JP2014115545A - Photosensitive coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-containing photosensitive coloring composition which has high sensitivity while containing a dye and has high brightness after subjecting to heat treatment at 230°C and to provide a color filter having high brightness formed by using the photosensitive coloring composition.SOLUTION: There is provided a photosensitive coloring composition which comprises: (A) a coloring agent; (B) a binder resin; (C) a photopolymerization initiator: (D) a sensitizer; and (E) a photopolymerizable monomer, wherein (A) the coloring agent contains a dye, (C) the photopolymerization initiator contains [C1] an oxime ester compound and [C2] an acylphosphine oxide compound and (D) the sensitizer contains a benzophenone compound.

Description

  The present invention relates to a photosensitive coloring composition used for producing a color filter used in a color liquid crystal display device, a color imaging device, an organic EL display device, and the like, and a color including a filter segment formed using the same. It relates to filters.

  As an image display device using a color filter, for example, (A) a backlight as a light source, a liquid crystal as an optical shutter, and a combination of color filters having color adjustment functions (color conversion function, color separation function, color correction function, etc.) And (B) a synthetic white organic EL light source, and an organic EL display device comprising a combination of color filters having a color adjustment function (color conversion function, color separation function, color correction function, etc.).

  In the color liquid crystal display device of (A), a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light that has passed through the first polarizing plate and passes through the second polarizing plate. This is a display device that performs display by controlling the amount of light, and the type using twisted nematic (TN) type liquid crystal is the mainstream. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  In general, a color filter is formed in a fine strip (stripe) shape formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) are arranged in parallel or intersecting with each other, or the fine filter segments are arranged in a constant vertical and horizontal arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) has been used.

  A transparent electrode for driving a liquid crystal is generally formed on the color filter used in the color liquid crystal display device by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 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.

  The quality required for a color liquid crystal display device includes high image quality, low power consumption, and the like, and color filters with high brightness, high contrast, and high resolution are required to achieve them. In particular, in recent years, from the viewpoint of power consumption, the brightness of color filters has been increasing. When a color filter with high brightness is used, the light transmittance is high, so that the number of backlights that are light sources can be reduced and power consumption can be reduced.

  As the synthetic white light source of the organic EL display device of (B), there are a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having a number of peaks in the visible light region. Synthetic white light is obtained by mixing or layering.

  Since the organic EL display device can directly turn on / off the light source of the pixel by a TFT (thin film transistor) or the like, it is possible to perform black display by turning off the light emission of the designated pixel. Therefore, a deflecting plate used in the liquid crystal display device is not required in the light emitting device, and it is not necessary to control the liquid crystal body. For this reason, the amount of transmitted light in the display device increases, and energy consumption can be greatly reduced by turning off the light emitting device in black display. In addition, it is possible to reproduce true dark black, and the contrast ratio can be increased. As an organic EL color display device in which the problems in the liquid crystal display device are solved, for example, a product such as “XEL-1” manufactured by SONY is already on the market. (For example, see Patent Document 1)

  The organic EL display device is different from the liquid crystal color display device in that it has excellent display performance such as a high contrast ratio, a wide viewing angle, a fast response speed, and a wide color reproducibility. In particular, in order to obtain a high color gamut, it is necessary to increase the color purity of each color filter segment in the color filter. When the color purity is increased, the light use efficiency (lightness Y value) of the light source is lowered, and there is a problem that the power consumption increases. Therefore, in organic EL display devices, color filters with high brightness are required as in color liquid crystal display devices.

  In any of these display devices, attention has been focused on dye-based color materials in order to achieve high brightness that cannot be achieved with pigments in recent years. However, when a segment pattern is formed using a coloring composition containing a dye as a coloring agent, a high brightness can be obtained as compared with a coloring composition containing a coloring agent containing only a conventional pigment system, but sufficient coating is achieved. Since it is difficult to obtain a cured film, there are problems such as a change in hue due to the elution of the coloring composition into the developer, a pattern peeling due to a decrease in adhesion to the glass substrate, and a decrease in the remaining film rate.

  In particular, in a coloring composition for a color filter used in an organic EL display device, it is necessary to increase the amount of a coloring agent in the coloring composition in order to form a high color purity filter segment. Compared with the weak coloring power, a large amount of dye is required to achieve the same hue as the pigment. As a result, the above-mentioned problems appear remarkably.

  In order to solve such problems, it is necessary to increase the sensitivity of the coloring composition. Generally, (1) imparting a reactive double bond to the binder resin, and (2) a photopolymerizable monomer. Selection or increase of the monomer, (3) selection or increase of the high-sensitivity photopolymerization initiator, etc.

  However, there is a limit to the improvement in sensitivity only by providing a double bond to the binder resin, and when the amount of the photopolymerizable monomer is increased, problems such as tackiness occur. On the other hand, in increasing the amount of photopolymerization initiator, the effect of improving the sensitivity is great, but there is a problem that the brightness is lowered by coloring in the heat treatment step depending on the type of photopolymerization initiator.

Japanese Patent Laid-Open No. 2005-10091

  Therefore, in the present invention, a dye-containing photosensitive coloring composition that has high sensitivity while containing a dye and has high lightness even after heat treatment at 230 ° C., and a high-lightness color formed using the photosensitive coloring composition. The purpose is to provide a filter.

  As a result of intensive studies, the inventors of the present invention have high sensitivity while containing a dye by using a specific photopolymerization initiator (C) and a specific sensitizer (D). The inventors have found that a photosensitive coloring composition capable of forming a color filter with high brightness even after heat treatment can be obtained, and have reached the present invention.

  That is, the present invention contains a colorant (A), a binder resin (B), a photopolymerization initiator (C), a sensitizer (D), and a photopolymerizable monomer (E). A coloring composition, wherein the colorant (A) contains a dye, the photopolymerization initiator (C) contains an oxime ester compound [C1] and an acylphosphine oxide compound [C2], and is a sensitizer (D ) Contains a benzophenone compound.

  In addition, the present invention relates to the photosensitive coloring composition, wherein the content of the dye in the colorant (A) is 15% by weight or more based on the total amount of the colorant.

  The present invention also relates to the above photosensitive coloring composition, wherein the dye contains a salt-forming compound of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye.

