JP2016151637A - Production method of filter segment for color filter, filter segment for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent generation of cracks or changes in a hue in a color layer and to achieve excellent lightness and a contrast ratio even when a positive resist etching system using a colored composition comprising an acrylic resin is employed.SOLUTION: A production method of a filter segment for a color filter is provided, which includes steps of: forming a coating film by using a colored composition comprising a colorant [A], an acrylic resin [B], and an organic solvent on a substrate (step (i)); applying a positive resist [C] on the coating film, exposing and patterning the resist by etching (step (ii)); and stripping the positive resist [C] remaining after the (step (ii)) by using a stripping solvent [D] (step (iii)). A difference in the solubility parameter (SP value) between the acrylic resin [B] and the stripping solvent [D] is 0.3 to 3.0 (cal/cm)).SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a color filter filter segment used in a color liquid crystal display device, a color image pickup tube element, and the like by an etching method, a color filter filter segment obtained using the same, and a color filter. .

In the liquid crystal display device, a liquid crystal material and a pixel are interposed between two polarizing plates, a voltage is applied to each pixel to change the alignment state of the liquid crystal material, and the degree of polarization of light passing through the first polarizing plate is changed. It is a display device that changes and controls the transmitted light passing through the second polarizing plate to display the screen.
By providing a color filter between the two polarizing plates, color display becomes possible, and it has come to be used for televisions, personal computers, monitors and the like.

  The color filter is provided with a grid-like light-shielding film black matrix (hereinafter referred to as BM) for the purpose of preventing color mixture of transmitted light and increasing display contrast on a transparent substrate such as a glass plate, and then a plurality of colors (usually red, Green and blue) filter segments are provided. The filter segments are as fine as several microns to several hundreds of microns, and the filter segments are arranged in the form of fine bands (stripes) of two or more different hues (stripe arrangement), or are arranged vertically and horizontally. (Delta arrangement) etc. The filter segment and the BM are formed by drying at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. by applying a coloring composition.

  In a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  Further, as a patterning method, a negative photosensitive coloring composition or a positive photosensitive coloring composition is used, and a photomask having a predetermined pattern by various radiations such as ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. The resist is exposed to a photo resist and baked as necessary. Thereafter, unnecessary portions are developed and removed, and the baking process is repeated. A photolithography method or a positive resist on a non-photosensitive coloring composition. Etching methods, etc. are known in which a photolithographic process is used, and after etching, a positive resist is peeled off to obtain a filter segment.

  In order to improve the color reproduction characteristics of color filters and the light-shielding property of black matrix, which are required in recent years, it is necessary to increase the content of the colorant in the photosensitive coloring composition or to increase the film thickness. . However, in such a method using a negative photosensitive coloring composition or a positive photosensitive coloring composition, sensitivity reduction, developability, and resolution are deteriorated in a method of increasing the content of the colorant. In the method of increasing the film thickness, the exposure light does not reach the bottom of the film and the pattern shape becomes defective.

  In addition, when a photopolymerization initiator is used for photolithographic processing by photocuring, coloring due to a color unique to the photopolymerization initiator, a decrease in heat resistance, a decrease in light transmittance, a decrease in resolution, and the like may occur. On the other hand, since patterning by etching is not easily affected by photocuring, it is possible to form a filter segment with an excellent pattern shape even when the colorant content is high or the film thickness is large. .

  However, in the etching method, a step of removing a positive resist that is no longer necessary is required, and resistance to a peeling solvent is required (for example, Patent Document 1). Therefore, as a resin of the coloring composition conventionally used for such an etching method, it is necessary to use a resin having excellent resistance such as polyimide made of polyamic acid or the like (for example, Patent Documents 2 to 4). ). On the other hand, when trying to perform patterning formation by an etching method with a coloring composition using an acrylic resin excellent in transparency, there are problems such as cracking, missing, or hue change in the pattern due to the peeling solvent. It was the current situation that happened.

JP 2001-188364 A JP 2000-136253 A JP 2003-121633 A JP 2009-051891 A

  The manufacturing method of the color filter of the present invention can achieve both excellent lightness and contrast ratio without occurrence of cracks or hue change in the colored layer even in a positive resist etching method using a coloring composition containing an acrylic resin. An object of the present invention is to provide a color filter that can be suitably used in the field of electronic materials that require high-precision processing.

  As a result of intensive investigations, the present inventors have determined that in a positive resist etching method using a colored composition containing an acrylic resin, the difference in solubility parameter (SP value) with the acrylic resin is within a specific range. The present inventors have found that the above-described problems can be solved by stripping the positive resist using the solvent [D], and have reached the present invention.

That is, the present invention includes a step (i) of forming a coating film on a substrate using a coloring composition containing a colorant [A], an acrylic resin [B], and an organic solvent, and a positive resist [C]. On the coating film, exposing and patterning by etching, and removing the positive resist [C] remaining after the step (ii) with a peeling solvent [D] (iii) The filter segment manufacturing method for color filter, wherein the difference in solubility parameter (= SP value) between the acrylic resin [B] and the release solvent [D] is 0.3 to 3.0 (cal / cm ³ ) ^{1 The present} invention relates to a method for producing a filter segment for a color filter, which is characterized by being ^{/ 2} .

  The present invention also relates to the method for producing a filter segment for a color filter, wherein the peeling solvent [D1] has a boiling point of 260 ° C. or lower.

