 mgKOH / g, More preferably, it is the range of 10-60 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the urethane resin obtained by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the time stability of the urethane resin is increased.

  The weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the urethane resin dispersant (D-3) is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3, It is in the range of 000 to 50,000. When the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor.

<(D-4) Other dispersant>
When the colored resin composition of the present invention further contains (D) a dispersant, in addition to the above-mentioned various dispersants (D-1) to (D-3), other dispersants (hereinafter referred to as “dispersant ( D-4) ”may be included.
Other dispersants include, for example, polyallylamine dispersants, dispersants composed of monomers and macromonomers having amino groups, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, and polyether phosphates. Examples thereof include a dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

  Specific examples of such a dispersant include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (manufactured by Shinetsu) Chemical products), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and other series names can be mentioned.

The above dispersants (D-1) to (D-4) may be used alone or in combination of two or more.
In addition, also about the above-mentioned dispersing agent (D-1)-(D-4), you may remove a low molecular weight component similarly to the above-mentioned (B) polymer. In that case, as in the case of the polymer (B), the low molecular weight component may be removed by the various methods described above, and a copolymer having a low low molecular weight component may be produced by controlling the polymerization process.

  The colored photopolymerizable composition of the present invention includes (D-1) a graft copolymer containing a nitrogen atom and (D-2) an acrylic block copolymer containing a nitrogen atom among the various dispersants described above. And (D-3) one or more dispersants selected from urethane resin dispersants are preferably included, and (D-2) an acrylic block copolymer containing nitrogen atoms is particularly preferable.

In the colored resin composition of the present invention, the content of the (D) dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less, based on the pigment (A). Moreover, it is 5 weight% or more normally, Preferably it is 7 weight% or more, Most preferably, it is 10 weight% or more.
In addition, the weight ratio of the (A) pigment to the (D) dispersant is preferably 2 or more and more preferably 4 or more from the viewpoint that the dissolution time in the development step described later can be shortened. Particularly preferably, it is 5 or more. (D) When the content ratio of the dispersant is too small, the adsorption to the pigment is insufficient, aggregation cannot be prevented, and the viscosity or gelation may occur. Problems such as aggregation and thickening may occur. On the other hand, if the amount is too large, the ratio of the pigment is relatively reduced, so the coloring power is low, and the film thickness becomes too thick for the color density. Poor control may occur.

<(E) Photopolymerization initiators and / or thermal polymerization initiators>
The colored resin composition of the present invention preferably further contains (E) a photopolymerization initiator and / or a thermal polymerization initiator for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the colored resin composition of the present invention contains (B) a resin having an ethylenic double bond as a polymer component, or (F) an ethylenic compound as a polymerizable monomer component described later, Photoinitiators that have the function of directly absorbing or photosensitized to cause decomposition reaction or hydrogen abstraction reaction to generate polymerization active radicals and / or thermal polymerization initiators that generate polymerization active radicals by heat It is preferable to contain. In the present invention, the component (E) as a photopolymerization initiator is a photopolymerization initiator (hereinafter sometimes referred to as (E-1) component) or a polymerization accelerator (hereinafter referred to as (E-2). ), And a sensitizing dye (hereinafter, sometimes referred to as (E-3) component).

<Photopolymerization initiators>
The (E) photopolymerization initiators that may be contained in the colored resin composition of the present invention are usually (E-1) a photopolymerization initiator and, if necessary, added (E-3). Used as a mixture with an additive such as a dye sensitizer and (E-2) a polymerization accelerator, and directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical It is a component having

  (E) Photopolymerization initiators (E-1) Examples of photopolymerization initiators include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; Hexaarylbiimidazole derivatives described in JP-A-10-300922, JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazoles described in JP-A-10-39503 Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A and the like .

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  As biimidazole derivatives, 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole 2 amount 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  The halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl). Vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2- And trichloromethyl-5-furyl-1,3,4-oxadiazole.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl). ) -S-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s -Triazine etc. are mentioned.

Examples of the α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like The

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.
In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- ( acetophenone derivatives such as p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone are also included.

Among these (E-1) photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, and thioxanthone derivatives are more preferable.
Moreover, the coloring resin composition of this invention can mix | blend (E-2) a polymerization accelerator further as needed, especially when (E) photoinitiators are included. (E-2) Examples of the polymerization accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

One of these (E-1) photopolymerization initiator and (E-2) polymerization accelerator may be used alone, or two or more thereof may be used in combination.
(E-3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, these (E) photopolymerization initiators ((E-1) photopolymerization initiator, (E-2) polymerization accelerator, and (E-3) sensitizing dye) are contained. The ratio is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less in the total solid content. If the content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if the content is extremely high, the solubility of the unexposed part in the developer is reduced, leading to poor development or an initiator. Due to the influence of the light itself, that is, due to the light absorption characteristics of the initiator itself, the luminance may decrease when the transmittance of the pixel decreases.

  In the colored resin composition of the present invention, (E-3) a sensitizing dye may be used in the photopolymerization initiator (E) for the purpose of increasing the sensitivity. (E-3) As the sensitizing dye, an appropriate dye is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc. A coumarin dye having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin described in JP-A-3-239703, JP-A-5-289335, etc. Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. 5-107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  Among these (E-3) sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. (E-3) Particularly preferred as the sensitizing dye is, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone. Benzophenone compounds such as 3,3′-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethyl) Aminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzo Azole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1, 3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, p-dialkylaminophenyl group-containing compounds such as p-diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone such as 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone is most preferred.

<Thermal polymerization initiators>
Specific examples of the thermal polymerization initiators that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-carbonitrile), 2, 2′-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis {2 -Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2 '-Azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropionamide], 2,2'-azobis (N-cyclo Xyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionate), 2,2′-azobis (2 , 4,4-trimethylpentene) and the like. Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable. .

  Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butyl peroxypivale Di (3,5,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (T-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) Cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t- Butyl peroxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) Hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2, 3-dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) peroxy Mixtures of benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide may be mentioned.

In addition, some of the above-described (E-1) photopolymerization initiators also function as thermal polymerization initiators. Therefore, you may use the compound selected from the examples given as an example of (E-1) photoinitiator as a thermal-polymerization initiator.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
When the ratio of the thermal polymerization initiators in the colored resin composition is too small, the film is not sufficiently cured and the durability as a color filter may be insufficient. If the amount is too large, the degree of thermal shrinkage increases, and cracking and cracking may occur after thermosetting. Moreover, the tendency for storage stability to fall is seen. Therefore, the content of the thermal polymerization initiators is preferably in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the colored resin composition of the present invention.