  In the present invention, the xanthene acid dye is C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, and C.I. I. It is at least 1 sort (s) selected from the group which consists of Acid Red 388, It is related with the said photosensitive coloring composition characterized by the above-mentioned.

  In addition, the present invention relates to the photosensitive coloring composition, wherein the colorant (A) further contains a blue pigment.

  Moreover, this invention comprises the filter segment formed from the said photosensitive coloring composition on a base material, The color filter characterized by the above-mentioned.

  The photosensitive coloring composition of the present invention uses a specific photopolymerization initiator (C) and a specific sensitizer (D), so that even if it contains a dye, it is highly sensitive and after heat treatment at 230 ° C. A high brightness color filter can be formed.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.
Further, “CI” mentioned below means a color index (CI).

  The photosensitive coloring composition of the present invention comprises a colorant (A), a binder resin (B), a photopolymerization initiator (C), a sensitizer (D), and a photopolymerizable monomer (E). The colorant (A) contains a dye, the photopolymerization initiator (C) contains an oxime ester compound and an acyl phosphine oxide compound, and the sensitizer (D) contains Contains benzophenone compounds.

<Colorant (A)>
The photosensitive coloring composition of this invention contains the coloring agent (A), and can form the filter segment of each color which comprises a color filter.
As content of the said coloring agent, it is preferable that it is the range of 10 to 45 weight% on the basis of solid content of the photosensitive coloring composition, More preferably, it is the range of 15 to 40 weight%. When the content is 10% by weight or less, color reproducibility is insufficient when the color filter is used in a general film thickness range (about 1.0 to 3.0 μm). Moreover, when content is 45 weight% or more, the sensitivity fall of the photosensitive coloring composition will be caused, and pattern peeling will occur easily.

"dye"
The colorant (A) is characterized by containing a dye and can be used in combination with an organic or inorganic pigment. Moreover, dye can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
The content of the dye in the colorant is preferably 5% by weight or more and 100% by weight or less, more preferably 15% by weight or more, based on the total amount of the colorant (100% by weight). In the case of 5% by weight or more, the brightness improvement of the color filter becomes more effective.

  As the dye in the present invention, any of what is generally called a dye such as an oil-soluble dye, an acid dye, a direct dye, a basic dye, a mordant dye, and an acid mordant dye can be used. The dye may be used in the form of a lake, or may be in the form of a salt-forming compound of a dye and a nitrogen-containing compound.

Dyes have good spectral characteristics and excellent color developability, but their light resistance and heat resistance are problematic, and their characteristics are not sufficient for use as components for touch panels that require high reliability. There is a case.
Therefore, in order to improve these disadvantages, in the case of a basic dye, it is preferable to use a salt-forming compound salted with an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.
In the case of acidic dyes and direct dyes, a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, and the like, and a salt formed using a resin component having these functional groups It is preferable in terms of resistance to use as a salt compound, or to sulfonamid and use as a sulfonic acid amide compound.

  As dyes, xanthene dyes, diphenylmethane dyes, triphenylmethane dyes, quinoline dyes, thiazine dyes, thiazole dyes, flavin dyes, auramine dyes, safranine dyes, phloxine dyes, methylene blue dyes, etc. Can be used.

Among these, it is preferable to use a xanthene dye, a quinoline dye, or a triphenylmethane dye.
Xanthene dyes are preferred because they exhibit a red / purple color and when used in a red filter segment or a blue filter segment, the lightness becomes high. A quinoline dye is preferred because it exhibits a yellow color and has high brightness when used in a red filter segment or a green filter segment. Triphenylmethane dyes are preferred because they exhibit a blue color and become brighter when used in blue filter segments.

(Xanthene dyes)
The xanthene dye is red or purple and preferably has any form of an oil-soluble dye, an acid dye, a direct dye, or a basic dye. In addition, when these dyes are used in a rake form, such as inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amide compounds of acidic dyes, etc. Form may be sufficient.

Among these, it is preferable to contain at least one xanthene-based oil-soluble dye, xanthene-based acid dye, salt-forming compound of xanthene-based acid dye, or sulfonic acid amide compound of xanthene-based acid dye because of excellent hue.
Particularly preferred is a salt forming compound of a xanthene acid dye or a sulfonic acid amide compound of a xanthene acid dye because high heat resistance, light resistance and solvent resistance can be imparted. Among these, a salt forming compound of a xanthene acid dye is preferable.

A red or purple color means C.I. I. Solvent Red, C.I. Oil soluble dyes such as I. solvent violet, C.I. I. Basic Red, C.I. Basic dyes such as I. basic violet, C.I. I. Acid Red, C.I. Acid dyes such as I. acid violet, C.I. I. Direct Red, C.I. I. Direct dyes such as direct violet, and the like.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as a xanthene acid dye.

  The xanthene dye used in the present invention has a transmittance of 90% or more in the region of 650 nm in the transmission spectrum, a transmittance of 75% or more in the region of 600 nm, a transmittance of 5% or less in the region of 500 to 550 nm, 400 nm. In this region, the transmittance is preferably 70% or more. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

Of these, xanthene-based basic dyes and xanthene-based acid dyes have spectral characteristics with high transmittance at 400 to 450 nm, but are used for image display devices using color filters that require high reliability. In some cases, light resistance and heat resistance are problems, and the characteristics may not be sufficient.
Therefore, in order to improve these drawbacks, the xanthene-based basic dye is preferably a salt-forming compound obtained by salt formation using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.
In addition, xanthene-based acid dyes are chlorinated using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc., and a resin component having these functional groups to form a salt forming compound, From the viewpoint of resistance, it is preferable to use a salt-forming compound or a sulfonamidated sulfonic acid amide compound.

  Among these, a salt component of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye is preferable because of excellent hue and resistance, and further, a counter component that functions as a counter ion. It is more preferable to use a compound prepared by using a quaternary ammonium salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Of the xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and resistance.

Hereinafter, the form of the xanthene dye used in the present invention will be specifically described in detail.
(Xanthene oil-soluble dye)
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like.
Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

(Xanthene basic dye)
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.

(Xanthene acid dyes)
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

  The xanthene-based dye used in the present invention is preferably a salt-forming compound of a xanthene-based acid dye and a nitrogen-containing compound, and a xanthene-based acid dye prepared by chlorination using a quaternary ammonium salt as the nitrogen-containing compound. Since it is particularly preferable to use a salt compound or a xanthene-based acid dye after sulfonamidation, these two forms will be described in detail below.