  The present invention also relates to the method for producing a filter segment for a color filter, wherein the peeling solvent [D1] is an aliphatic alcohol or an aliphatic ester.

In the color filter filter segment, the solubility parameter (SP value) of the peeling solvent [D] is 8.0 to 11.0 (cal / cm ³ ) ^1/2 . It relates to a manufacturing method.

  Moreover, this invention relates to the filter segment for color filters manufactured by the said manufacturing method.

  The present invention also relates to a color filter including the filter segment.

  According to the production method of the present invention, even in a positive resist etching method using a colored composition using an acrylic resin, there is no occurrence of cracks or hue change in the colored layer, and it is possible to achieve both excellent brightness and contrast ratio. It becomes.

Hereinafter, the present invention will be described in detail.
Note that “CI” in this specification means a color index (CI).

"Method for manufacturing filter segments for color filters"
The method for producing a filter segment for a color filter according to the present invention includes a step (i) of forming a coating film using a coloring composition containing a colorant [A], an acrylic resin [B], and an organic solvent, and a positive resist. Step (ii) of applying and exposing [C] on the coating film, patterning by etching, and step of removing the positive resist [C] remaining after step (ii) with a peeling solvent [D] (iii) And a difference in solubility parameter (= SP value) between the acrylic resin [B] and the release solvent [D] is 0.3 to 3.0 (cal / cm ^3). The present invention relates to a method for producing a filter segment for a color filter, characterized in that it is ^1/2 .
Further, by using such a positive resist etching method, the coloring composition has a higher colorant than a negative photosensitive coloring composition or a method of directly patterning using a positive photosensitive coloring composition. Even if it is a density | concentration, in the photolithographic processing process, since it is not influenced by photocuring, it can be set as the thing excellent in patterning property.

<< Step (i) >>
Step (i) is a step of forming a coating film using the colored composition.
The coloring composition containing the colorant [A], the acrylic resin [B], and the organic solvent is coated on a base material such as a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, and the like. Is 0.2 to 10 μm, and is dried if necessary.

<< Step (ii) >>
Step (i) is a step in which a positive resist [C] is applied onto the coating film, exposed, and patterned by etching.
On the substrate coated with the colored composition obtained in the step (i), first, a positive resist [C] is applied to a dry film thickness of 0 by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so as to be 1 to 4.0 μm.

  Subsequently, the dried coating film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the coating film, if necessary.

  Thereafter, the filter segment can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove the dissolved portion (exposed portion) and forming a desired pattern by etching. Furthermore, in order to accelerate the thermal crosslinking of the filter segment formed by development, heating can be performed as necessary. According to the positive resist etching method, it is possible to form a filter segment with higher accuracy than the photolithography method.

In the development / etching, an organic alkali such as dimethylbenzylamine or triethanolamine is used as an alkali developer, and an aqueous solution such as sodium carbonate or sodium hydroxide can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

<Positive resist (C)>
In the resist stripping method of the present invention, the target resist can be generally applied to a known positive resist. The positive resist in the present invention includes a chemically amplified resist.

  When the typical thing of the resist which can apply the resist peeling solvent of this invention is illustrated, what consists of a quinonediazide type photosensitizer and alkali-soluble resin is mentioned in a positive type, for example.

  The resist material composed of the quinonediazide-based photosensitizer and the alkali-soluble resin is preferable for the application of the resist stripping solvent of the present invention. Examples of the agent and the alkali-soluble resin include 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, and 1,2-naphthoquinonediazide-5. -Sulphonic acids, esters or amides of these sulfonic acids, and alkali-soluble resins include polyvinylphenol, polyvinyl alcohol, acrylic acid or methacrylic acid copolymers such as phenol, o-cresol, m-cresol , P-cresol, xyle And Lumpur such one or more phenols, formaldehyde, etc. novolak resins prepared from aldehydes such as para-formaldehyde.

  A chemically amplified resist is also a preferable resist to which the resist stripping solvent of the present invention is applied. A chemically amplified resist generates an acid upon irradiation and forms a pattern by changing the solubility of the irradiated portion in the developer by a chemical change caused by the catalytic action of this acid. Containing an acid-generating compound to be generated and an acid-sensitive group-containing resin that decomposes in the presence of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, an alkali-soluble resin, a crosslinking agent, and an acid generator What consists of an agent is mentioned.

  The resist applied to the substrate is pre-baked, for example, on a hot plate to remove the solvent, and a resist film having a thickness of usually about 0.1 to 4.0 μm is formed. The pre-baking temperature varies depending on the type of solvent or resist used, and is usually 20 to 200 ° C., preferably about 50 to 150 ° C. The resist film is then exposed through a mask as necessary using a known irradiation device such as a high-pressure mercury lamp, metal halide lamp, ultra-high pressure mercury lamp, KrF excimer laser, ArF excimer laser, soft X-ray irradiation device, electron beam drawing device. After exposure, after baking is performed as necessary to improve developability, resolution, pattern shape, etc., development is performed, and a resist pattern is formed. The development of the resist is usually performed using an alkaline developer. As the alkaline developer, for example, an aqueous solution or aqueous solution of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide (TMAH), or the like is used.

<< Process (iii) >>
Step (iii) is a step of stripping the positive resist [C] remaining after step (ii) with a stripping solvent [D].
At this time, by using a release solvent having a specific solubility parameter (= SP value) as the release solvent [D], the brightness, A filter segment having an excellent contrast ratio can be obtained.