<(F) polymerizable monomer>
The colored resin composition of the present invention preferably further contains (F) a polymerizable monomer as required. (F) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it is an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred). The ethylenic compound means that when the colored resin composition of the present invention is irradiated with actinic rays, it is cured by addition polymerization by the action of the photopolymerization initiators described above, or when heated. It is a compound having an ethylenic double bond that is cured by addition polymerization by the action of the thermal polymerization initiators. In addition, the (F) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and means the concept containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

  Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate. And acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. And condensates of glycerin and the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products thereof.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These ethylenic compound monomers may be used singly, but since it is difficult to use a single compound for production, two or more of them may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the colored resin composition of the present invention, more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture mainly composed of succinic acid ester. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

  The content of the polymerizable monomer (F) is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight in the total solid content of the colored resin composition of the present invention. % Or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to (A) pigment is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 100%. % By weight or less, more preferably 80% by weight or less. (F) When there are too many polymerizable monomers, it is possible that the solubility with respect to an alkaline developing solution will fall remarkably when it is set as a composition. On the other hand, if the amount is too small, the crosslink density may decrease and the curability may decrease.

<Surfactant>
The colored resin composition of the present invention may further contain a surfactant. Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.

  Examples of the anionic surfactant include alkyl sulfate ester surfactants such as “Emar 10” manufactured by Kao Corporation, and alkylnaphthalene sulfonate surfactants such as “Perex NB-L” manufactured by Kao Corporation. And special polymer surfactants such as “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

Examples of the cationic surfactant include alkylamine salt surfactants such as “Acetamine 24” manufactured by Kao Corporation, and quaternary ammonium salt interfaces such as “Cotamine 24P” and “Coatamine 86W” manufactured by Kao Corporation. Examples include activators. Of these, quaternary ammonium salt surfactants are preferred, and stearyltrimethylammonium salt surfactants are more preferred.

  Nonionic surfactants include, for example, “SH8400” manufactured by Tore Silicone; silicone surfactants such as “KP341” manufactured by Silicone; “FC430” manufactured by Sumitomo 3M; Dainippon Ink and Chemicals, Inc. "F470" manufactured by KK; fluorine-based surfactants such as "DFX-18" manufactured by Neos; polyoxyethylene-based surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation, etc. . Of these, silicone surfactants are preferable, and so-called polyether-modified or aralkyl-modified silicone surfactants having a structure in which a side chain of a polyether group or an aralkyl group is added to polydimethylsiloxane are more preferable.

Two or more surfactants may be used in combination, for example, silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer. And combinations of surfactants. Of these, a combination of silicone surfactant / fluorine surfactant is preferable.
Examples of the silicone surfactant / fluorine surfactant combination include a polyether-modified silicone surfactant / oligomer-type fluorine surfactant combination. Specifically, for example, “TSF4460” manufactured by GE Toshiba Silicone / “DFX-18” manufactured by Neos, “BYK-300” manufactured by BYK Chemie / “S-393” manufactured by Seimi Chemical Co., “KP340 manufactured by Shin-Etsu Silicone Co., Ltd.” "F-478" manufactured by Dainippon Ink & Chemicals, "SH7PA" manufactured by Tore Silicone, "DS-401" manufactured by Daikin, "L-77" manufactured by Nihon Unicar, and "FC4430" manufactured by Sumitomo 3M The combination of is mentioned.

  In the colored resin composition of the present invention, the content of these surfactants is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more in the total solid content. is there. Further, it is usually used in the range of 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less. By controlling the surfactant content within this range, there is no possibility that the overcoat will be repelled when the overcoat is applied in the actual line, and the coating film may be cracked after curing. The film is less likely to wrinkle.

<Other ingredients>
The colored resin composition of the present invention has, in addition to the above-mentioned components, a polymer other than the polymer (B) (hereinafter sometimes referred to as “other polymer”), a dispersion aid, an organic carboxylic acid, and / or organic. A carboxylic acid anhydride, a plasticizer, a dye, a thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver and the like may be contained.

  Examples of other polymers include: “In the chromatograph obtained by gel permeation chromatography (GPC), the area of components having a polystyrene-equivalent weight average molecular weight (Mw) of 5000 or less excludes peak areas of unreacted monomers and polymerization solvents. Except for not controlling it to “20% or less with respect to the total area”, the same polymer as the polymer (B) described above may be mentioned.

In the colored resin composition of the present invention, a part of the polymer (B) may be replaced with another polymer as long as the effects of the present invention are not impaired. By appropriately containing other polymers, for example, solubility in a developer can be adjusted.
The other polymer is usually 80 of (B) polymer contained in the colored resin composition of the present invention.
It is made to contain by substituting the weight percent or less, preferably 70 weight percent or less. Further, it is usually contained by replacing 5% by weight or more, preferably 10% by weight or more of the polymer (B) with this.

If the amount of the other polymer is too large, undissolved matter may be generated in the non-image area on the substrate or the pattern shape after baking may be poor. If the amount is too small, the solubility in the developer may be reduced. The effect may not be fully manifested.
As the other polymer, the copolymer is preferably compared to the copolymer of (B-1) epoxy group-containing (meth) acrylate and another radical polymerizable monomer described in the section of (B) polymer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction; B-4) (Meth) acrylic resins.

The colored resin composition of the present invention may contain a dispersion aid for improving the dispersibility of the pigment, improving the dispersion stability, and the like. Examples of the dispersion aid include pigment derivatives.
Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole And derivatives such as dioxazine pigments.

  Examples of the substituent of these pigment derivatives include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. These substituents may be directly bonded to the pigment skeleton, or may be bonded via an alkyl group, an aryl group, a heterocyclic group or the like. Of the substituents, a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group are preferable, and a sulfonic acid group is more preferable.

A plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.
Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, diketo Examples include sulfonic acid derivatives of pyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments. Among these, sulfonic acid derivatives of Pigment Yellow 138, sulfonic acid derivatives of Pigment Yellow 139, sulfonic acid derivatives of Pigment Red 254, sulfonic acid derivatives of Pigment Red 255, sulfonic acid derivatives of Pigment Red 264, and sulfonic acid of Pigment Red 272 are preferable. A sulfonic acid derivative of Pigment Red 209, a sulfonic acid derivative of Pigment Orange 71, and a sulfonic acid derivative of Pigment Violet 23.

The dispersing aid may not be a derivative of the pigment itself mentioned above but may be a compound having a similar chemical structure.
In the colored resin composition of the present invention, the content ratio of these dispersion aids is usually 0.1% by weight or more and usually 30% by weight or less, preferably 200%, based on the pigment component (A). % By weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less. This is because if the added amount is small, the effect is not exhibited, and conversely, if the added amount is too large, the dispersibility and dispersion stability may be deteriorated.

The colored resin composition of the present invention preferably contains no phosphoric acid acrylate content or is 5% by weight or less based on the total solid content. Phosphoric acid acrylate is often used mainly as an adhesion improver, but has a high polarity and tends to inhibit the adsorption of the pigment and the dispersant, so that reaggregation of the pigment easily occurs. For this reason, there exists a possibility that the viscosity of a colored resin composition may rise and stability may fall. This reaggregation is accelerated by the moisture contained in the composition.

Examples of the phosphoric acid acrylate include compounds described in JP-A-2006-343648.
When the colored resin composition of the present invention is used in a color filter as described later, an organic compound having a molecular weight of 1000 or less is used in order to further reduce the residual undissolved resin composition while maintaining high pattern adhesion. Carboxylic acid and / or organic carboxylic acid anhydride may be contained. These are preferably contained when the urethane resin dispersant is included as the aforementioned (D) dispersant.