(Salt-forming compounds of xanthene acid dyes)
In the present invention, the xanthene-based acidic dye is formed by chlorination using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc., and a resin component having these functional groups, Since it can provide high heat resistance, light resistance, and solvent resistance, it is preferable to use this salt-forming compound.

  Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

-Salt-forming compound composed of xanthene-based acid dye and quaternary ammonium salt compound In the present invention, the salt-forming compound composed of the above-mentioned xanthene-based acid dye and quaternary ammonium salt compound is used for heat resistance and light resistance. From the viewpoint of solvent resistance, it is most preferable.

Quaternary ammonium salt compound A quaternary ammonium salt compound has an amino group, and its cation part becomes a counter of a xanthene acid dye.

  A preferred form of the quaternary ammonium salt compound that is a counter component of the salt-forming compound is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is necessary not to inhibit color development of the dye component and to cause no color change.

The molecular weight of the cation moiety serving as a counter for the quaternary ammonium salt compound is preferably in the range of 190 to 900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (1). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and the solubility in a solvent may be further lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the coloring component in the molecule is lowered, so that the color developability is lowered and the lightness is also lowered. More preferably, the molecular weight of the cation moiety is in the range of 240 to 850, and particularly preferably in the range of 350 to 800.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

  Moreover, it is preferable to use the compound represented by following General formula (1) as a quaternary ammonium salt compound.

[一般式（１）中、Ｒ₁〜Ｒ₄は、それぞれ独立に、炭素数１〜２０のアルキル基またはベンジル基を示し、Ｒ₁、Ｒ₂、Ｒ₃、又はＲ₄の少なくとも２つが、Ｃの数が５〜２０個である。Ｙ^-は無機または有機のアニオンを表す。]

[In General Formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , or R ₄ are The number of C is 5-20. Y ^- is representative of an inorganic or organic anion. ]

The solubility with respect to a solvent becomes favorable because the number of C of the side chain of at least 2 of R < ₁ > -R < ₄ > shall be 5-20. When R _{1 to} R ₄ have 3 or more alkyl groups having a C number smaller than 5, the solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if an alkyl group having a C number exceeding 20 is present in the side chain, the color forming property of the salt-forming compound may be impaired.

The component of Y ⁻ constituting the anion of the quaternary ammonium salt compound may be an inorganic or organic anion, but is preferably a halogen, usually chlorine.

Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (with a molecular weight of the cation moiety of 74), tetraethylammonium chloride (with a molecular weight of the cation moiety of 122), and monostearyltrimethylammonium chloride (with a molecular weight of the cation moiety). 312), distearyldimethylammonium chloride (cation part molecular weight 550), tristearyl monomethylammonium chloride (cation part molecular weight 788), cetyltrimethylammonium chloride (cation part molecular weight 284), trioctylmethylammonium chloride ( The molecular weight of the cation moiety is 368), dioctyldimethylammonium chloride (the molecular weight of the cation moiety is 270), monolauryltrimethyla Monium chloride (cation part molecular weight 228), dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride (cation part molecular weight 536), triamylbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium chloride (cation part molecular weight 612), benzyldimethylstearylammonium chloride (Molecular weight of the cation moiety is 388) and benzyldimethyloctyl ammonium chloride (molecular weight of the cation moiety is 248) , Or dialkyl (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride (hydrogenated tallow) (molecular weight of the cationic moiety is from 438 to 550) is preferably used and the like.

As products, Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Kao Corporation, Lion Corporation's Arcade 210-80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75 or 2HP flakes and the like, among others QUARTAMIN D86P (distearyldimethylammonium chloride), or Arquad 2HT-75 (di (alkyl C ₁₄ -C ₁₈₎ dimethyl ammonium chloride) Etc. are preferable.

The quaternary ammonium salt compound may be in the form of a resin having a cationic group, particularly an amino group or an ammonium group in the side chain, and capable of forming a quaternary ammonium salt structure by reacting and salting with a xanthene acid dye. . (See Reference 1)
(Reference 1) Japanese Patent Application No. 2011-150752

Resin having a cationic group in the side chain The quaternary ammonium salt compound may be in the form of a resin. The resin having a cationic group in the side chain is a vinyl resin containing a structural unit represented by the following general formula (2), and the cationic group in the general formula (2) is an anion of a xanthene acid dye. A salt-forming compound can be obtained by forming a salt with a functional group.

［一般式（２）中、Ｒ₅は水素原子、または置換もしくは無置換のアルキル基を表す。Ｒ₆〜Ｒ₈は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、または置換されていてもよいアリール基を表し、Ｒ₆〜Ｒ₈のうち２つが互いに結合して環を形成しても良い。Ｑはアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ₉−、−ＣＯＯ−Ｒ₉−を表し、Ｒ₉はアルキレン基を表す。Ｙ^-は無機または有機のアニオンを表す。］

[In General Formula (2), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{6 to} R ₈ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{6 to} R ₈ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₉ —, —COO—R ₉ —, and R ₉ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

Method for Producing Salt-Forming Compound A salt-forming compound comprising a xanthene acid dye and a quaternary ammonium salt compound can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, after the xanthene acid dye is dissolved in water, the quaternary ammonium salt compound is added and the chlorination treatment may be performed while stirring. Here, the sulfonic acid group (—SO ₃ H), sodium sulfonate group (—SO ₃ Na) part in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

  The salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (2) and a xanthene acid dye are dissolved, It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain represented by the formula (2) and an aqueous solution of a xanthene acid dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the xanthene acid dye are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the xanthene-based acidic dye is water-soluble and can be removed by washing with water. The resin having a cationic group in the side chain to be used and the xanthene acid dye may be used alone or in a plurality of types having different structures.

Examples of the salt-forming compound include C.I. I. Acid Red 289 and C.I. I. By using a salt-forming compound of Acid Red 52 and a quaternary ammonium salt compound having a molecular weight of the counter cation moiety of 350 to 800, it has excellent solvent solubility and is more heat resistant when used in combination with a pigment described later. Excellent in light resistance, light resistance and solvent resistance. In addition, it is presumed that the salt formation compound that is favorable when used in combination with the pigment is adsorbed on the pigment while being dissolved and dispersed in the solvent. At this time, the primary particle diameter of the pigment is preferably 20 to 100 nm.
Although the coloring composition of this invention is mentioned later, the form of the red coloring composition used together with the blue coloring composition used together with a blue pigment and the red pigment is preferable.