  As the peeling treatment method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  The obtained coating film may be heated and cured (post-baked) as necessary. The heating temperature is preferably in the range of 140 to 230 ° C., and a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. The dry film thickness of the filter segment is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm.

<Peeling solvent [D]>
As the peeling solvent [D], a conventionally known solvent can be used, and it is not particularly limited as long as it is a solvent capable of dissolving a positive resist, but the acrylic resin [B] contained in the coloring composition and the peeling solvent [D] The difference in solubility parameter (= SP value) of D] is 0.3 to 3.0 (cal / cm ³ ) ^1/2 .
By using such a peeling solvent [D], even if the acrylic resin [B] is used, it is possible to obtain a coating film that does not generate cracks or change in hue in the step of peeling the positive resist.
More preferably, the difference in solubility parameter (SP value) between the acrylic resin [B] and the peeling solvent [D] is 1.0 to 2.0 (cal / cm ³ ) ^1/2 . By being in this range, the colored composition can be hardly dissolved in the peeling solvent.

Further, the value of the solubility parameter (SP value) is preferably 8.0 to 13.0 (cal / cm ³ ) ^1/2 , and the solubility parameter (SP) of the acrylic resin [B] and the release solvent [D]. As long as the difference in value is 0.3 to 3.0 (cal / cm ³ ) ^1/2 , the solubility parameter (SP value) of the acrylic resin [B] is the solubility parameter ( It may be any of the case where it is larger than the SP value) or the case where the value of the solubility parameter (SP value) of the peeling solvent [D] is larger than the solubility parameter (SP value) of the acrylic resin [B].
More preferably, the value of the solubility parameter (SP value) is 8.0 to 11.0 (cal / cm ³ ) ^1/2 . By being in this range, the positive resist can be easily peeled off, and the peeled piece of the positive resist does not remain on the filter segment.

  Here, the solubility parameter (SP value) is an index indicating ease of dissolution of the non-electrolytic organic solvent, and values described in POLYMER HANDBOOK FOURTH EDITION Volume 2 (published by WILEY-INTERSCIENCE) can be used.

The peeling solvent [D] preferably has a boiling point of 260 ° C. or lower, more preferably 60 to 260 ° C., and still more preferably 85 to 200 ° C.
When the boiling point is higher than 260 ° C., the solvent tends to remain on the substrate after pattern formation, and the solvent may remain in the post-baking process to cause cracks on the pixels, which may be a problem when creating a panel. There is.
In addition, when the boiling point is lower than 60 ° C., the volatility is high, and the coating film may be dried before being taken out from the stripping solvent and moved to cleaning, so that the dissolved portion of the positive resist may remain.
By using such a stripping solvent, the positive resist is excellent in solubility, and the strip of the positive resist does not remain on the filter segment.

Specific examples of the peeling solvent [D] include <boiling point (° C.) / SP value (cal / cm ³ ) ^1/2 > and illustrated as diacetone alcohol <166 / 9.19>, 2-ethyl 1 -Butanol <147 / 10.5>, 1-hexanol <157 / 10.7>, 1-octanol <195 / 10.6>, 1-pentanol <138 / 11.1>, 1-heptanol <176 / 10.6>, 2-ethylhexanol <184 / 9.48>, dimethylacetamide <165 / 10.8>, isobutyl alcohol <108 / 10.5>, N, N-dimethylformamide <153 / 10.6> , Toluene <111 / 9.00>, tripropylene glycol <273 / 9.19>, butyl lactate <186 / 9.39>, ethyl lactate <155 / 10.0>, methylcyclohexanone <168 / 9.29> , Maleic acid di Ethyl <225 / 9.92>, acetonitrile <82 / 11.9>, tert-butyl alcohol <83 / 10.6>, sec-butyl alcohol <99 / 10.8>, hexane <69 / 7.30> , Octane <125 / 7.60>, butyl decanol stearylate <259 / 8.12>, ethylene glycol diethyl ether <83 / 8.31>, isobutyl acetate <118 / 8.31>, trimethyl-3,5 , 5-hexanol <194 / 8.41>, methyl amyl ketone <151 / 8.51>, diethyl oxalate <185 / 8.60>, tripropylene glycol <265 / 9.20>, diethyl ketone <101 / 8.80>, allyl alcohol <97 / 11.8>, benzyl alcohol <205 / 12.1>, furfuryl alcohol <170 / 12.5>, d Nord <78 / 12.7> methanol <65 / 14.5> formamide <210 / 19.2> Water <100 / 23.0> and the like, without limitation.

Further, among these peeling solvents [D], alcohols or esters are preferable, and aliphatic alcohols or aliphatic esters are more preferable because there are no spots on the pixels at the time of peeling.
Specific examples of such a peeling solvent include diacetone alcohol, 2-ethyl 1-butanol <, 1-hexanol, 1-octanol, 1-pentanol, 1-heptanol, 2-ethylhexanol, isobutyl alcohol, and tripropylene. Glycol, tert-butyl alcohol, sec-butyl alcohol, butyl decanol stearyl, trimethyl-3,5,5-hexanol, tripropylene glycol, ethanol, methanol, butyl lactate, ethyl lactate, diethyl maleate, acetonitrile, isobutyl acetate And diethyl oxalate.

  More preferably, it is an aliphatic alcohol having 3 or more carbon atoms or an aliphatic ester having 3 or more carbon atoms, and more preferably an aliphatic alcohol having 5 or more and 8 or less carbon atoms in order to improve the solubility of the positive resist. It is an aliphatic ester having 5 to 8 carbon atoms.