Specific examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids.
Aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, (meth) acrylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid; and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and a carboxylic acid in which a carboxyl group is bonded to the phenyl group through a carbon bond.

Among these, those having a molecular weight of 600 or less are preferable, and those having a molecular weight of 50 to 500 are particularly preferable. Specifically, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.
Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specifically, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Aliphatic carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride Things. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

Among these, those having a molecular weight of 600 or less are preferable, and those having a molecular weight of 50 to 500 are particularly preferable. Specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.
In the colored resin composition of the present invention, the content ratio of these organic carboxylic acids or / and organic carboxylic acid anhydrides is generally 0.01% by weight or more, preferably 0.03% by weight or more, based on the total solid content. Preferably it is 0.05 weight% or more, and is 10 weight% or less normally, Preferably it is 5 weight% or less, More preferably, it is 3 weight% or less.

The colored resin composition of the present invention may contain a dye, such as an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinoneimine dye, a quinoline dye, a nitro dye, a carbonyl dye, or a methine dye. Etc.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
Examples of phthalocyanine dyes include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  The colored resin composition of the present invention may contain a plasticizer. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, Examples include dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The content of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content.

The colored resin composition of the present invention may contain a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t- Examples include butyl-p-cresol, β-naphthol and the like. The content of these thermal polymerization inhibitors is preferably in the range of 3% by weight or less based on the total solid content.
<Preparation method of colored resin composition>
The colored resin composition of the present invention may be prepared by mixing the materials constituting the composition at once or sequentially. However, as described below, a pigment dispersion is prepared in advance, and other materials are prepared. It is preferred to mix the components.

Hereinafter, although an example of the method of preparing the colored resin composition of this invention is demonstrated, there is no restriction | limiting in particular in a preparation method, It is not necessarily limited to the method described below.
As described above, the colored resin composition of the present invention is preferably used as a colored resin composition for a color filter from the viewpoint of “merits of the present invention” and the like. Specifically, it is preferably used as a color filter pixel or black matrix forming material, and particularly preferably used as a pixel forming material.

The colored resin composition for a color filter of the present invention may be photocurable (photopolymerizable) or thermopolymerizable depending on the production process of the color filter to be applied.
The colored resin composition of the present invention is prepared by first preparing a pigment dispersion containing at least (A) a pigment, (B) a polymer, (C) a solvent, and optionally (D) a dispersant. F) It is preferable to prepare by mixing a polymerizable monomer and other components optionally used.

First, a predetermined amount of (A) pigment, (B) polymer, (C) solvent, and optionally (D) dispersant is weighed, and in the dispersion treatment step, (A) the pigment is dispersed to obtain an ink-like liquid (pigment dispersion). Body). In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By carrying out this dispersion treatment, the pigment is made fine, so that the coating characteristics of the colored resin composition are improved and the transmittance of the product color filter substrate and the like is improved. (A) When dispersing the pigment, as described above, it is preferable to use a dispersion aid or the like as appropriate.

  When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.

  The ink-like liquid obtained by the dispersion treatment includes (F) a polymerizable monomer, (E) a photopolymerization initiator and / or a thermal polymerization initiator, another polymer (a polymer other than the polymer (B)), and an interface. A colored resin composition is obtained by mixing an optional component such as an activator and, if necessary, the polymer (B) as a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and a mixing process, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

<Application of colored resin composition>
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This is supplied onto the substrate to form a color filter and a component of the display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a black matrix or a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display using them will be described.

<Manufacture of color filter substrates>
Next, the color filter of the present invention (hereinafter sometimes referred to as “color filter substrate”) will be described.
The color filter of the present invention is characterized by having pixels formed on the substrate using the above-described colored resin composition.

<Transparent substrate (support)>
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, or various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, for improvement of surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc. May be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.

<Black Matrix>
The color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green and blue colors. The colored resin composition of the present invention is used as a coating liquid for forming a black matrix or pixels that are usually red, green and blue.

The black matrix is formed on the transparent substrate using a light shielding metal thin film or a coating liquid for forming a black matrix (which may be the colored resin composition of the present invention). As the light shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate and perchloric acid and / or nitric acid are applied to chromium. Other materials are etched using an etchant appropriate for the material, and finally the positive photoresist is stripped with a special stripper to form a black matrix. can do.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When utilizing the coating liquid for black matrix formation, a black matrix is formed using the colored resin composition containing a black (A) pigment. For example, black pigments such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc. A black matrix can be formed in the same manner as in the following method for forming red, green and blue pixel images using a colored resin composition containing a black pigment.

  When a color filter (pixels) is manufactured by an inkjet method, first, a partition pattern (black matrix) is provided on a substrate, and pixels are formed in the pattern (hereinafter sometimes referred to as “inside a pixel bank”). Ink (colored resin composition) is directly applied to produce a color filter. Since ink droplets can be drawn at a desired position, high productivity and cost reduction of the color filter can be achieved.

  The black matrix of the color filter by the ink jet method not only functions as a light blocking function that is conventionally required, but also functions as a partition to prevent the RGB ink driven into the pixel bank from being mixed. The film thickness is thicker than that of the color filter according to (1). Usually, the film thickness is 1.5 μm or more, preferably about 1.8 to 2.5 μm, more preferably about 2.0 to 2.3 μm. ). In addition, in order to prevent color mixing of RGB ink, liquid repellent treatment is often applied to the upper surface of the black matrix.

Therefore, it was formed using a photosensitive material including a black color material from a conventionally used chromium compound such as chromium, chromium oxide and chromium nitride, and a black matrix made of a light-shielding metal material such as nickel and tungsten alloy. A resin black matrix is preferred.
When the color filter of the present invention is produced by the inkjet method, the resin black matrix may be formed by a general photolithography method using the photosensitive coloring resin composition for black matrix as described above. Subsequently, the surface of the transparent substrate is made hydrophilic and the black matrix pattern is made liquid repellent by chemical treatment or physical treatment, respectively.

<Formation of pixels>
The method for forming the pixel varies depending on the type of the colored resin composition to be used. First, a case where a photopolymerizable composition is used as the colored resin composition and pixels are formed by photolithography will be described as an example.
On a transparent substrate provided with a black matrix, a colored resin composition of one of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film, and image exposure is performed through this photomask. A pixel image is formed by development and, if necessary, thermal curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

  The colored resin composition for color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, and there is no influence of mist adhering when using the spin coating method. It is preferable from a viewpoint.

  If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.

Next, a case where pixels are formed by an inkjet method will be described.
In the pixel bank on the substrate provided with the resin black matrix, the colored resin composition of the present invention is used to draw with an inkjet apparatus, and the composition is completely cured by drying, photocuring and / or heat curing, A color filter is obtained by forming pixels. In addition, as the colored resin composition for pixel formation, three colors of R (red), G (green), and B (blue) are often used, but are not limited thereto.

<Drying of coating film>
Drying of the coating film formed by applying the colored resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried.
The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

  The temperature condition for reheat drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. It is the range below ℃. Moreover, although it depends on the heating temperature, the drying time is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the polymer may be decomposed to cause thermal polymerization and cause poor development. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature. Preferred drying conditions are 0.1 to 1 Torr, and the drying time is in the range of 10 seconds to 60 minutes.

