JP5736932B2 - Red coloring composition for color filter, and color filter - Google Patents

Description

  The present invention relates to a red coloring composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is. The red coloring composition can be applied to red and magenta color filters.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. 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.

  On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. 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.

  Quality items required for the color filter include contrast ratio and brightness. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.
Furthermore, as described above, since color liquid crystal devices have been used for televisions, personal computer monitors, etc., there is a demand for a wide color reproduction region and high reliability as well as higher contrast and higher brightness for color filters. It is high.

Also, C-MOS (Complementary Metal Oxide Semico
A color imaging tube element typified by nductor (complementary metal oxide semiconductor), CCD (Charge Coupled Device) or the like has a red filter layer (R), a green filter layer (G) and a light receiving element on the light receiving element. In general, color separation is performed by disposing color filters each having an additive mixed primary color filter segment of the blue filter layer (B). Further, since high sensitivity can be obtained compared to the primary color filter, a color filter having filter segments of cyan, magenta, and yellow (CMY) corresponding to the complementary colors of red, green, and blue is often used. Complementary color filters are often used in video cameras and the like that are difficult to use an auxiliary light source such as a flash.
In recent years, there is an increasing demand for high transmittance, that is, lightness and high reliability even for color filters used in color image pickup tube elements.

  Color filter manufacturing methods include dyeing methods using dyes and salt-forming dyes as colorants, dye dispersion methods, pigment dispersion methods using pigments as colorants, printing methods, electrodeposition methods, and inkjet methods. . Among these, the dyeing method or the dyeing and dispersing method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  In general, the pigment particles are subjected to a micronization treatment and a pigment dispersion in which the micronized pigment is brought close to the primary particles as much as possible is used to suppress light scattering by the pigment and achieve high contrast. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

  Conventionally, as colorants used for forming red filter segments (pixels) and magenta color filter segments (pixels), diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, and naphthol pigments that are generally excellent in durability and color tone Pigments, azo pigments and the like are often used.

  In a display device such as a liquid crystal display device using a conventional cold cathode tube type backlight, a combination of a diketopyrrolopyrrole pigment or an anthraquinone pigment and a quinophthalone pigment is combined with a red filter segment. A wide color display area could be achieved.

In the case of the magenta color filter segment, quinacridone pigments, rhodamine lake pigments and the like have been used.
However, as described above, the color filter is required to have higher brightness and a wider color reproduction region.
In order to solve the above problems, a technique has been proposed in which a dye, not a pigment, is dissolved as a colorant in a resin or the like (see, for example, Patent Document 1).

  Also, a magenta color filter ink containing a red pigment, a red acidic dye, and a primary amine salt compound having a rosin structure has been studied. However, although the color developability was good, it was inferior in heat resistance and light resistance and could not be used (for example, see Patent Document 2).

JP-A-6-75375 JP-A-11-189733

  The object of the present invention is excellent in color characteristics, heat resistance, light resistance, solvent resistance, no foreign matter generation in the coating film, stable red coloring composition for color filters, and color characteristics using the same, The object is to provide a color filter having excellent heat resistance, light resistance and solvent resistance.

  As a result of intensive studies to solve the above problems, the present inventors have, as a colorant for a red coloring composition for a color filter, a xanthene acid dye and a resin having a cationic group in a side chain. By using a colorant containing a salt-forming compound (A) and a red pigment, a high brightness and a wide color reproduction range are possible, and no foreign matter is generated on the coating film. The present invention has been made based on knowledge.

  That is, the present invention relates to a red coloring composition for a color filter comprising at least a colorant and a resin, wherein the colorant comprises a xanthene acid dye and a resin having a cationic group in the side chain (A ) And a red pigment. The present invention relates to a red coloring composition for a color filter.

[一般式（１−２）中、Ｒ1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。Ｒ2〜Ｒ4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、Ｒ2〜Ｒ4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−Ｒ5−、―ＣＯＯ−Ｒ5−を表し、Ｒ5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 the present invention, the resin having a cationic group in the side chain is a vinyl resin containing a structural unit represented by the following general formula (1-2): Related to things.
General formula (1-2)

[In general formula (1-2), R1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. R2 to R4 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and two of R2 to R4 are They may combine to form a ring. Q represents an alkylene group, an arylene group, -CONH-R5-, -COO-R5-, and R5 represents an alkylene group. Y- represents an inorganic or organic anion. ]

In the present invention, the xanthene acid dye is C.I. I. The present invention relates to the above-mentioned red coloring composition for color filters, which is classified as Acid Red.
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. The red coloring composition for color filters as described above, which is at least one selected from the group consisting of Acid Red 388.