(Sulphonic acid amide compound of xanthene acid dye)
The xanthene-based acid dye in the present invention is preferably sulfonated to give a sulfonic acid amide compound because high heat resistance, light resistance, and solvent resistance can be imparted.
The sulfonic acid amide compound of a xanthene acid dye that can be preferably used for the colorant of the present invention has —SO ₃ H, —SO ₃ Na, for example, C.I. I. Acid Red 52, C.I. I. A xanthene acid dye such as Acid Red 289 can be chlorinated by a conventional method to convert —SO ₃ H to —SO ₂ Cl, and this compound can be produced by reacting with an amine having an —NH ₂ group.

Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
For example, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.

(Diphenylmethane dye and triphenylmethane dye xanthene dye)
The diphenylmethane dye and the triphenylmethane dye are blue (blue) dyes and have spectral characteristics having high transmittance at 400 to 440 nm.

(Diphenylmethane acid dyes and triphenylmethane acid dyes)
Examples of the diphenylmethane acid dyes and triphenylmethane acid dyes include Food Blue No. 101 (CI Acid Blue 1), Acid Pure Blue (CI Acid Blue 3), and Lake Blue I (C.I. Acid Blue 5), Lake Blue II (C.I. Acid Blue 7), Food Blue No. 1 (C.I. Acid Blue 9), C.I. I. Acid Blue 22, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. It is preferable to use Acid Blue 109.

(Diphenylmethane basic dye and triphenylmethane basic dye)
The diphenylmethane-based basic dye and the triphenylmethane-based basic dye are colored when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminotriphenylmethane-based basic dye is preferable in terms of good blue, red and green coloring. .
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Diaminotriphenylmethane basic dye, Triaminotriphenylmethane basic The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable. Further, diphenylnaphthylmethane basic dye and / or triphenylmethane basic dye are preferable.

  Specifically, C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 25 (Basic Blue GO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green), C.I. I. Basic violet 1 (methyl violet), 3 (crystal violet), 14 (Magenta) and the like.

(Raking of diphenyl and triphenylmethane dyes)
As a form in which a triarylmethane dye is raked, specifically, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. CI pigment blue 62, CI pigment violet 3, CI pigment violet 27, CI pigment violet 39, and the like.

More specifically, C.I. Pigment Blue 1, C.I. Pigment Violet 3, C.I. And CI pigment violet 39. Or C.I. I. Basic Blue 26, C.I. I. Basic Blue 7, C.I. I. Basic violet 1, C.I. I. Basic violet 3 (crystal violet) raked with phosphotungsten / molybdic acid.
Among these, C.I. I. Pigment Blue 1 is preferably used.

(Quinoline dyes)
Examples of quinoline dyes include C.I. I. Acid Yellow 2, C.I. I. Acid Yellow 3, C.I. I. Acid Yellow 5, C.I. I. Direct Yellow 5, C.I. I. Direct Yellow 119, C.I. Examples thereof include commercially available dyes such as I. Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Disperse Yellow 160, and Acid Yellow 3. Among these, C.I. containing a benzoquinoline skeleton. I. Acid Yellow 5 is preferable in terms of brightness.

(Other dyes)
As thiazine-based dyes, Lath's Violet obtained by oxidizing P-phenylenediamine in the presence of hydrogen sulfide under FeCl ₂ , methylene blue, methylene green B, C.I. basic blue 9, 17, 24, 25, Solvent Blue 8, CI Basic Green 5, CI Direct Red 70, and the like.

  The thiazole dye is a dye having a thiazole ring, and specifically, CI basic yellow 1, CI basic violet 44, 46, CI basic blue 116, CI Acid Yellow 186, Direct Yellow 7, 8, 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, CI Direct Orange 18, CI Direct Red 11, etc. Is mentioned.

  Examples of flavin dyes include C.I. I. Basic yellow 1 etc. are mentioned.

  Examples of auramine dyes include C.I. I. Basic yellow 2, 3, etc. are mentioned.

  Examples of safranine dyes include C.I. I. Basic Red 2 etc. are mentioned.

  Examples of phloxine dyes include C.I. I. Basic red 12 etc. are mentioned.

  Examples of methylene blue dyes include C.I. I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), 25 (Basic Blue GO), 24 (New Methylene Blue NX) and the like.

《Other colorants》
The colorant [A] can be used in combination with inorganic and organic pigments.

  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. 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.

  In particular, when a colored composition is used for a blue filter segment, the spectral spectrum has a high transmittance in the vicinity of 425 to 500 nm having a characteristic peak of many backlights by using a blue pigment in combination. This is preferable because a high brightness can be obtained as a blue filter segment rather than a colorant combining a conventional blue pigment and other pigments.

  Examples of the green pigment 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 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. 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 185.

  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 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.

Examples of red pigments 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. It is particularly preferable to use Pigment Red 177.

<Miniaturization of pigment>
The pigment used in the present invention is preferably used after being refined, but the refinement method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used, and examples thereof are exemplified in the present invention. Thus, the salt milling process by the kneader method which is 1 type of wet grinding can be performed.

The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically 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.

<Binder resin (B)>
The binder resin (B) contained in the coloring composition of the present invention is one that disperses the coloring agent (A), or that is dyed or penetrated, and includes conventionally known thermoplastic resins, thermosetting resins, and the like. Can be mentioned. The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (lightness reduction) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  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 or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having an ethylenically unsaturated active double bond include polymers having reactive substituents such as hydroxy groups, carboxyl groups, amino groups, and reactive groups such as isocyanate groups, aldehyde groups, and epoxy groups. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a substituent or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly Ji glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, vinyl ethers such as isobutyl vinyl ethers, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When the binder resin (B) is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that functions as an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the colorant carrier and the solvent. The balance of the aromatic groups is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The binder resin (B) is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant (A). If it is less than 20 parts by weight, the film formability and various resistances are insufficient, and if it is more than 500 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

<Photopolymerization initiator (C)>
Since the photosensitive coloring composition of the present invention is cured by ultraviolet irradiation and forms a filter segment by a photolithographic method, a photopolymerization initiator (C) or the like is added to form a solvent development type or alkali development type colored resist material. Adjust with.
The photopolymerization initiator (C) includes an oxime ester compound [C1] and an acyl phosphine oxide compound [C2]. If necessary, other photopolymerization initiators can be used in combination.