"Color filter"
Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a filter segment for a color filter produced by a method for producing a filter segment of the present invention using a colored composition on a base material such as a transparent substrate. The color filter comprises a black matrix, at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or a black matrix, at least one magenta filter segment, at least one cyan filter A segment, and at least one yellow filter segment.

  As the substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  If the black matrix is formed in advance before forming the filter segment on the substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used. A thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The dry film thickness of the filter segment is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

"Coloring composition"
The coloring composition of the present invention contains a colorant [A], an acrylic resin [B], and an organic solvent. By using the acrylic resin [B], a filter segment having excellent brightness can be obtained.

<Colorant [A]>
The coloring composition of the present invention includes, as the colorant [A], pigments such as inorganic pigments and organic pigments, oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, dyes such as acid mordant dyes, In the case where the dye is used after being raked, a form such as a salt-forming compound of the dye and the nitrogen-containing compound can be used. Of these, pigments having high color developability and high heat resistance are preferred, and organic pigments are usually used.
These colorants can be used singly or as a mixture of two or more at any ratio as required.

The content of the colorant [A] is preferably 5% by weight or more and less than 20% by weight in 100% by weight of the colored composition. When the content is in this range, it is preferable for expanding the color reproduction region.
The content of the colorant is preferably 5% by weight or more and less than 60% by weight in 100% by weight of the total solid content of the colored composition. According to the method for producing a positive etching resist of the present invention, it is possible to obtain a filter segment that is excellent not only in lightness and contrast ratio but also in pattern shape even when the colorant concentration is high.

  Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments such as copper phthalocyanine, aluminum phthalocyanine, copper halide phthalocyanine, and metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, Anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments Examples thereof include pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

Examples of red pigments that can be used include 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, 17 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.
Examples of orange pigments that work in the same way as red pigments include C.I. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61 can be used.
Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. It is particularly preferable to use Pigment Red 242.

  Examples of green pigments that can be used 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 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  Examples of blue pigments that can be used 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. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  Examples of yellow pigments that can be used 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. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, or 180.

  Examples of purple pigments that can be used 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 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

[Miniaturization of pigment]
The pigment used in the colored composition of the present invention is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Acrylic resin [B]>
The coloring composition of the present invention contains an acrylic resin [B]. By including the acrylic resin [B], the dispersion stability of the colored composition of the present invention becomes better, and when the colored pixel layer of the color filter is formed using the colored composition for a color filter, It is possible to obtain a colored pixel layer with a small amount of developability and good pattern shape.
Furthermore, the acrylic resin [B] is highly colorless and can provide a colored pixel layer with high brightness.

Moreover, the acrylic resin [B] of the present invention has a difference in solubility parameter (= SP value) between the acrylic resin [B] and the peeling solvent [D] of 0.3 to 3.0 (cal / cm ³ ). ^{By being 1/2,} it is possible to obtain a coating film in which cracks are not generated and hue is not changed in the step of peeling the positive resist.
More preferably, the acrylic resin [B] of the present invention has a difference in solubility parameter (SP value) between the acrylic resin [B] and the peeling solvent [D] of 1.0 to 2.0 (cal / cm ³ ). ^1/2 . By being in this range, the colored composition can be hardly dissolved in the peeling solvent.

The solubility parameter (SP value) of acrylic resin [B] is preferably 8.0 to 13.0 (cal / cm ³ ) ^1/2 , and acrylic resin [B] and release solvent [D ] Has a solubility parameter (SP value) difference of 0.3 to 3.0 (cal / cm ³ ) ^1/2 , the solubility parameter (SP value) of the acrylic resin [B] has a value of the peeling solvent [ Either the solubility parameter (SP value) of the release solvent [D] or the solubility parameter (SP value) of the acrylic resin [B] is greater than the solubility parameter (SP value) of the release solvent [D]. It may be.
More preferably, when the value of the solubility parameter (SP value) of the acrylic resin [B] is 8.5 to 11.0 (cal / cm ³ ) ^1/2 , in the step of peeling the positive resist, This is preferable because the object can be a coating film free from cracks, peeling spots, and hue changes.

Here, the solubility parameter of the resin is a value calculated by the Fedors method.
When two or more kinds of resins are mixed and used, the value of the solubility parameter of the mixed resin calculated from the following formula can be obtained as the solubility parameter of the resin.

_{δ Pmix = a 1 δ P1 +} a 2 δ P2 + a 3 δ P3 + ··· + a n δ Pn
δ _Pmix : solubility parameter of mixed resin δ _P1 : solubility parameter of resin 1 δ _P2 : solubility parameter of resin 2 δ _P3 : solubility parameter of resin 3
・
δ _Pn : Solubility parameter of resin n a ₁ : Weight fraction of resin 1 in mixed resin a ₂ : Weight fraction of resin 2 in mixed resin a ₃ : Weight fraction of resin 3 in mixed resin
・
a _n: weight fraction of the resin n in the mixed resin

The acrylic resin [B] preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.
Moreover, when using with the form of an alkali etching type coloring composition, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. It is also preferable to use a resin having an ethylenically unsaturated double bond.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group.
Specifically, an acrylic resin having an acidic group is preferably used as the alkali-soluble resin because of its high heat resistance and transparency.

  Examples of the resin having an ethylenically unsaturated double bond include resins having an ethylenically unsaturated double bond introduced by the following methods (i) and (ii).