The present invention also relates to the above red coloring composition for a color filter, wherein the red pigment is a diketopyrrolopyrrole pigment and / or an anthraquinone pigment and / or a monoazo or disazo pigment.
In the present invention, the red pigment is C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 48: 1, 166, C.I. I. Pigment red 220, C.I. I. Pigment red 242, and C.I. I. The red coloring composition for a color filter as described above, which is any one selected from the group consisting of CI Pigment Orange 38.

  The present invention also relates to the above red coloring composition for a color filter, wherein the colorant further contains a yellow pigment.

  The present invention also relates to the above-mentioned red coloring composition for color filters, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also provides a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one red filter segment is formed of the red coloring composition for a color filter. The present invention relates to a color filter.

  In the present invention, a salt-forming compound (A) composed of a xanthene acid dye and a resin having a cationic group in the side chain, and a red coloring composition for a color filter using a colorant and a resin containing a red pigment are used. By using a color filter, it is possible to obtain a color filter having high brightness and a wide color reproduction region and having excellent resistance by using a salt-forming compound.

  Moreover, the red coloring composition for color filters of the present invention contains a salt-forming compound (A) comprising a xanthene-based acidic dye and a resin having a cationic group in the side chain as a colorant, so that the conventional diketo is used. Compared with the coloring composition for color filters in which a pyrrolopyrrole pigment and an anthraquinone pigment are combined, the transmittance of the spectral spectrum is maintained higher in the vicinity of 590 to 630 nm. Therefore, it effectively acts on a peak in the vicinity of 600 to 650 nm of many backlights such as cold cathode fluorescent lamps, and high brightness can be obtained.

Hereinafter, the present invention will be described in detail.
In addition, “CI” described below means a color index (CI).
The red coloring composition for a color filter of the present invention comprises a colorant carrier containing a resin, a salt-forming compound (A) comprising a red pigment and a xanthene acid dye as a coloring agent, and a resin having a cationic group in the side chain; Is a red coloring composition for color filters.

<Colorant>
As a coloring agent of the red coloring composition for color filters of this invention, the salt-forming compound (A) which consists of a xanthene-type acidic dye and resin which has a cationic group in a side chain, and a red pigment are included.

  By combining and mixing the salt-forming compound (A) and the red pigment, the spectral spectrum has a high transmittance in the vicinity of 600 to 650 nm having the characteristic peak of many backlights as described above. Therefore, it is possible to obtain higher brightness and wider color reproducibility than a conventional color filter combining a diketopyrrolopyrrole pigment and an anthraquinone pigment. Furthermore, by salting an acidic dye, it can have high heat resistance, light resistance and solvent resistance.

(Salt-forming compound comprising a xanthene acid dye and a resin having a cationic group in the side chain (A))
The salt-forming compound (A) will be described. The xanthene-based acid dye used in the salt-forming compound (A) comprising a xanthene-based acid dye and a resin having a cationic group in the side chain exhibits red, purple, and has a dye form. .

  A red or purple color means C.I. I. Acid Red, C.I. Acid dyes such as I. Acid Violet, C.I. I. Direct Red, C.I. I. Direct belongs to direct dyes such as violet. Here, since the direct dye has a sulfonic acid group, it is regarded as synonymous with an acid dye in the present invention.

  Furthermore, the salt-forming compound (A) belongs to a salt-forming dye that is salted and modified with these xanthene-based acid dyes (including direct dyes) and a resin having a cationic group in the side chain serving as a counter ion. .

[Xanthene acid dyes]
The acidic dye of the xanthene dye will be described. Examples of acidic dyes of xanthene 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 (food 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. Acid Violet 9, C.I. I. Acid Violet 9, C.I. I. It is preferable to use Acid Violet 30.

  Among them, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. It is preferable to use Acid Red 388.