  The content of these photopolymerization initiators (C) is preferably 0.5 to 20% by weight based on the solid content of the photosensitive coloring composition (100% by weight). If it is less than 0.5% by weight, the adhesion to the substrate is poor, and if it exceeds 20% by weight, there may be a problem in developability or a decrease in lightness after heat treatment at 230 ° C. From these viewpoints, 1 to 18% by weight is more preferable, and further preferably 1.5 to 15% by weight.

<< Oxime ester compound [C1] >>
Examples of the oxime ester compound [C1] include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ) Ethylidene) hydroxylamine and the like.
These compounds can be used alone or in combination of two or more at any ratio as required.

  Among them, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is preferable because a high residual film ratio can be obtained. In the blue coloring composition, a filter segment with high brightness can be obtained because of its low yellowing degree, so that 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) ] Is preferable.

<< Acylphosphine compound [C2] >>
Examples of the acylphosphine compound [C2] include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl 2,4,4-trimethyl-pentylphosphine oxide, represented by the chemical formula (3). And bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
These compounds can be used alone or in combination of two or more at any ratio as required.

  Among these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are preferable because the inside of the colored coating becomes harder and pattern peeling is less likely to occur. More preferred is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

<< Other photoinitiators >>
Examples of the photopolymerization initiator that can be used in combination include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2 -Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Phenyl] -2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methyl Ruthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Acetophenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, etc. Benzoin compounds, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra ( t-butyl par Benzophenone compounds such as xoxycarbonyl) benzophenone, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6- Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl -S-triazine, 2- (naphth-1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine compounds such as 6-triazine and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl)- Imidazole compounds such as 4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone Compounds, borate compounds, carbazole compounds, and the like.
These photopolymerization initiators may be used alone or in combination of two or more at any ratio as required.

<Sensitizer (D)>
The colored composition of the present invention is characterized by containing a benzophenone compound as a sensitizer in order to further enhance the reaction of the photopolymerization initiator.
The benzophenone compound is derived from its skeleton and exhibits absorption over a wide range of 300 to 400 nm, thereby enhancing the reaction of the photopolymerization initiator.

  The content of the sensitizer (D) is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (C) contained in the colored composition. From the viewpoint of photocurability and developability. Is more preferably 5 to 50 parts by weight.

<Benzophenone compound>
Examples of the benzophenone compound include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, and the like.
These compounds can be used alone or in combination of two or more at any ratio as required.

  Among these, 4,4′-bis (diethylamino) benzophenone is preferable because curing of the inside of the coating film is further promoted by enhancing the reaction of the photopolymerization initiator.

《Other sensitizers》
Other sensitizers that can be used in combination include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzopol Derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives , Spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenance Lenquinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butyl Tilperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like.
These sensitizers can be used alone or in combination of two or more at any ratio as required.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

<Photopolymerizable monomer (E)>
The photopolymerizable monomer (E) of the present invention includes a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include til (meth) acrylamide, N-vinylformamide, acrylonitrile, and isocyanurate compounds.
These photopolymerizable monomers can be used singly or in combination of two or more at any ratio as required.

  Among these, isocyanurate compounds are preferable because a color filter with high brightness can be obtained. In particular, compounds having a structure such as acryloyl group, allyl group, and epoxy group in the molecule (for example, tris- (2-acryloxyethyl) isocyanurate, 1,3,5-triglycidyl isocyanuric acid, etc.) cure the coating film. Is more preferable because it becomes stronger.

  The content of the photopolymerizable monomer (E) is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (A), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Organic solvent>
In the coloring composition of the present invention, the coloring agent (A) is sufficiently dispersed and permeated in the coloring agent carrier, and applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation of the filter segment. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

  The content of the organic solvent is such that the colored composition can be adjusted to an appropriate viscosity, and a filter segment having a desired uniform film thickness can be formed. Therefore, 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant (A). It is preferable to use it in the quantity.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 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-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, 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 Monopropyl 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These 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 alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate It is preferable to use glycol acetates such as ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the weight (100% by weight) of the total solid content of the photosensitive coloring composition. If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The photosensitive coloring composition of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or in combination of two or more at any ratio as required.

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. 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 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  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.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. 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- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, 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.

  As for content of a hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned.

  The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant (A).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The content of the adhesion improver 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.

<Method for producing colored composition>
The coloring composition of the present invention comprises a colorant (A) in a colorant carrier such as a binder resin (B) and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill. Using various dispersing means such as a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor, finely disperse to give a colorant dispersion, and if necessary, a binder resin ( B), photopolymerization initiator (C), sensitizer (D), photopolymerizable monomer (E), polyfunctional thiol, UV absorber, polymerization inhibitor, storage stabilizer, solvent, and other ingredients It can be produced by stirring. In the photosensitive coloring composition containing two or more kinds of colorants, the colorant dispersions may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. . In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

(Dispersing 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 great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  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, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a dye derivative is used, those having a quinophthalone skeleton and an azo skeleton are preferable from the viewpoint of lightness.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant (A) from the viewpoint of improving dispersibility. is there. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to 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 addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715 or Lactimon, Lactimon-WS or Bykumen, etc., Japan Lubrizol SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, manufactured by Ciba Japan , 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 45 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajimoto Fine Techno Co., Ltd. PB821, PB822, PB824, etc. are mentioned.

  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.

  When a resin-type dispersant and a surfactant are added, the amount 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 content 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 content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is provided with a filter segment and / or a black matrix formed from the photosensitive coloring composition of the present invention on a substrate, and a general color filter includes, for example, a black matrix, And red, green and blue filter segments. The filter segment may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As the base material of the color filter, glass plates such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc. with high transmittance for visible light, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A transparent substrate such as a resin plate or a reflective substrate can be used. These substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like. 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 for driving the liquid crystal after forming the panel.

  If the BM is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the BM, chromium, a 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, but is not limited thereto. It is also possible to form TFTs on the transparent substrate or the reflective substrate in advance and use it as a driving substrate for a liquid crystal display device, and to form pixels on it. A color filter in which a filter segment is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, so that the aperture ratio can be greatly increased and the image quality and low power consumption of the color liquid crystal display device can be achieved. Can do.