Moreover, when the colored resin composition of this invention is photopolymerizable, an exposure process is performed following this drying process.
<Exposure process>
Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.

  The light source used for said image exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

When the color filter of the present invention is produced by photolithography, the process further proceeds to a development process.
<Development process>
The color filter of the present invention uses an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after image exposure with the above-mentioned light source to the coating film using the colored resin composition of the present invention. By performing development in this manner, an image can be formed on the substrate and manufactured. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- Or trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Organic alkali compound may be mentioned.

These alkaline compounds may be a mixture of two or more.
Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred. The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

<Heat curing (firing) treatment>
The color filter after development is preferably subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or more, preferably 150 ° C. or more, and usually 280 ° C. or less, preferably 250 ° C. or less, and the time is 5 minutes or more and 60 minutes or less. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

In the case of producing a color filter by an ink jet method, if the colored resin composition of the present invention is photopolymerizable, after the exposure step, if it is thermosetting, after the coating step by the ink jet method, thermosetting Process. Preferred conditions for the thermosetting treatment are the same as described above.
In addition to the manufacturing method described above, the color filter of the present invention is (1) (B) a colored resin composition of the present invention containing a polyimide resin as a polymer is applied to a substrate, and a pixel image is formed by an etching method. It can also be produced by a method of forming Also, (2) a method of directly forming a pixel image on a transparent substrate by a printing press using the colored resin composition of the present invention as a colored ink, and (3) using the colored resin composition of the present invention as an electrodeposition liquid. And a method of depositing a colored film on the ITO electrode having a predetermined pattern by immersing the substrate in this electrodeposition solution, and (4) a film coated with the colored resin composition of the present invention is attached to a transparent substrate And a method of forming a pixel image by peeling and image exposure and development, and (5) a method of forming a pixel image with an ink jet printer using the colored resin composition of the present invention as a colored ink.

As a method for producing the color filter, a method suitable for this is employed according to the composition of the colored resin composition of the present invention.
<Formation of transparent electrode>
The color filter of the present invention forms a transparent electrode such as ITO on the image as it is and is used as a part of components such as a color display and a liquid crystal display device. However, the surface smoothness and durability are improved. Therefore, if necessary, a top coat layer such as polyamide or polyimide can be provided on the image. In some cases, the transparent electrode may not be formed in applications such as a planar alignment type driving system (IPS mode).

<Liquid crystal display device (panel)>
Next, the manufacturing method of the liquid crystal display device (panel) of this invention is demonstrated. In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to the counter substrate to form a liquid crystal cell. Liquid crystal is injected into the cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or higher, preferably 1 × 10 ⁻³ Pa or higher, and usually 1 × 10 ⁻⁷ Pa or lower, preferably 1 × 10 ⁻⁶ Pa or lower. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

<Organic EL display>
When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 4, first, a pattern (pixel 20 or adjacent pixel 20) formed on a transparent support substrate 10 by a colored resin composition. A color filter in which a resin black matrix (not shown) provided between the layers is formed is formed, and an organic light-emitting body 500 is laminated on the color filter with the organic protective layer 30 and the inorganic oxide film 40 interposed therebetween. Thus, an organic EL element can be manufactured. Note that at least one of the pixel 20 and the resin black matrix is manufactured using the colored resin composition of the present invention.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Reference Examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
<Synthesis Example 1 Polymer a: Synthesis of poly (benzyl methacrylate-co-methacrylic acid)>
Into a flask equipped with a condenser, nitrogen introduction tube, stirrer and thermometer, the inside of which was purged with nitrogen was charged with 1.9 g of cuprous chloride as a catalyst, 348 g of anisole as a solvent, and 118 g of t-butyl methacrylate as a monomer. , 220 g of benzyl methacrylate, 3.32 g of pentamethyldiethylenetriamine as a ligand, and 2.706 g of ethyl bromoisobutyrate as an initiator were bubbled with nitrogen for 15 minutes, and then charged into the above flask. Heated for hours.

  After completion of the reaction, the polymerization reaction solution was added to methanol / water (2000 mL / 500 mL) to precipitate the polymer. The precipitated polymer was collected and suspended in 1000 ml of methanol, and then 300 ml of water was added to precipitate the polymer. Thereafter, the obtained polymer was vacuum-dried to obtain poly (benzyl methacrylate-co-t-butyl methacrylate). The weight average molecular weight (Mw) in terms of polystyrene of the polymer determined by gel permeation chromatography (GPC) was 16000, and the molecular weight distribution was 1.2.

  Next, 60 g of the above poly (benzyl methacrylate-co-t-butyl methacrylate) was dissolved in 540 g of toluene in a flask equipped with a condenser, a stirrer and a thermometer, and then paratoluenesulfonic acid monohydrate. 754g was added and it heated at 80 degreeC for 1.5 hours. Precipitation gradually occurred during heating, and after completion of heating, the supernatant was removed to obtain a polymer precipitate. To the polymer precipitate, 290 g of 1,4-dioxane was added to dissolve the precipitate, and 1.754 g of paratoluenesulfonic acid monohydrate was added, followed by heating at 80 ° C. for 6 hours. Thereafter, 0.877 g of paratoluenesulfonic acid monohydrate was added, and the mixture was further heated at 80 ° C. for 7 hours. Thereafter, the mixture was cooled to room temperature, and the reaction solution was dropped into 1.5 L of hexane to obtain a polymer precipitate. The polymer precipitate was dried under vacuum to obtain polymer a: poly (benzyl methacrylate-co-methacrylic acid).

The structure of polymer a was confirmed by ¹ H-NMR using heavy DMSO as a solvent, and the composition ratio of benzyl methacrylate units and methacrylic acid units in the polymer was 59/41 (molar ratio).
The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of polymer a was 10,500, and the molecular weight distribution was 2.1. In all polymer component peaks excluding the peaks of unreacted monomers and polymerization solvent components, the area ratio of polystyrene equivalent weight average molecular weight (Mw) of 5000 or less was 17%, and the area ratio of 8000 or less was 33%. The acid value was 175 mgKOH / g.

<Synthesis Example 2 Polymer d: Synthesis of poly (benzyl methacrylate-co-methacrylic acid)>
2.59 g of cuprous chloride was charged as a catalyst in a condenser, a nitrogen inlet tube, a stirrer, and a thermometer flask, the inside of which was purged with nitrogen, and 461 g of anisole as a solvent and 161 g of t-butyl methacrylate as a monomer. , 300 g of benzyl methacrylate, 4.53 g of pentamethyldiethylenetriamine as a ligand, and 2.77 g of ethyl bromoisobutyrate as an initiator were bubbled with nitrogen for 15 minutes, and then charged into the flask. Heated for hours.