  In the transmission spectrum, the xanthene acid dye used in the present invention has a transmittance of 90% or more in the region of 650 nm, a transmittance of 75% or more in the region of 600 nm, a transmittance of 5% or less in 550 nm, and a region of 400 nm. Those having a transmittance of 70% or more are preferred. 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 of 550 nm is 10% or less, and the transmittance is 75% or more in the region of 400 nm.

  As the xanthene acid dye, a rhodamine acid dye is preferably used in terms of excellent color developability.

[Resin having a cationic group in the side chain]
Next, the resin having a cationic group in the side chain as the cationic component of the xanthene acid dye will be described.

  The preferable form of resin which has a cationic group in the side chain which is a cation component of the salt-forming compound (A) is colorless or white.

  Here, colorless or white means a so-called transparent state, and is defined as a state where 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 resin having a cationic group in the side chain for obtaining the salt-forming compound (A) is not particularly limited as long as it has at least one onium base in the side chain. From the viewpoint of availability, etc., ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable. In view of storage stability (thermal stability), ammonium salts, iodonium salts, and sulfonium salts are preferable. More preferably, it is a salt. More preferred is an ammonium salt.

Moreover, as resin which has a cationic group in the side chain of this invention, the vinyl-type resin containing the structural unit represented by the following general formula (1-2) is used.
General formula (1-2)

[一般式（１−２）中、Ｒ₁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。
Ｒ₂〜Ｒ₄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、Ｒ₂〜Ｒ₄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−Ｒ₅−、−ＣＯＯ−Ｒ₅−を表し、
Ｒ₅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 (1-2), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring.
Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —,
R ₅ represents an alkylene group.
Y ^- is representative of an inorganic or organic anion. ]

In General Formula (1-2), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, and n-
A butyl group, i-butyl group, t-butyl group, n-hexyl group, and cyclohexyl group are exemplified. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, R ₁ is most preferably a hydrogen atom or a methyl group.
In general formula (1-2), R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl. Groups.

Here, as the alkyl group in R _{2 to} R ₄ , for example, a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n -Tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3) -Tetramethylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and pinanyl etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R _{2 to} R ₄ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R _{2 to} R ₄ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group, or aryl group represented by R _{2 to} R ₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R _{2 to} R ₄ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

_Two of R _{2 to} R ₄ may be bonded to each other to form a ring.

In general formula (1-2), the Q component linking the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. However, among them, —CONH—R ₅ — and —COO—R ₅ — are preferable because of polymerizability and availability. R ₅ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component Y ⁻ in the general formula (1-2) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  In order to obtain a vinyl resin containing a structural unit represented by formula (1-2) which is a preferred embodiment of the present invention, an ethylenically unsaturated monomer having an ammonium base is copolymerized as a monomer component. Obtained not only by the method, but also by obtaining a vinyl resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, then reacting with an onium salting agent and ammonium chloride. May be.

  Below, the specific example of the ethylenically unsaturated monomer which can be used in order to obtain the vinyl-type resin containing the structural unit represented by General formula (1-2) which is a preferable aspect of this invention is shown. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meta ) Alkyl (meth) acrylate quaternary ammonium salts such as acryloyloxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Alkyl (meth) acryloylamide quaternary ammonium salts such as ammonium chloride, dimethyl Luzia Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

Alternatively, an alkoxycarbonylalkyl halide can also be used as the onium chlorinating agent. The alkoxycarbonylalkyl halide is represented by the following general formula (3).
General formula (3)

Z-R ₆ -COOR ₇

[In General Formula (3), Z is a halogen such as chlorine or bromine, preferably bromine, and R ₆ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. R ₇ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. ]

Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ₇ It is obtained by hydrolysis and conversion to carboxylate ions (—COO ⁻ ). Thereby, the ethylenically unsaturated monomer which has a carboxybetaine structure and has an ammonium base can be obtained.

  In addition, as described above, a copolymer resin obtained by copolymerizing an ethylenically unsaturated monomer having an amino group with another ethylenically unsaturated monomer is combined with an onium chloride agent in the same manner as described above. By reacting, a copolymer resin having a quaternary ammonium base can be obtained.

  In addition, examples of the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (1-2) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, Maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferred.

  Specific examples of such vinyl monomers include the following compounds. Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  In addition, the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (1-2) may further include a copolymer unit derived from a monomer having an acid group.