  The dry film thickness of the filter segment and the black matrix 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.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine 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.
In order to increase UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  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 for a liquid crystal display mode in which colorization is performed using a color filter such as.

The organic EL display device includes a color filter and an organic light emitter, and can be applied to, for example, a passive drive type organic EL display device and an active drive type organic EL display device.
The white light source at this time is not limited, and any of a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having many peaks in the visible light region can be used.

  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.

  Moreover, the measuring method of the weight average molecular weight (Mw) of resin and the ammonium salt value of resin which has a cationic group in a side chain 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 (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Ammonium salt value of a resin having a cationic group in the side chain)
The ammonium salt value of the resin having a cationic group in the side chain is a value converted to the equivalent of potassium hydroxide after being obtained by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator. Represents the ammonium salt value of the solid content.

  Subsequently, manufacturing method of binder resin solution used in Examples and Comparative Examples, manufacturing method of resin for salt-forming dye, manufacturing method of dye, manufacturing method of dye-containing solution, manufacturing method of micronized pigment, pigment dispersant solution A method for preparing the pigment and a method for producing the pigment dispersion are described.

<Method for producing binder 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 70.0 parts of propylene glycol monoethyl ether acetate, heated to 80 ° C., and the reaction vessel was filled with nitrogen. After the substitution, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) )) A mixture of 7.4 parts and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.
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-1) which is an alkali-soluble resin.

(Acrylic resin solution (B-2))
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight, and the acrylic resin solution (B -2) was prepared. The weight average molecular weight (Mw) was 18000.

(Acrylic resin solution (B-3))
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 100 parts of propylene glycol monomethyl ether acetate, heated to 120 ° C., purged with nitrogen in the flask, and then dropped. From the tube, a mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours.
The inside of the flask was purged with air, and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. Then, the reaction was terminated, and a resin solution having a weight average molecular weight of about 12,000 was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40%, and a resin solution (B-3) A solution was prepared.

<Method for producing salt dye resin>
(Preparation of resin 1 having a cationic group in the side chain)
74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethylmethyl chloride methacrylate, and 15.6 parts of methyl ethyl ketone were homogenized. Thereafter, the mixture was placed in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 1 having a cationic group in the side chain whose resin component was 40% by weight. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Preparation of resin 2 having a cationic group in the side chain)
74.1 parts of isopropyl alcohol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 15.7 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, 15.0 parts of hydroxyethyl methacrylate, methacrylic acid After 2.5 parts and 15.6 parts of methyl ethyl ketone were made uniform, they were charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain Resin 2 having a cationic group in the side chain whose resin component was 40% by weight. The ammonium salt value of the obtained resin was 33 mgKOH / g.

<Dye production method>
《Xanthene dyes》
(Xanthene dye (A-1))
In the following procedure, C.I. I. A xanthene dye (A-1), which is a xanthene salt forming compound composed of Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced.
51 parts of vinyl-based resin 1 was added to 2000 parts of water, and after sufficient stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A xanthene dye (A-1), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Xanthene dye (A-2))
In the following procedure, C.I. I. A xanthene dye (A-2), which is a salt-forming compound composed of Acid Red 52 and Resin 2 having a cationic group in the side chain, was produced.
51 parts of the resin 2 having a cationic group was added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A xanthene dye (A-2), which is a salt-forming compound of Acid Red 52 and Resin 2 having a cationic group in the side chain, was obtained. At this time, C.I. in the xanthene dye (A-2) was obtained. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Xanthene dye (A-3))
In the following procedure, C.I. I. A xanthene dye (A-3), which is a salt-forming compound composed of Acid Red 289 and Resin 1 having a cationic group in the side chain, was produced.
88 parts of the resin 1 having a cationic group in the side chain was added to 2000 parts of a 10% methanol aqueous solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise to the previous resin solution little by little. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 43 parts of C.I. I. A xanthene dye (A-3), which is a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. in the xanthene dye (A-3) was obtained. I. The content of the effective pigment component derived from Acid Red 289 was 25% by weight.

(Xanthene dye (A-4))
In the following procedure, C.I. I. A xanthene dye (A-4), which is a salt-forming compound composed of Acid Red 52 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety is 550), was prepared.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, mixed and stirred sufficiently, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A xanthene dye (A-4), which is a salt-forming compound of Acid Red 52 and distearyldimethylammonium chloride, was obtained. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Xanthene dye (A-5))
In the following procedure, C.I. I. A xanthene dye (A-5), which is a salt-forming compound composed of Acid Red 52 and dialkyl (alkyl is C14 to C18) dimethylammonium chloride (Arcade 2HT-75) (the molecular weight of the cation moiety is 438 to 550), is prepared. did.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, mixed and stirred sufficiently, heated to 70 to 90 ° C., and then Arcard 2HT-75 is added dropwise little by little. Arcade 2HT-75 may be dissolved in water and used as an aqueous solution. After dropping Arcade 2HT-75, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A xanthene dye (A-5), which is a salt-forming compound of Acid Red 52 and dialkyl (alkyl is C14 to C18) dimethylammonium chloride, was obtained. At this time, C.I. in the xanthene dye (A-5) was obtained. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

(Xanthene dye (A-6))
In the following procedure, C.I. I. A xanthene dye (A-6), which is a salt-forming compound composed of Acid Red 87 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety is 550), was prepared.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 87 is dissolved, sufficiently mixed and stirred, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A xanthene dye (A-6), which is a salt-forming compound of Acid Red 87 and distearyldimethylammonium chloride, was obtained. At this time, C.I. in the xanthene dye (A-6) was obtained. I. The content of the effective pigment component derived from Acid Red 87 was 25% by weight.

(Xanthene dye (A-7))
As a sulfonic acid amide compound of a xanthene acid dye, C.I. I. Acid Red 52 was converted to a sulfonyl chloride by a conventional method and then reacted with a theoretical equivalent of 2-ethylhexylamine in dioxane to obtain C.I. I. A xanthene dye (A-7) which is a sulfonic acid amide compound of Acid Red 52 was obtained. (Based on the description in JP-A-6-194828.) At this time, C.I. I. The content of the effective pigment component derived from Acid Red 52 was 25% by weight.