(Method (i))
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

(Method (ii))
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

  The weight average molecular weight (Mw) of the acrylic resin [B] is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80,000 in order to disperse the colorant [A] preferably. It is a range. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  As the acid value of the acrylic resin [B], a resin having an acid value of 20 to 300 mgKOH / g is preferably used from the viewpoint of dispersibility, penetrability, developability, and resistance of the colorant. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The acrylic resin [B] is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the colorant [A] because the film formability and various resistances are good, and the colorant concentration is high and good. Since color characteristics can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  In addition, the colored composition of the present invention may contain other thermoplastic resin, curing agent, curing accelerator, and the like as necessary within the range not impairing the effects of the present invention. Other thermoplastic resins include, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited, and can react with thermosetting compounds. Any curing agent may be used as long as it is. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used.
These may be used alone or in combination of two or more.

<Organic solvent>
In the coloring composition of the present invention, the colorant [A] is sufficiently dispersed in a dye carrier such as an acrylic resin [B], and the dry film thickness is 0.2 to 10 μm on a transparent substrate such as a glass substrate. Used to facilitate the formation of filter segments.

Examples of the organic solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2- Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butane Diol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-di Chlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl Lucol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert -Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene Glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropylene Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl Ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl Ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These organic solvents can be used alone or in admixture of two or more at any ratio as required.

Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.
By using a colored composition containing an acrylic resin, amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc., which are generally used when polyimide resin is used, β- Compared with lactones such as propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone, the hue of the pigment is not impaired, and the brightness and contrast ratio are high. Filter segments can be formed.

  The organic solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5000 parts by weight, with respect to 100 parts by weight of the colorant [A] in the coloring composition.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling property of the colored composition on a substrate such as a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination.
In general, the leveling agent content is preferably 0.003 to 1.0 part by weight with respect to 100 parts by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate. Can be made.

  Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant [A] in the coloring composition.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.

<The manufacturing method of a coloring composition>
The coloring composition of the present invention comprises a coloring agent [A] in a coloring agent carrier such as an acrylic resin [B] and / or various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. A colorant dispersion is produced by finely dispersing the mixture using an acrylic resin [B], an organic solvent, a leveling agent, a storage stabilizer, and other components as necessary. Can be manufactured. Moreover, the coloring composition containing 2 or more types of coloring agents may be produced by mixing each coloring agent dispersion separately in a coloring agent carrier and / or an organic solvent.

When the colorant [A] is dispersed in the acrylic resin [B] and / or the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion, a coloring composition obtained by dispersing the pigment in a resin and / or solvent using the dispersion aid is used. If so, a color filter excellent in transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment in the colorant [A].

[Dispersion aid]
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing re-aggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has spectral characteristics and viscosity stability. Will be better.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving the dispersibility of the added colorant. It is. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, more preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

  The resin-type dispersant has a colorant affinity part that has the property of adsorbing to the added colorant, and a part that is compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., Ciba Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 , 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The amount of the resin-type dispersant and the surfactant added is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant [A]. . When the blending amount of the resin type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

  The colored composition is removed by means of centrifugal separation, sintering filter, membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to carry out.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

Moreover, the measuring method of the weight average molecular weight (Mw) of resin and the chromaticity of a coating film is as follows.
(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

  Then, the manufacturing method of the acrylic resin solution used for the Example and the comparative example, the refinement | purification process pigment, and a coloring agent dispersion is demonstrated.

<Method for producing acrylic resin solution>
(Acrylic resin solution (B-1))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device was charged with 40.0 parts of propylene glycol monoethyl ether acetate and 30.0 parts of 3-methoxybutanol and heated to 80 ° C. After warming and purging the inside of the reaction vessel with nitrogen, 0.4 part of 2,2′-azobisisobutyronitrile and 29.6 parts of ethylenically unsaturated monomer were added from the dropping tube with methacrylic acid (MAA): Methyl methacrylate (MMA) = 20 wt%: A mixture adjusted to 80 wt% was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 8,000.
After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the previously synthesized resin solution had a non-volatile content of 20% by weight. Ethyl ether acetate was added to obtain an acrylic resin solution (B-1).
The solubility parameter of this resin is 10.4 (cal / cm ³ ) ^1/2 .

(Acrylic resin solution (B-2))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 70.0 parts of propylene glycol monoethyl ether acetate, heated to 80 ° C., and the reaction vessel was filled with nitrogen. After the substitution, 3.8 parts of methacrylic acid, 4.1 parts of 2-hydroxyethyl methacrylate, 7.4 parts of benzyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix M-” manufactured by Toagosei Co., Ltd.) 110 ") and 7.4 parts of 2,2'-azobisisobutyronitrile (0.4 parts) were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 30,000.
After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the previously synthesized resin solution had a non-volatile content of 20% by weight. Ethyl ether acetate was added to obtain an acrylic resin solution (B-2) which is an alkali-soluble resin.
The solubility parameter of this resin is 11.4 (cal / cm ³ ) ^1/2 .

(Acrylic resin solution (B-3))
(Stage 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage. The mixture was added dropwise over 2.5 hours to conduct a polymerization reaction.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, The reaction was carried out for 5 hours to obtain a resin solution having a weight average molecular weight of about 12,000. The added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal, and the weight average molecular weight is about 13 1,000 resin solutions were obtained.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% to obtain an acrylic resin solution (B-3).