  As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto Include mono (meth) acrylate, and the like of both terminal carboxy polymers such monomethacrylate.

  Examples of a method for obtaining a vinyl resin containing a structural unit represented by the general formula (1-2) suitable for the present invention include anionic polymerization, living anion polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical. Known methods such as polymerization can be used. Of these, free radical polymerization or living radical polymerization is preferred.

In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4)
-Methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropio) Nitrile) or 2,2′-azobis [2- (2-imidazolin-2-yl) propane]. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) Pamphlet of International Publication No. 96/030421 (Reference 6) Pamphlet of International Publication No. 97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-411117 It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

The amount of the cationic group present in the resin having a cationic group in the side chain used in the present invention is not particularly limited, but the cation salt value of the resin is preferably 10 to 200 mgKOH / g, More preferably, it is 20-130 mgKOH / g. The cation salt value is expressed as an onium salt value, a quaternary ammonium salt value, or an amine salt value.
Further, among them, the amount of ammonium base and amine base present in the acrylic resin containing the structural unit represented by formula (1-2) suitable for the present invention is such that the ammonium salt value of the resin and the amine salt value are 10 -200 mgKOH / g is preferable, and 20-130 mgKOH / g is more preferable.

  If it is less than 10 mgKOH / g, the concentration of the pigment derived from the xanthene-based acidic dye is low, the resin component increases, and it does not function as a colorant component. Moreover, when it becomes larger than 200 mgKOH / g, a dye component will increase and solvent solubility will fall.

  Although the molecular weight of the vinyl-type resin containing the structural unit represented by General Formula (1-2) used for this invention is not specifically limited, The conversion weight measured by the gel permeation chromatography (GPC). The average molecular weight is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  Moreover, it is preferable that the vinyl-type resin containing the structural unit represented by General formula (1-2) suitable for this invention has the characteristic melt | dissolved in the solvent widely used for the coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

  In the resin having a cationic group in the side chain, the total content of the structural unit represented by the general formula (1-2) is not particularly limited, but is contained in the resin having a cationic group in the side chain. When the total structural unit is 100% by weight, the total content of the structural unit represented by the general formula (1-2) is 5% by weight or more from the viewpoint of solvent solubility and coloring power of the salt-forming compound. It is preferable that it is 10 to 50 weight%.

[Salt formation]
The salt-forming compound (A) used in the present invention is a resin having a cationic group in the side chain and agitated or vibrated in an aqueous solution in which a xanthene-based acidic dye is dissolved, or having a cationic group in the side chain And an aqueous solution of xanthene acid dye can be easily obtained by mixing under stirring or vibration. In the aqueous solution, the cationic 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.

  As an aqueous solution used for salt formation, a mixed solution of water and a water-soluble organic solvent may be used to dissolve the resin having a cationic group in the side chain and the xanthene-based acidic dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

  The use ratio of the red pigment and the salt-forming compound (A) is preferably 1 to 80 parts by weight of the salt-forming compound (A) with respect to 100 parts by weight of the red pigment. More preferably, it is 5 to 60 parts by weight. If the addition amount of the salt-forming compound (A) is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 80 parts by weight, the hue changes, which is not preferable.

  The salt-forming compound (A) is particularly preferably C.I. I. Acid Red 52 and C.I. I. By using Acid Red 289, it is excellent in solvent solubility, and when used in combination with a red pigment, it has excellent heat resistance, light resistance, and solvent resistance. Moreover, what becomes favorable when the salt-forming compound (A) is used in combination with the red pigment is that the salt-forming compound (A) is adsorbed to the red pigment while being dissolved and dispersed in the solvent.

(Red pigment)
As the red pigment used in the red coloring composition of the present invention, conventionally used red pigments having the following color indexes and / or orange-based red pigments can be used.

  C. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 97, 122, 123, 146, 149, 166, 168, 169, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 270, 272, 273, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, and 287 Etc.

  Examples of orange red pigments include C.I. I. Pigment Orange 13, 34, 36, 38, 43, 51, 55, 59, 61, 71 and 73 can be used.

  These red pigments may be used alone or in combination of two or more.

  Among these, as the red pigment used in the red coloring composition of the present invention, diketopyrrolopyrrole pigments and / or anthraquinone pigments and / or monoazo or disazo pigments are preferably used. In particular, it is very preferable to contain a diketopyrrolopyrrole pigment as a red pigment from the viewpoint of achieving high brightness.