《Triphenylmethane dye》
(Triphenylmethane dye (A-8))
2-Amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) is dissolved in a 9 mol% sodium hydroxide solution and sufficiently mixed and stirred to obtain its sodium salt. This 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) sodium salt aqueous solution is heated to 85 ° C., and then Victoria Pure Blue dye (CI Basic Blue 7) is added dropwise little by little. The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After the Victoria pure blue dye is added dropwise, the mixture is stirred at 85 ° C. for 55 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and is a salt-forming compound of Victoria pure blue dye and 2-amino-1-naphthalenesulfonic acid (tobias acid) The triphenylmethane dye (A-8) was obtained. At this time, C.I. in the triphenylmethane dye (A-8) was obtained. I. The content of the effective pigment component derived from Basic Blue 7 was 60% by weight.

<Quinoline dye>
(Preparation of quinoline dye (A-9))
In the following procedure, C.I. I. A quinoline dye (A-9), which is a salt-forming compound comprising Acid Yellow 5 and Resin 1 having a cationic group in the side chain, was prepared.
The resin 1 having a cationic group in the side chain of 51 parts is added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. Prepare an aqueous solution in which Acid Yellow 5 is dissolved, and add dropwise to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 32 parts of Acid Yellow 5 and side chains are cations. A quinoline dye (A-9), which is a salt-forming compound with the resin 1 having a functional group, was obtained. At this time, C.I. in the quinoline dye (A-9) was obtained. The content of the effective pigment component derived from I. Acid Yellow 5 was 33% by weight.

<Method for producing dye-containing solution>
(Preparation of dye-containing solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a dye-containing solution (DA-1) containing a xanthene dye.

Xanthene dye (A-1): 20.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 80.0 parts

(Preparation of dye-containing solution (DA-2 to 7))
Hereinafter, except changing the xanthene dye (A-1) to the xanthene dyes (A-2 to 7) shown in Table 1, the xanthene dye was changed in the same manner as the dye-containing solution (DA-1). A dye-containing solution (DA-2 to 7) was prepared.

(Preparation of dye-containing solution (DA-8))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a dye-containing solution (DA-8) containing a triphenylmethane dye.

Triphenylmethane dye (A-8): 11.0 parts Acrylic resin solution (B-1): 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Preparation of dye-containing solution (DA-9))

The following mixture was stirred and mixed so as to be uniform and then filtered through a 5.0 μm filter to prepare a dye-containing solution (DA-9) containing a quinoline dye.

Quinoline dye (A-9): 11.0 parts Acrylic resin solution (B-1): 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

<Production method of fine pigment>
(Blue refined pigment (PB-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), 120 The mixture was kneaded 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 (PB-1) was obtained.

(Purple refinement treatment pigment (PV-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.) are charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. 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 processing pigment (PV-1).

(Red refined pigment (PR-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 (PR254) ("Irga Fore Red B-CF" manufactured by BASF), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C for 8 hours. Kneaded. The mixture was poured into 2000 parts 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 salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts of red refinement | purification processing pigments (PR-1).

(Red refined pigment (PR-2))
Anthraquinone red pigment C.I. I. 100 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. . The mixture was poured into 4000 parts 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 salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts of red refinement | purification processing pigments (PR-2).

(Green refined pigment (PG-1))
C. Halogenated copper phthalocyanine green pigment I. Pigment Green 36 (PG36) (“Rionol Green 6YK” manufactured by Toyocolor Co., Ltd.) 120 parts, 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 15 hours. did. The mixture was put into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of green refinement processing pigments (PG-1).

(Yellow refined pigment (PY-1))
Metal complex yellow pigment C.I. I. 100 parts of Pigment Yellow 150 (PY150) (LANXESS “E4GN”), 1500 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. The kneaded product is put into 5000 parts of warm water and stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. After drying for a while, 95 parts of yellow refined pigment (PY-1) was obtained.

<Method for preparing pigment dispersant solution>
A pigment dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) was diluted with propylene glycol monomethyl ether acetate to prepare a pigment dispersant solution having a nonvolatile content of 30% by weight.

<Method for producing pigment dispersion>
(Pigment dispersion (DB-1))
Uniformly 12.0 parts of blue refined pigment (PB-1), 32.5 parts of acrylic resin solution (B-1), 5 parts of pigment dispersant solution, and 50.5 parts of propylene glycol monomethyl ether acetate (PGMAc) The mixture was stirred and mixed, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 3 hours using zirconia beads having a diameter of 0.5 mm, and filtered with a 5 μm filter. A pigment dispersion (DB-1) was obtained.

(Pigment dispersion (DV-1, DR-1, DR-2, DG-1, DY-1))
The pigment dispersion (DV-1, DR) was prepared in the same manner as the pigment dispersion (DB-1) except that the blue refinement treatment pigment (PB-1) was changed to each color refinement treatment pigment shown in Table 2. -1, DR-2, DG-1, DY-1).

[Examples 1-18, Comparative Examples 1-12]
<Preparation of photosensitive coloring composition>
After the mixture (parts by weight) shown in Tables 3 to 7 was uniformly stirred and mixed, the mixture was filtered through a 1 μm filter, and the blue photosensitive coloring compositions (RB-1 to RB-1) of Examples 1 to 14 and Comparative Examples 1 to 6 were used. 20), green photosensitive coloring compositions (RG-1 to 5) of Examples 15 and 16 and Comparative Examples 8 and 9, red photosensitive coloring compositions (RR-) of Examples 17 to 19 and Comparative Examples 10 and 11 1-5) were produced.

Abbreviations in Tables 3 to 7 are shown below.
<Photopolymerizable monomer>
Photopolymerizable monomer a: Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Photopolymerizable monomer b: Tris- (2-acryloxyethyl) isocyanurate (“A-9300” manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Photopolymerization initiator>
<< Oxime ester compound [C1] >>
Photopolymerization initiator a: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“IRGACURE OXE-01” manufactured by BASF)
Photopolymerization initiator b: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
("IRGACURE OXE 02" manufactured by BASF)
<< Acylphosphine oxide compound [C2] >>
Photopolymerization initiator c: (2,4,6-trimethylbenzoyl-diphenylphosphine oxide, “LUCIRIN TPO” manufactured by BASF)
Photopolymerization initiator d: (acylphosphine oxide organic compound) bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide ("IRGACURE 819" manufactured by BASF)
<< Other photoinitiators >>
Photopolymerization initiator e: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“IRGACURE 379” manufactured by BASF)
Photopolymerization initiator f: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF)
<Sensitizer>
Sensitizer a: 4,4′-bis (diethylamino) benzophenone (“EAB-F” manufactured by Hodogaya Chemical)
Sensitizer b: 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)

<Solvent>
PGMAc: Propylene glycol monomethyl ether acetate

<Evaluation of photosensitive coloring composition>
About the obtained photosensitive coloring composition (RB-1-20, RG-1-5, RR-1-5), evaluation of a color characteristic, a remaining film rate, a sensitivity, and pattern peeling was performed by the following method. . The results are shown in Tables 8-10.