  After completion of the reaction, the polymerization reaction solution was added to methanol / water (2000 mL / 500 mL) to precipitate the polymer. The precipitated polymer was collected and suspended in 1000 ml of methanol, and then 300 ml of water was added to precipitate the polymer. Thereafter, the obtained polymer was vacuum-dried to obtain poly (benzyl methacrylate-co-t-butyl methacrylate). The polystyrene-reduced weight average molecular weight (Mw) of the polymer determined by gel permeation chromatography (GPC) was 42900, and the molecular weight distribution was 1.2.

Next, after dissolving 60 g of the above poly (benzyl methacrylate-co-t-butyl methacrylate) in 540 g of toluene in a flask equipped with a condenser, a stirrer and a thermometer,
1.754 g of paratoluenesulfonic acid monohydrate was added and heated at 80 ° C. for 1.5 hours. Precipitation gradually occurred during heating, and after completion of heating, the supernatant was removed to obtain a polymer precipitate. To the polymer precipitate, 290 g of 1,4-dioxane was added to dissolve the precipitate, and 1.754 g of paratoluenesulfonic acid monohydrate was added, followed by heating at 80 ° C. for 6 hours. Thereafter, 0.877 g of paratoluenesulfonic acid monohydrate was added, and the mixture was further heated at 80 ° C. for 7 hours. Thereafter, the mixture was cooled to room temperature, and the reaction solution was dropped into 1.5 L of hexane to obtain a polymer precipitate. The polymer precipitate was vacuum-dried to obtain polymer d: poly (benzyl methacrylate-co-methacrylic acid).

The structure of the polymer d was confirmed by ¹ H-NMR using heavy DMSO as a solvent, and the composition ratio of benzyl methacrylate units and methacrylic acid units in the polymer was 59/41 (molar ratio).
The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of polymer d was 21,900, and the molecular weight distribution was 2.3. In all polymer component peaks excluding the peak of unreacted monomer and polymerization solvent component, the area ratio of polystyrene equivalent weight average molecular weight (Mw) of 5000 or less was 7%, and the area ratio of 8000 or less was 10%. The acid value was 170 mgKOH / g.

<Synthesis Example 3 Polymer e: Synthesis of poly (benzyl methacrylate-co-methacrylic acid)>
1.69 g of cuprous chloride as a catalyst was charged into a condenser, a nitrogen inlet tube, a stirrer, and a thermometer-equipped flask whose inside was replaced with nitrogen, and 900 g of anisole as a solvent.
After bubbling a mixed solution of 108 g of t-butyl methacrylate as the monomer, 192 g of benzyl methacrylate, 2.96 g of pentamethyldiethylenetriamine as the ligand, and 6.01 g of ethyl bromoisobutyrate as the initiator for 15 minutes, It was charged in and heated at 40 ° C. for 6 hours.

  After completion of the reaction, the polymerization reaction solution was added to methanol / water (2000 mL / 500 mL) to precipitate the polymer. The precipitated polymer was collected and suspended in 1000 ml of methanol, and then 300 ml of water was added to precipitate the polymer. Thereafter, the obtained polymer was vacuum-dried to obtain poly (benzyl methacrylate-co-t-butyl methacrylate). The polystyrene-reduced weight average molecular weight (Mw) of the polymer determined by gel permeation chromatography (GPC) was 9200, and the molecular weight distribution was 1.1.

Next, after dissolving 60 g of the above poly (benzyl methacrylate-co-t-butyl methacrylate) in 540 g of toluene in a flask equipped with a condenser, a stirrer and a thermometer,
1.754 g of paratoluenesulfonic acid monohydrate was added and heated at 80 ° C. for 1.5 hours. Precipitation gradually occurred during heating, and after completion of heating, the supernatant was removed to obtain a polymer precipitate. To the polymer precipitate, 290 g of 1,4-dioxane was added to dissolve the precipitate, and 1.754 g of paratoluenesulfonic acid monohydrate was added, followed by heating at 80 ° C. for 6 hours. Thereafter, 0.877 g of paratoluenesulfonic acid monohydrate was added, and the mixture was further heated at 80 ° C. for 7 hours. Thereafter, the mixture was cooled to room temperature, and the reaction solution was dropped into 1.5 L of hexane to obtain a polymer precipitate. The polymer precipitate was vacuum dried to obtain polymer e: poly (benzyl methacrylate-co-methacrylic acid).

The structure of the polymer e was confirmed by ¹ H-NMR using heavy DMSO as a solvent, and the composition ratio of benzyl methacrylate units and methacrylic acid units in the polymer was 60/40 (molar ratio).
The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of polymer e was 6400, and the molecular weight distribution was 1.9. In all polymer component peaks excluding unreacted monomers and polymerization solvent component peaks, the area ratio of polystyrene equivalent weight average molecular weight (Mw) of 5000 or less was 33%, and the area ratio of 8000 or less was 71%. The acid value was 160 mgKOH / g.

<Synthesis Example 4 Polymer f: Synthesis of poly (benzyl methacrylate-co-methacrylic acid)>
100 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was placed in a condenser equipped with nitrogen, a nitrogen introduction tube, a dropping funnel, a stirrer, and a thermometer-equipped flask, and the temperature was raised to 91 ° C. 71.6 g of benzyl methacrylate as monomer, 28.4 g of methacrylic acid, and 3.5 g of 2,2′-azobis (2-methylbutyronitrile) as catalyst were dissolved in 50 g of propylene glycol monomethyl ether acetate to prepare a monomer solution and dropped. Placed in funnel. The monomer solution was dropped into the flask from the funnel over 3 hours. Then, after heating for 4 hours while maintaining the temperature range of 91 ° C to 93 ° C, the temperature was raised to 101 ° C and heated for 1 hour, followed by cooling to poly (benzyl methacrylate-co-methacrylic acid): A PGMEA solution of polymer f was obtained.

The structure of the polymer f was confirmed by ¹ H-NMR using heavy DMSO as a solvent, and the composition ratio of benzyl methacrylate units and methacrylic acid units in the polymer was 55/45 (molar ratio).
The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of the polymer f was 10700, and the molecular weight distribution was 3.3. In all polymer component peaks excluding the peak of unreacted monomer and polymerization solvent component, the area ratio of polystyrene equivalent weight average molecular weight (Mw) of 5000 or less was 35%, and the area ratio of 8000 or less was 49%. The acid value was 175 mgKOH / g.

<Synthesis Example 5 Polymer b: Synthesis of low molecular weight Cut poly (benzyl methacrylate-co-methacrylic acid)>
A dropping funnel and a flask equipped with a stirrer were charged with 200 g of the PGMEA solution of polymer f obtained in Synthesis Example 4 and further diluted with 500 g of THF. While stirring the polymer solution, 450 ml of hexane was added dropwise from the dropping funnel to the diluted polymer solution. The whole amount of hexane was dropped, and then allowed to stand, and the supernatant was removed to obtain a polymer precipitate. After adding 600 g of THF to the polymer precipitate and dissolving with stirring, 400 ml of hexane was dropped from the dropping funnel. The whole amount of hexane was dropped, and then allowed to stand, and the supernatant was removed to obtain a polymer precipitate. Furthermore, 600 g of THF was added to the polymer precipitate and dissolved by stirring, and then 600 ml of hexane was added dropwise from the dropping funnel. The whole amount of hexane was dropped, and then allowed to stand, and the supernatant was removed to obtain a polymer precipitate. The polymer precipitate was vacuum-dried to obtain a powdery polymer b. The structure of the polymer was confirmed by ¹ H-NMR using heavy DMSO as a solvent, and the composition ratio of benzyl methacrylate units and methacrylic acid units in the polymer was 55/45 (molar ratio).