The weight ratio of the structural units in the resin solution (B-3) was as follows: tetrahydrophthalic anhydride: 22.0% by weight, styrene: 15.0% by weight, dicyclopentanyl methacrylate; 29.3% by weight, glycidyl Total of methacrylate and acrylic acid ester-linked to the glycidyl end; 37.4% by weight.
The solubility parameter of this resin is 10.9 (cal / cm ³ ) ^1/2 .

(Acrylic resin solution (B-4))
(Stage 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. As a catalyst required for the reaction of 74.6 parts of benzyl methacrylate, 28.3 parts of acrylic acid, 18.3 parts of dicyclopentanyl methacrylate, and the precursor at this stage, from the dropping tube at a temperature, 1.0 azobisisobutyronitrile. Part of the mixture was added dropwise over 2.5 hours to conduct a polymerization reaction.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 19.7 parts of glycidyl methacrylate and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as a catalyst required for the reaction of the precursor at this stage. Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12,500 was obtained.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% to obtain a resin solution (B-4).

The weight ratio of the structural units in the resin solution (B-4) was: acrylic acid; 13.0% by weight, benzyl methacrylate; 53.0% by weight, dicyclopentanyl methacrylate; 13% by weight, and ester-bonded to the acrylic acid terminal. Glycidyl methacrylate; 21.0% by weight.
The solubility parameter of this resin is 11.2 (cal / cm ³ ) ^1/2 .

(Acrylic resin solution (B-5))
A flask equipped with a condenser and a stirrer was charged with 3 parts of 2,2′-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate, and then 1,2,2,6,6-pentamethylpiperidyl methacrylate 1 Parts, 15 parts of methacrylic acid, 34 parts of 2-hydroxyethyl methacrylate, 20 parts of N-phenylmaleimide, 15 parts of styrene, 10 parts of benzyl methacrylate, 5 parts of n-butyl methacrylate and 2,4-diphenyl-4-4 as a molecular weight regulator 5 parts of methyl-1-pentene (trade name: NOFMER MSD, manufactured by Nippon Oil & Fats Co., Ltd.) was charged and purged with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain an acrylic resin solution having a weight average molecular weight of 12,500. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to obtain an acrylic resin solution (B-5) which is an alkali-soluble resin.
The solubility parameter of this resin is 11.6 (cal / cm ³ ) ^1/2 .

(Acrylic resin solution (B-6))
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of ethylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and monosuccinic acid. (2-methacryloyloxyethyl) 10 parts by weight, N-phenylmaleimide 30 parts by weight, benzyl methacrylate 25 parts by weight, styrene 20 parts by weight and α-methylstyrene dimer (chain transfer agent) 2.5 parts by weight, After substituting with nitrogen, the reaction solution was heated to 80 ° C. with gentle stirring and polymerized for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was continued for another hour, whereby the weight average molecular weight was increased. 12,000 acrylic resins were obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to obtain an acrylic resin solution (B-6) which is an alkali-soluble resin.
The solubility parameter of this resin is 10.9 (cal / cm ³ ) ^1/2 .

(Acrylic resin solution (B-7))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device was charged with 40.0 parts of propylene glycol monoethyl ether acetate and 30.0 parts of 3-methoxybutanol and heated to 80 ° C. After warming and substituting the inside of the reaction vessel with nitrogen, 0.4 parts of 2,2′-azobisisobutyronitrile and 29.6 parts of ethylenically unsaturated monomer were methyl methacrylate (MMA): A mixture adjusted to methacrylic acid (MAA): glycerin monomethacrylate (GLM) = 33 wt%: 15 wt%: 52 wt% was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 8,000.
After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the previously synthesized resin solution had a non-volatile content of 20% by weight. Ethyl ether acetate was added to obtain an acrylic resin solution (B-7).
The solubility parameter of this resin is 13.2 (cal / cm ³ ) ^1/2 .

<Manufacture of refined pigments>
(Red refined pigment (PR254-1))
Red pigment C.I. I. Pigment Red 254 (PR254) ("Irga Fore Red B-CF" manufactured by BASF) 152 parts, 8 parts of a pigment derivative of the chemical formula (1), 1600 parts of sodium chloride, and 190 parts of diethylene glycol 1 gallon kneader (Inoue Seisakusho) And kneaded at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 It was dried for 1 day at 0 ° C. to obtain a red refined pigment (PR254-1).

Chemical formula (1)

(Red refined pigment (PR177-1))
Red pigment C.I. I. 500 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 3500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a red-refined pigment (PR177-1) was obtained.

(Red refined pigment (PR242-1))
Red pigment C.I. I. 200 parts of Pigment Red 242 (“NOVOPERM SCARLET 4RF” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. As a result, a red refined pigment (PR242-1) was obtained.

(Green refined pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG58-1) was obtained.

(Yellow refined pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Blue refined pigment (PB15: 6-1))
Blue pigment C.I. I. Pigment Blue 15: 6 (PB15: 6) (“Lionol Blue ES” manufactured by Toyocolor Co., Ltd.) 500 parts, 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a blue refined pigment (PB15: 6-1) was obtained.

(Purple refinement treatment pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 500 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC all day and night, and obtained the purple refinement | purification processed pigment (PV23-1).

<Method for producing pigment dispersion>
(Red pigment dispersion (PR-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a red pigment dispersion (PR-1) was produced.