[Color characteristics evaluation]
The obtained blue photosensitive coloring composition (RB-1 to 20) is formed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm so that y = 0.06 in a C light source using a spin coater. Each blue coloring composition was applied to the substrate, and the substrate was baked at 230 ° C. for 20 minutes. Thereafter, the color characteristics (x, y, Y) of the obtained filter segment were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.).
Similarly, the green photosensitive coloring compositions (RG-1 to RG-5) were applied to a film thickness such that y = 0.600 using a C light source and evaluated.
Similarly, the red photosensitive coloring compositions (RR-1 to RR-5) were applied to a film thickness such that x = 0.640 in a C light source and evaluated.

<Residual film ratio>
The obtained colored composition for a color filter was applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 0.7 mm using a spin coater at a rotation speed at which the film thickness after drying was 3.0 μm, and the pressure was reduced. After drying, the thickness T1 of the colored film was measured. Then, exposure was performed with an integrated light quantity of 50 mJ / cm ² with ultraviolet rays having an illuminance of 30 mW / cm ² using a super high pressure mercury lamp through a photomask. Then, a colored film obtained by using a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. as a developer, developing by a shower developing method at a developer pressure of 0.1 mPa, and baking at 230 ° C. for 20 minutes in an oven. The film thickness T2 was measured.
In addition, as a film thickness meter, a surface shape measuring device DEKTAK150 (manufactured by ULVAC-ES) was used.

Using the film thicknesses T1 and T2 of the obtained colored film, the remaining film ratio (%) was calculated from the following formula, and four-stage evaluation was performed based on the following criteria. Δ is a level that is not problematic in practice, ○ is a level that is practically excellent, and ◎ is a level that is very good.
Remaining film ratio (%) = (T2 / T1) × 100

◎: 75% or more ○: 70% or more and less than 75% △: 60% or more and less than 70% ×: less than 60%

<Sensitivity at the time of patterning>
The photosensitive coloring composition was coated on a 100 mm × 100 mm, 0.7 mm thick glass substrate using a spin coater, and after drying under reduced pressure, a 3.0 μm coating film was obtained. Next, using an ultrahigh pressure mercury lamp, ultraviolet rays were exposed through a photomask having a stripe pattern of 100 μm width (pitch 200 μm). Thereafter, this substrate was developed by a shower developing method using a 00.2 wt% sodium carbonate aqueous solution at 23 ° C. as a developer at a developer pressure of 0.1 mPa, and heated at 150 ° C. for 30 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive composition, and this was set as an appropriate development time. The pattern film thickness at the formed 100 μm photomask portion was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure amount, the higher the sensitivity and the better the photosensitive composition. The rank of evaluation is as follows.

◎: Less than 50 mJ / cm ² : Good level ○: 50 mJ / cm ² or more and less than 100 mJ / cm ² : Inferior to ◎, but a practical level Δ: 100 mJ / cm ² or more: Level not suitable for practical use ×: Pattern cannot be formed: Level not suitable for practical use

<Evaluation of pattern peeling>
About the board | substrate produced for the said sensitivity evaluation, it observed and evaluated using the optical microscope about the pattern in a 100 micrometer photomask part. The rank of evaluation is as follows.

○: Good without peeling or chipping: Good level △: No peeling but partial chipping: Inferior to ○, but practical level ×: Many peelings and chipping: Unsuitable level for practical use

  As shown in Tables 8 to 10, the photopolymerization initiator (C) contains an oxime ester compound [C1] and an acylphosphine oxide compound [C2], and the sensitizer (D) contains a benzophenone compound. By using a coloring composition, the composition satisfies the photolithography characteristics such as the remaining film ratio, sensitivity, and pattern peeling while containing a dye, and exhibits high brightness.

In particular, when the photosensitive coloring compositions of Example 1 and Example 13 were compared, higher brightness was obtained in Example 13 using the isocyanurate compound as a photopolymerizable monomer.
Moreover, when the photosensitive coloring composition of Example 1 and Example 2, 3 was compared, when the photosensitive resin was included as binder resin, there was no pattern peeling and the sensitivity was more favorable.

From the above results, the photosensitive coloring composition of the present application can provide a colored film with excellent pattern shape and high brightness, and the colored film has excellent performance even when the dye content is high. I was able to confirm that As a result, it was possible to form a color filter with high brightness.
That is, the photosensitive coloring composition of the present invention can be preferably used not only in a color liquid crystal display device but also in a case where a thin film or a wide color gamut is required, such as a color imaging device and an organic EL display device. Is.

Claims (6)

  A coloring composition containing a colorant (A), a binder resin (B), a photopolymerization initiator (C), a sensitizer (D), and a photopolymerizable monomer (E). The colorant (A) contains a dye, the photopolymerization initiator (C) contains an oxime ester compound [C1] and an acyl phosphine oxide compound [C2], and the sensitizer (D) contains a benzophenone compound. A photosensitive coloring composition characterized by comprising:   The photosensitive coloring composition according to claim 1, wherein the content of the dye in the coloring agent (A) is 15% by weight or more based on the total amount of the coloring agent.   The photosensitive coloring composition according to claim 1 or 2, wherein the dye contains a salt-forming compound of a xanthene acid dye and / or a sulfonic acid amide compound of a xanthene acid dye.   Xanthene acid dyes are C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, and C.I. I. 4. The photosensitive coloring composition according to claim 3, wherein the photosensitive coloring composition is at least one selected from the group consisting of Acid Red 388.   The photosensitive coloring composition according to claim 1, wherein the colorant (A) further contains a blue pigment.   A color filter comprising a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 5 on a substrate.