  The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of polymer b was 15000, and the molecular weight distribution was 2.9. In all polymer component peaks, the area ratio of polystyrene equivalent weight average molecular weight (Mw) of 5000 or less was 16%, and the area ratio of 8000 or less was 27%. The acid value was 160 mgKOH / g.

<Synthesis Example 6 Polymer g: Synthesis of poly (cyclohexyl methacrylate-co-methacrylic acid)>
Into a condenser with a nitrogen-substituted condenser, a nitrogen introducing tube, a dropping funnel, a stirrer, and a thermometer, 80 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was added and 20 g of propylene glycol monomethyl ether (PGME) was added. The temperature was raised to ° C. A monomer solution is prepared by dissolving 71 g of cyclohexyl methacrylate and 29 g of methacrylic acid as a monomer and 3.5 g of 2,2′-azobis (2-methylbutyronitrile) as a catalyst in 50 g of propylene glycol monomethyl ether acetate, and placing it in a dropping funnel. It was. The monomer solution was dropped into the flask from the funnel over 3 hours. Thereafter, after heating for 4 hours while maintaining the temperature range of 91 ° C. to 93 ° C., the temperature was raised to 101 ° C. and heated for 1 hour. Thereafter, cooling was performed to obtain a PGMEA / PGME solution of polymer g. The structure of the polymer was confirmed by ¹ H-NMR using heavy DMSO as a solvent, and the composition ratio of cyclohexyl methacrylate units and methacrylic acid units in the polymer was 55/45 (molar ratio).

  The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of polymer g was 12700, and the molecular weight distribution was 2.5. In all polymer component peaks excluding the peaks of unreacted monomers and polymerization solvent components, the area ratio of polystyrene-equivalent weight average molecular weight (Mw) of 5000 or less was 23%, and the area ratio of 8000 or less was 39%. The acid value was 180 mgKOH / g.

<Synthesis Example 7 Polymer c: Synthesis of low molecular weight Cut poly (cyclohexyl methacrylate-co-methacrylic acid)>
In a dropping funnel and a flask equipped with a stirrer, 165 g of the PGMEA / PGME solution of polymer g obtained in Synthesis Example 6 was added, and 200 g of THF was further diluted. While stirring the polymer solution, 900 ml of hexane was dropped from the dropping funnel to the diluted polymer solution. The whole amount of hexane was dropped, and then allowed to stand, and the supernatant was removed to obtain a polymer precipitate. After adding 400 g of THF to the polymer precipitate and stirring and dissolving, 550 ml of hexane was added dropwise from the dropping funnel. The whole amount of hexane was dropped, and then allowed to stand, and the supernatant was removed to obtain a polymer precipitate. The polymer precipitate was vacuum-dried to obtain a powdery polymer c. The structure of the polymer was confirmed by ¹ H-NMR using heavy DMSO as a solvent, and the composition ratio of cyclohexyl methacrylate units and methacrylic acid units in the polymer was 55/45 (molar ratio).

  The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) of polymer c was 16000, and the molecular weight distribution was 2.3. In all polymer component peaks, the area ratio of polystyrene equivalent weight average molecular weight (Mw) of 5000 or less was 13%, and the area ratio of 8000 or less was 25%. The acid value was 180 mgKOH / g.

<Synthesis Example 8: Synthesis of polymer h>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred in a flask equipped with a nitrogen-substituted condenser, nitrogen introducing tube, dropping funnel, stirrer and thermometer while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2-methyl was further added. 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours.

Next, the reaction vessel was purged with air, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. . Thereafter, 28.5 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
The polymer thus obtained had a weight average molecular weight Mw measured by GPC of about 8400 and an acid value of 33 mgKOH / g.

<Synthesis Example 9: Synthesis of Polymer i>
10.0 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 45.0 parts by weight of benzyl methacrylate, and 45.0 parts by weight of methacrylic acid are added to 150 parts by weight of propylene glycol monomethyl ether acetate. After dissolution, 0.25 parts by weight of azobisisobutyronitrile was added under a nitrogen atmosphere, and after reacting at 70 ° C. for 7 hours, nitrogen bubbling was stopped and the temperature was raised to 100 ° C. and stirred for 1 hour. To this, 0.582 parts by weight of tetraethylammonium chloride was added, stirred and dissolved at 80 ° C., and a solution in which 11.1 parts by weight of glycidyl methacrylate and 18.5 parts by weight of propylene glycol monomethyl ether acetate were mixed for 1 hour. It was dripped. The reaction solution was stirred for 30 hours while maintaining at 80 ° C. to obtain an acrylic resin having a weight average molecular weight of 45,000 and an acid value of 105.

<Synthesis Example 10: Synthesis of Polymer j>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2.2′-azobis-2-methyl was added. 8.47 parts by weight of butyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 part by weight of trisdimethylaminomethylphenol and 0.12 part by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. . Thereafter, 56.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the polymer thus obtained was 8400, and the acid value was 80 mgKOH / g.

<Examples 1-4 and Comparative Examples 1-4>
[1] Pigment dispersion for colored resin composition
[1-1] Examples 1 to 4 and Comparative Examples 1 to 3
(A) C.I. I. Pigment Red 254 (average primary particle size: about 30 nm, pigment-1) 9.78 parts by weight, (B) as a polymer (in each comparative example, as an alternative to (B) polymer) listed in Table 2 3.26 parts by weight of polymer in terms of solid content, and also a polymer dispersant “Disperbyk2000” (acrylic block copolymer, manufactured by Big Chemie Co., Ltd.) and a B block having a quaternary ammonium base (dimethylbenzylammonium base) A block copolymer consisting of no A block, amine value 10 mgKOH / g (in terms of solids), acid value 0 mgKOH / g) in terms of solids 1.96 parts by weight, 60.00 as solvent Propylene glycol monomethyl ether acetate is added so as to be parts by weight, and 225 parts by weight of zirconia beads having a diameter of 0.5 mm are added to a stainless steel container. And dispersed for 6 hours with a paint shaker to prepare a red pigment dispersion.

[1-2] Comparative Example 4
(A) C.I. I. Pigment Red 254 (average primary particle diameter of about 50 nm, pigment-
2) is replaced with 9.78 parts by weight, (B) the polymer described in Table-2 is 3.26 parts by weight in terms of solids, and “Disperbyk2000” manufactured by BYK Chemie is in terms of solids. 1.96 parts by weight, propylene glycol monomethyl ether acetate is added so that the solvent becomes 60.00 parts by weight, 225 parts by weight of zirconia beads having a diameter of 0.5 mm are filled in a stainless steel container, and 6 hours with a paint shaker A red pigment dispersion was prepared by dispersing.