Red refined pigment (PR254-1): 12.0 parts resin type dispersant: 1.0 part ("EFKA4300" manufactured by BASF)
Acrylic resin solution (B-1): 35.0 parts Solvent PGMAC: 42.0 parts (Propylene glycol monomethyl ether acetate): 52.0 parts

(Red pigment dispersion (PR-2 to 3), yellow pigment dispersion (PY-1), green pigment dispersion (PG-1), blue pigment dispersion (PB-1 to 4), purple pigment dispersion ( PV-1))
The red pigment dispersion is the same as the red pigment dispersion (PR-1) except that the colorant, resin-type dispersant, acrylic resin solution, and solvent are changed to the compositions and blending amounts (parts by weight) shown in Table 1. Body (PR-2 to 3), yellow pigment dispersion (PY-1), green pigment dispersion (PG-1), blue pigment dispersion (PB-1 to 4), purple pigment dispersion (PV-1) Was made.

In Table 1, EFKA4300 and BYK-LPN6919 are as follows.
EFKA4300: “EFKA4300” manufactured by BASF
BYK-LPN6919: “BYK-LPN6919” manufactured by Big Chemie Japan

(Blue pigment dispersion (PB-5 to 10))
Disperse the blue pigment in the same manner as the red pigment dispersion (PR-1), except that the colorant, resin-type dispersant, acrylic resin solution, and solvent were changed to the compositions and blending amounts (parts by weight) shown in Table 2. A body (PB-5 to 10) was prepared.

<Method for producing colored composition>
(Coloring composition ((R-R1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a colored composition (R-R1).

Pigment dispersion (PR-1): 29.2 parts Acrylic resin solution (B-1): 36.3 parts Solvent: 34.5 parts Propylene glycol monomethyl ether acetate (PGMAC)

(Coloring composition (P-R2-3), (R-G1), (R-B1-12))
After stirring and mixing the mixture shown in Tables 3 to 5 and the blending amount (parts by weight) uniformly, the mixture was filtered through a 1 μm filter, and the coloring composition was the same as the coloring composition (R-R1). The product ((R-R1-3), (R-G1), (R-B1-12)) was obtained.

<Solubility parameter (SP value) and boiling point of peeling solvent [D]>
The SP value (cal / cm ³ ) ^1/2 and boiling point (° C.) of the stripping solvent used are shown.

[Example 1]
(Filter segment (F-R1))
<< Step (i) >>
The coloring composition (R-R1) is applied to a film thickness of x = 0.657 and y = 0.320 using a C light source on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater. Next, it was dried under reduced pressure, then heated at 70 ° C. for 20 minutes and allowed to cool to obtain a coating film.
<< Step (ii) >>
A positive resist (manufactured by AZ Electronic Materials Co., Ltd .: AZ P1350; PGMAC solution) was applied to the coating film by rotating it at 800 rpm for 10 seconds using a spin coater, and irradiated with 150 mJ / cm ² of ultraviolet rays. Next, spray development and etching were performed with an alkali developer composed of a 0.238 wt% tetramethylammonium hydroxide aqueous solution to remove the positive resist and the colored composition in the exposed portion, and then washed with ion-exchanged water.
The development and etching time was the time until the substrate surface was exposed.
<< Process (iii) >>
In order to peel off the positive resist remaining in the obtained coating film, the positive resist was peeled off by immersing in diethyl oxalate, which is a peeling solvent [D], for 2 minutes. The obtained coating film was heated in an oven at 230 ° C. for 20 minutes to obtain a filter segment (F-R1).

[Examples 2-3]
(Filter segment (F-R2 to F-R3))
Except having changed into the coloring composition described in Table 7, and peeling solvent [D], it carried out similarly to manufacture of the filter segment (F-R1), and obtained the filter segment (F-R2-F-R3).

[Example 4]
(Filter segment (F-G1)
In << Step (i) >> in the manufacture of the filter segment (F-R1), the colored composition described in Table 7 was applied to a film thickness of x = 0.290 and y = 0.600 with a C light source, A filter segment (F-G1) was obtained in the same manner as in the production of the filter segment (F-R1) except that the peeling solvent [D] in << Step (iii) >> was changed to the solvent described in Table 7.

[Examples 5 to 18, Comparative Examples 1 to 8]
(Filter segment (F-B1 to F-B20)
In << Step (i) >> in the production of the filter segment (F-R1), the colored composition described in Table 7 was applied to a film thickness of x = 0.141 and y = 0.084 with a C light source, A filter segment (F-B1 to F-B20) was obtained in the same manner as in the manufacture of the filter segment (F-R1) except that the peeling solvent in << Step (iii) >> was changed to the solvent described in Table 7. .

<Evaluation method>
The color characteristics, contrast ratio (CR) and peeling solvent resistance of the filter segments obtained in Examples and Comparative Examples were evaluated by the following methods. Table 7 shows the evaluation results.
[Brightness (Y)]
The brightness (Y) of the substrate obtained by producing the filter segment was measured with a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).

[Contrast ratio (CR)]
When the filter segment was prepared, three coated substrates were prepared so that the dry film thickness was about 2 μm by changing the rotation speed in << Step (i) >>. Thereafter, filter segments having different film thicknesses were obtained in the same manner as in << Step (ii) >> to << Step (iii) >>. The film thickness and the contrast ratio were measured, respectively, and the contrast ratio (CR) at a film thickness of 2 μm was determined from the three points by the primary correlation method.