  Specifically, examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254, 255, 264 and the like are preferable, and examples of the anthraquinone pigment include C.I. I. Pigment Red 177 is preferred. Examples of monoazo or disazo pigments include C.I. I. Pigment red 166, 220, 242 and C.I. I. Pigment Orange 38 is preferred.

  In the combination of the salt-forming compound (A) and the red pigment, C.I. I. A salt-forming compound (A) containing Acid Red 52 and C.I. I. Pigment Red 254 combination, C.I. I. A salt-forming compound (A) containing Acid Red 289 and C.I. I. Pigment Red 254 combination, C.I. I. A salt-forming compound (A) containing Acid Red 289 and C.I. I. Pigment Red 242, or C.I. I. A salt-forming compound (A) containing Acid Red 52 and C.I. I. The combination with CI Pigment Red 242 is very preferable in that there are few generation | occurrence | production of a coating-film foreign material, it is excellent in heat resistance, light resistance, and solvent resistance, and also can achieve high brightness.

  In addition to the salt-forming compound (A) and the red pigment described so far, the colorant used in the red coloring composition of the present invention may be used in combination with a yellow pigment.

Examples of the yellow pigment used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4,
5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194, and 199, or the like can be used.

  Among them, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferred.

  In addition to the colorant comprising the salt-forming compound (A) and the red pigment, the hue can be adjusted by using a yellow pigment as a complementary color.

[Miniaturization of pigment]
The red pigment used in the red coloring composition of the present invention and the optional pigment are preferably refined by a salt milling treatment. The primary particle diameter of the 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, with respect to 100 or more pigment particles, the volume of each particle is obtained by approximating it with a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

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

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) 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% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

  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 resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

<Resin>
The resin is one that disperses a colorant, particularly a salt-forming compound, or one that dyes and permeates the salt-forming compound, and examples thereof include thermoplastic resins and thermosetting resins.
The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl 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 for an alkali development resist for color filters, no coating foreign matter is generated after the salt-forming compound (A) is applied. The stability of the salt-forming compound (A) in the resist material is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the dye is not easily trapped in the resin and dye mixture, and the dye has a degree of freedom. The components tend to aggregate and precipitate, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the dye is easily trapped in the resin and dye mixture, Dye components are less likely to agglomerate and precipitate, and even when exposed to active energy rays to form a film, the resin is three-dimensionally cross-linked to fix the dye molecules, and the solvent can be removed in the subsequent development process. It is estimated that the dye component is less likely to aggregate and precipitate.

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

  When the resin is used as a photosensitive coloring composition for a color filter, from the viewpoints of dispersibility, penetrability, developability, and heat resistance of the pigment and salt-forming compound, the colorant adsorbing group and alkali-soluble during development are used. The balance of carboxyl groups that act as groups, aliphatic groups and aromatic groups that act as affinity groups for colorant carriers and solvents is important for the dispersibility, penetrability, developability, and even durability of pigments and salt-forming compounds. 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, no fine pattern remains.

  Since the resin has good film formability and various resistances, the resin is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight), and has a high colorant concentration and good color. Since the characteristics can be expressed, it is preferably used in an amount of 500% by weight or less.

(Thermoplastic resin)
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, and polyimide resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with 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.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

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

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

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

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

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

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

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

(Thermosetting resin)
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.

<Solvent>
In the red coloring composition of the present invention, a colorant is sufficiently dispersed and permeated in a colorant carrier, and applied to a substrate such as a glass substrate so that a dry film thickness is 0.2 to 5 μm. In order to make it easier to form, a solvent can be included.

Examples of the 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-propylacetate , 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 Methyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether Dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Acetate Amyl, isobutyl acetate, propyl acetate, and a dibasic acid ester and the like.

  Among them, since the dispersion and dissolution of the pigment of the present invention and the salt-forming compound (A) are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether It is preferable to use glycol acetates such as acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

  A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, it is 800 to 4000% by weight based on the total weight of the colorant (100% by weight). It is preferable to use it in the quantity.