[2] Change in Viscosity of Pigment Dispersion For the pigment dispersion obtained in [1], (i) viscosity after storage for 1 day at 23 ° C. after production (preparation), and (ii) after production, at 23 ° C. The viscosity (20 rpm) after standing in a thermostat for 3 months was measured using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd.
For the pigment dispersions of the examples and comparative examples, the above (i) (absolute value of initial viscosity) and the rate of increase in viscosity from (i) to (ii) (change in viscosity over time) were compared. The results are shown in Table-2.

In addition, the absolute value of the initial viscosity was evaluated as “◯” when 50 mPa · s or less, and “x” when it exceeded 50 mPa · s. In addition, with respect to the change in viscosity over time, the case of less than 20% was marked with ◯, and the case of more than 20% was marked with x.
[3] Preparation of colored resin composition
[3-1] Examples 1 to 4 and Comparative Examples 1 to 4
The pigment dispersion obtained in [1-1] and [1-2] was mixed with other components as described in Table 1 to prepare a colored resin composition.

[4] Production of colored resin film
Each of the colored resin compositions obtained in [3] was spin-coated on a glass substrate for a color filter and prebaked for 3 minutes on a hot plate at 80 ° C. At the time of application, the number of rotations was adjusted so that the film thickness would be a color coordinate x = 0.650 after drying.
[5] Production of colored plate The colored resin film obtained in [4] is exposed to 60 mJ / cm ² with a high-pressure mercury lamp, and then a 0.04 wt% aqueous potassium hydroxide solution (developer temperature 23 ° C.) is used. Then, 0.25 MPa spray development was performed. After rinsing with sufficient water, it was dried with clean air. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes. The thickness of the colored resin film after drying was about 2.4 μm.

[6] Measurement of contrast ratio of colored plate FIGS. 2A and 2B are schematic diagrams for explaining a method of measuring the chromaticity of parallel transmitted light and orthogonal transmitted light of the colored plate. It is. First, as shown in FIG. 2A, polarizing plates 33 and 35 are stacked on both sides of the colored plate obtained in the above [5] (hereinafter sometimes referred to as “colored plate 34”), and polarized. In a state where the polarization axes of the plates 33 and 35 are parallel to each other, the light L of the backlight 37 is applied from the side of the one polarizing plate 35 and the luminance Lp of the light transmitted through the other polarizing plate 33 (of the parallel transmitted light). Luminance) was measured using a color luminance meter “BM-5A” 32 manufactured by Topcon Technohouse under the condition of a 2 ° visual field.

Next, as shown in FIG. 2B, with the polarization axes of the polarizing plates 33 and 35 orthogonal to each other, the light 36 of the backlight 37 is applied from one polarizing plate 35 side, and the other polarizing plate 33. The luminance Lc (the luminance of the orthogonal transmitted light) transmitted through the light was measured with the color luminance meter 32 in the same manner as the above Lp.
A backlight 37 having an emission spectrum as shown in FIG. 1 was used. This spectrum was measured and calculated using a Konica Minolta spectral radiance meter CS-1000A and a filter “ND filter ND4” manufactured by Kenko in order to control the amount of light and facilitate the measurement.

The polarizing plates 33 and 35 have the spectral characteristics shown in FIG.
The contrast ratios of the colored plates of Examples and Comparative Examples obtained in [5] were calculated from the luminance Lp of parallel transmitted light and the luminance Lc of orthogonal transmitted light using the formula Lp / Lc. The results are shown in Table-2.

<Examples 5-6, Reference Examples 1-2, and Comparative Example 5>
[7] Pigment dispersion for colored resin composition
[7-1] Example 5 and Reference Example 1
[Preparation of pigment dispersion]
As pigments, 9.78 parts by weight of copper phthalocyanine pigment blue 15: 6, 3.26 parts by weight of polymer b in terms of solid content, and a polymer dispersant “Disperbyk 2000” (acrylic block copolymer, quaternary quaternary, manufactured by Big Chemie) AB block copolymer consisting of a B block having an ammonium base (dimethylbenzylammonium base) and an A block not having an amine base, the amine value is 10 mgKOH / g (in terms of solid content), and the acid value is 0 mgKOH / g) Was dispersed in a solid content, and 225 parts by weight of zirconia beads having a diameter of 0.5 mm as a solvent was filled in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.

[7-2] Example 6 and Reference Example 2
As pigments, 9.27 parts by weight of copper phthalocyanine pigment blue 15: 6, 3.09 parts by weight of polymer b in terms of solid content, and a polymer dispersant “Disperbyk2000” manufactured by BYK Chemie Co. as 2.64 in terms of solids content of the dispersant. A blue pigment dispersion was prepared in the same manner as in Example 5 and Reference Example 1 except that the amount was changed to parts by weight.

[7-3] Comparative Example 5
A blue pigment dispersion was prepared in the same manner as in Example 6 and Reference Example 2, except that 3.09 parts by weight of polymer f in terms of solid content was used instead of polymer b.
[8] Preparation of Colored Resin Composition Other components were mixed with the above pigment dispersions to prepare colored resin compositions shown in Tables 3 and 4.

[９]着色樹脂膜の製造
[９-１]着色樹脂膜の製造及び溶解時間の測定
あらかじめカラーフィルタ作成用ガラス基板にクロムを蒸着した後、２３０℃オーブンにて３０分間ポストベークを行った基板に、[８]で得られた着色樹脂組成物をそれぞれスピンコート塗布し、乾燥後、色座標ｙ=０.０７８となる膜厚になるよう、回転数を調整した。続いて、高圧水銀灯により８０ｍＪ／ｃｍ^２で露光した後、あらかじめ導電率が３.
２６ｍＳ／ｍに調製した炭酸ナトリウム水溶液（現像温度２６℃）を使用して０.０５Ｍ
Ｐａのスプレー現像を行った。尚、現像時間はあらかじめ測定した溶解時間が２５秒より短い際には４０秒現像を行い、溶解時間が２５秒より長い際はその溶解時間と比較して１５秒長く現像した。現像後、十分な純水で洗浄した後、クリーンエアにより乾燥した。その後、２３０℃オーブンにて３０分間ポストベークを行った後、着色樹脂膜の膜厚を測定したところおよそ２.２μｍであった。

[9] Manufacture of colored resin film
[9-1] Production of colored resin film and measurement of dissolution time It was obtained in [8] on a substrate that had been pre-baked in a 230 ° C oven for 30 minutes after chromium was vapor-deposited on a glass substrate for color filter preparation. Each of the colored resin compositions was applied by spin coating, and after drying, the number of revolutions was adjusted so that the film thickness would be the color coordinate y = 0.078. Subsequently, after exposure at 80 mJ / cm ² with a high-pressure mercury lamp, the conductivity is 3.
Using an aqueous sodium carbonate solution (development temperature 26 ° C.) adjusted to 26 mS / m, 0.05M
Pa spray development was performed. The development time was 40 seconds when the dissolution time measured in advance was shorter than 25 seconds, and 15 seconds longer than the dissolution time when the dissolution time was longer than 25 seconds. After development, the substrate was washed with sufficient pure water and then dried with clean air. Then, after performing post-baking for 30 minutes in 230 degreeC oven, when the film thickness of the colored resin film was measured, it was about 2.2 micrometers.