[Positive resist persistence]
The remaining area of the positive resist was confirmed with a microscope (OLYMPUS Optical "BX-51"). The evaluation was performed by measuring the remaining area of the positive resist in a 50 μm × 50 μm pixel. The remaining area of the positive resist after creation of the filter segment of the colored composition was evaluated according to the following criteria.

◎: No remaining ○: Less than 100 μm ² Δ: 100 μm ² or more and less than 500 μm ² ×: 500 μm ² or more

[Peeling solvent resistance]
The peeling solvent resistance was evaluated by the following method based on hue change, presence or absence of cracks, and presence or absence of peeling spots.
<< L * (1), a * (1), b * () using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) for the chromaticity of the coating film obtained in << Step (i) >>. 1)] was measured. Further, the presence or absence of cracks and the presence or absence of peeling spots were confirmed with a microscope ("BX-51" manufactured by Olympus Optical Co., Ltd.).

[Hue change]
<< Chromaticity [L * (2), a * (2), b] after immersing the coating film finished up to "Step (ii)" in a peeling solvent described in Table 7 for 30 minutes and then washing with ion exchange water * (2)] was measured, and the color difference ΔE * ab was determined by the following equation (1).

Formula (1) ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1 )] ² ] ^1/2

The smaller the color difference ΔE * ab, the less the change in chromaticity before and after the filter segment creation of the coloring composition, and it can be said that the coloring composition has good peeling solvent resistance. Evaluation was made according to the following criteria.

◎: ΔE * ab is less than 0.5 ○: ΔE * ab is 0.5 or more and less than 1.0 Δ: ΔE * ab is 1.0 or more and less than 3.0 ×: ΔE * ab is 3.0 or more

[Presence of cracks]
Cracks were confirmed with a microscope (OLYMPUS Optical “BX-51”). For the evaluation of cracks, the number of cracks in a 50 μm × 50 μm pixel was measured. It can be said that the colored composition has few cracks before and after the production of the filter segment and has a good peeling solvent resistance. Evaluation was made according to the following criteria.

◎: No crack ○: Less than 10 △: 10 or more and less than 50 ×: 50 or more

[Peeling spots]
Peeling spots were confirmed with a microscope (OLYMPUS Optical “BX-51”). For the evaluation of the spot, the area of the spot in a 50 μm × 50 μm pixel was measured. It can be said that the coloring composition has few stains before and after the filter segment preparation and has a good peeling solvent resistance. Evaluation was made according to the following criteria.

◎: No stain ○: Less than 100 μm ² Δ: 100 μm ² or more and less than 500 μm ² ×: 500 μm ² or more

As shown in Table 7, if the difference between the SP value of the acrylic resin and the SP value of the peeling solvent is 0.3 to 3.0 (cal / cm ³ ) ^1/2 , a colored composition having excellent peeling solvent resistance is obtained. Furthermore, it was possible to obtain a filter segment with high brightness and high contrast ratio.

In particular, when the peeling solvent [D] is an aliphatic alcohol or an aliphatic ester, there is no peeling spot on the pixel at the time of peeling, and the solubility parameter (SP value) is 8.0 to 11.0 (cal / In the case of cm ³ ) ^1/2 , the releasability was particularly excellent, and no positive resist remained.

On the other hand, if the difference between the SP value of the acrylic resin and the SP value of the peeling solvent is smaller than 0.3 (cal / cm ³ ) ^1/2 , the surface of the coloring composition is dissolved, and the resistance to the peeling solvent becomes poor. Lightness and low contrast ratio. In addition, when the difference between the SP value of the acrylic resin and the SP value of the peeling solvent is larger than 3.0 (cal / cm ³ ) ^1/2 , cracks and whitening occur on the surface of the colored composition, resulting in poor peeling solvent resistance. Low brightness and low contrast ratio.

<Color filter manufacturing method>
A black matrix was patterned on a glass substrate, and a red filter segment using a red colored composition (F-R1) was obtained by a method for producing a filter segment. Similarly, a green filter segment using the green coloring composition (F-G1) and a blue filter segment using the blue coloring composition (F-B1) were formed to obtain a color filter.
The obtained color filter had good peeling solvent resistance and good brightness and contrast ratio. Therefore, the color filter has good productivity and good pattern shape.

  Therefore, according to the present invention, a high-quality color filter can be produced in the filter segment manufacturing method using the positive resist etching method.

Claims (6)

A step (i) of forming a coating film on the substrate using a coloring composition containing a colorant [A], an acrylic resin [B], and an organic solvent, and a positive resist [C] on the coating film A filter for a color filter comprising: a step (ii) of applying, exposing to light, and patterning by etching; and a step (iii) of removing the positive resist [C] remaining after the step (ii) with a release solvent [D] A method for producing a segment, wherein a difference in solubility parameter (SP value) between the acrylic resin [B] and the peeling solvent [D] is 0.3 to 3.0 (cal / cm ³ ) ^1/2. A method for producing a filter segment for a color filter.   The method for producing a filter segment for a color filter according to claim 1, wherein the peeling solvent [D] has a boiling point of 260 ° C or lower.   The method for producing a filter segment for a color filter according to claim 1 or 2, wherein the peeling solvent [D] is an aliphatic alcohol or an aliphatic ester. The color according to any one of claims 1 to 3, wherein the solubility parameter (SP value) of the peeling solvent [D] is 8.0 to 11.0 (cal / cm ³ ) ^1/2. A method for producing a filter segment for a filter.   The filter segment for color filters manufactured by the manufacturing method of any one of Claims 1-4.   A color filter comprising the filter segment according to claim 5.