However, the dissolution time is that the colored resin composition in the unexposed area is completely dissolved in the developer when developed after applying, drying, and exposing the colored resin composition to the substrate by the above method. The time until the substrate is exposed.
[9-2] Measurement of developer stain on photocured portion After the substrate coated with the colored resin is exposed and developed for the development time described above, on the photocured portion remaining after development (FIG. ), The portion where the color changed locally with a 50 × optical microscope was observed as a developer stain. In FIG. 5, the left figure shows a pattern created by a linear mask pattern (width 5 mm, length 5 cm) after exposure and development, and the right figure shows the actual evaluation range (the dotted line is outside the evaluation range). . Since the thickness of the colored resin film in the 3.5 cm × 3.5 cm square frame in the 5 cm × 5 cm substrate is constant, the evaluation itself is based on the blackened portion in the square frame in the right diagram of FIG. I went. Specifically, less than 10% of the photocured portion blackened in the square frame, ◯, 10-30% Δ, and 30% or more x.

  Table 5 shows the results of investigation based on this evaluation method.

＜参考例１〜２：溶解時間と直線パターンの欠け評価＞
[１０]着色樹脂組成物の調製
前記の各顔料分散体に他の成分を混合して、表６および７で示す着色樹脂組成物を調製した。

<Reference Examples 1 and 2: Evaluation of chipping of dissolution time and linear pattern>
[10] Preparation of Colored Resin Composition Other components were mixed with the above pigment dispersions to prepare colored resin compositions shown in Tables 6 and 7.

  [10-1]

[１０-２]

[10-2]

[１１]着色樹脂膜の製造
[１１-１]着色樹脂膜の製造
カラーフィルタ作成用ガラス基板に上記の着色組成物をそれぞれスピンコート塗布し、乾燥後、色座標ｙ=０.１２０となる膜厚になるよう回転数を調整した。続いて、幅５０μｍ、長さ３０ｍｍの直線状パターンを有するフォトマスクを介して、高圧水銀灯により６０ｍＪ/ｃｍ^２で露光した後、現像温度を２３℃で０.２５ＭＰａのスプレー現像を行った。現像後、十分な純水で洗浄した後、クリーンエアにより乾燥した。その後、２３０℃オーブンにて３０分間ポストベークを行った後、着色樹脂膜の膜厚を測定したところおよそ１.８μｍであった。

[11] Manufacture of colored resin film
[11-1] Manufacture of colored resin film Each of the above colored compositions is spin-coated on a glass substrate for producing a color filter, and after drying, the number of revolutions is adjusted so that the color coordinate becomes y = 0.120. did. Subsequently, after exposure at 60 mJ / cm ² with a high-pressure mercury lamp through a photomask having a linear pattern with a width of 50 μm and a length of 30 mm, spray development was performed at a development temperature of 23 ° C. and 0.25 MPa. After development, the substrate was washed with sufficient pure water and then dried with clean air. Then, after performing post-baking for 30 minutes in 230 degreeC oven, when the film thickness of the colored resin film was measured, it was about 1.8 micrometers.

[11-2] Measurement of dissolution time of colored resin After exposure of a substrate coated with a colored resin, development with 0.04 wt% aqueous potassium hydroxide solution causes the colored composition in the unexposed area to be completely developed into the developer. The time from the dissolution to the exposure of the substrate was taken as the dissolution time. Specifically, the dissolution time was calculated based on the method described in [9-1] above.

[11-3] Evaluation of chipping of linear pattern Chip evaluation of a linear pattern was also performed on the colored resin compositions C4 and C5. Specifically, 10 patterns created by a linear mask pattern of 50 μm width and 3 mm length obtained in [11-1] were observed 10 times using an optical microscope, and the blue depression of the line Was counted as the number of bits. This was repeated twice. The results are shown in Table 8 below together with the dissolution time.

According to the present invention, it is possible to efficiently and stably disperse highly atomized pigments by controlling the weight average molecular weight of the polymer used in the colored resin composition. As a result, it is possible to provide a colored resin composition having high transmittance, high contrast, very excellent color characteristics, improved developer stains, and developability suitable for a plate making process. In addition, by providing the colored resin composition of the present invention, a color filter having a low film thickness can be produced, and a high-quality liquid crystal display device and an organic EL display using the obtained color filter substrate are provided. It can also be provided.

It is a figure showing the emission spectrum of the backlight 37 used in the Example. It is a typical figure for demonstrating the method to measure the chromaticity of the parallel transmission light and orthogonal transmission light of a colored plate in an Example. It is a figure which shows the spectral characteristics of the polarizing plates 33 and 35 used in the Example. It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention. It is a schematic diagram for demonstrating the evaluation method of the developing solution stain in an Example.

Explanation of symbols

32 color luminance meter
33, 35 Polarizing plate
34 Colored board
36 light
37 Backlight 10 Transparent support substrate
20 blue pixels
30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode
51 Hole injection layer 52 Hole transport layer 53 Light emitting layer
54 Electron injection layer 55 Cathode
100 Organic EL device
500 Organic light emitter

Claims (12)

(A) a pigment, (B) a polymer, (C) a solvent, (D) a dispersant and (F) a polymerizable monomer,
(B) In a chromatograph obtained by gel permeation chromatography (GPC) of a polymer, the area of a component having a polystyrene-equivalent weight average molecular weight (Mw) of 5000 or less excludes peak areas of unreacted polymerizable monomer and polymerization solvent. 20% or less of the total area ,
And (B) Mw of a polymer is 40000 or less, The colored resin composition characterized by the above-mentioned.   (B) In a chromatograph obtained by gel permeation chromatography (GPC) of a polymer, the area of a component having a polystyrene-equivalent weight average molecular weight (Mw) of 8000 or less excludes peak areas of unreacted polymerizable monomer and polymerization solvent. The colored resin composition according to claim 1, which is 35% or less based on the total area. The colored resin composition according to claim 1 or 2 , wherein the weight ratio of the pigment (A) to the dispersant (D) is 4 or more. (B) the polymer, and at least one or more hydrophobic group-containing vinyl monomer, one of claims 1 to 3 in which is a polymer of at least one type of hydrophilic group-containing vinyl monomer The colored resin composition according to item 1. The colored resin composition according to claim 4 , wherein the polymer (B) has a carboxyl group as at least one hydrophilic group. The colored resin composition according to claim 4 or 5 , wherein the hydrophilic group-containing vinyl monomer contains (meth) acrylic acid. The colored resin composition according to any one of claims 4 to 6 , wherein the acid value of the polymer (B) is 1 to 500 mgKOH / g. (E) The colored resin composition according to any one of claims 1 to 7, comprising a photopolymerization initiator and / or a thermal polymerization initiator. It is an object for color filters, The colored resin composition of any one of Claims 1-8 . A color filter characterized in that it comprises a pixel which is manufactured using the colored resin composition according to any one of claims 1-9. A liquid crystal display device comprising the color filter according to claim 10 . An organic EL display comprising the color filter according to claim 10 .

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