<Method for producing colored composition>
The red coloring composition of the present invention comprises a colorant comprising a red pigment, a xanthene acid dye, and a salt-forming compound (A) comprising a resin having a cationic group in the side chain, the resin, and if necessary It can be produced by dissolving or dispersing in a colorant carrier comprising a solvent. In the case of production by dispersion, it is preferably finely dispersed by using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, or an attritor together with a dispersion aid such as a pigment derivative. Can be manufactured. Moreover, the red coloring composition of the present invention can also be produced by mixing a salt-forming compound (A), another colorant such as a red pigment, or the like separately dissolved or dispersed in a colorant carrier.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained. In the present invention, the salt-forming compound (A) is a preferable combination that can also serve as a dispersion aid for the red pigment.

  Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.

In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (2).
P-Ln Formula (2)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo;
Phthalocyanine pigments such as copper phthalocyanine, copper halide phthalocyanine, metal-free phthalocyanine;
Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone;
Examples include quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments;

  Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

  The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably 3% by weight or more based on the total amount of the colorant (100% by weight) from the viewpoint of improving dispersibility. It is. From the viewpoint of heat resistance and light resistance, the total amount of the colorant is preferably 40% by weight or less, and most preferably 35% by weight or less, based on the total amount (100% by weight).

  The resin-type dispersant has a pigment-affinity part having a 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, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Examples include chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; and amphoteric surfactants such as alkylimidazolines. They can be used in combination, but are not necessarily limited to these.

  When a resin-type dispersant and a surfactant are added, the total amount of the colorant is based on (100% by weight), preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight. . When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is affected by an excessive dispersant. May affect.

  The red coloring composition of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer includes a monomer or an oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  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 Ether 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, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
In the red coloring composition for color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to a solvent developing type or an alkali developing type. It can be adjusted in the form of a colored resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant, and 10 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 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) -6-triazine, or 2,4-trichloromethyl- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide , Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; Alternatively, titanocene compounds and the like are used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant in the red coloring composition for color filters (100% by weight), from the viewpoint of photocurability and developability. More preferably, it is 10 to 150% by weight.

<Sensitizer>
Furthermore, the red coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, 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, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.

  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.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Amine compound>
Moreover, the coloring composition for color filters 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 red coloring 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 is preferably used in an amount of 0.003 to 0.5% by weight based on the total weight of the red coloring composition (100% by weight).

  As a particularly preferred leveling agent, it is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, has a hydrophilic group but has low solubility in water, and when added to a red coloring composition, It has the feature that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and the added amount that does not cause coating film defects due to foaming In this case, 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 polyoxyalkylene ethers such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene nonylphenyl ether;
Polyoxyalkylene esters such as polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Examples include alkylbetaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the red 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- D Ru-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 content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

<Other additive components>
The red coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. 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% by weight based on the total amount of the colorant (100% by weight).

  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 adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount (100% by weight) of the colorant in the red coloring composition.

<Removal of coarse particles>
The red coloring composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to remove the dust. Thus, it is preferable that a red 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 includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a red coloring composition for the color filter of the present invention. It is formed using.

The green filter segment can be formed using a conventional green coloring composition comprising a green pigment and a colorant carrier. Examples of the green pigment include C.I. I. Pigment Green 7,
10, 36, 37, 58, etc. are used.

  A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. As the blue pigment, a phthalocyanine pigment and / or a triarylmethane lake pigment or the like is used. As the phthalocyanine pigment, it is preferable to use a copper phthalocyanine blue pigment.
Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigments having ε-type and α-type structures are preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1.

  Examples of triarylmethane lake pigments include C.I. I. Pigment blue 1, 1: 2, 1: 3, C.I. I. Pigment Blue 2, 2: 1, 2: 2, C.I. I. Pigment blue 3, C.I. I. Pigment Blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10, 10: 1, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, 56: 1, C.I. I. Pigment blue 57, C.I. I. Pigment blue 58, C.I. I. Pigment blue 59, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62 and the like.

  Among these, C.I. I. It is preferable to use CI Pigment Blue 15: 6.

  In addition to the blue pigment, it is preferable to use a dioxazine pigment, an anthraquinone pigment, an azo pigment, or a quinacridone pigment exhibiting purple or red. Among them, it is preferable to use a dioxazine pigment in combination. Examples of the dioxazine pigment include C.I. I. Pigment Violet 23 is preferably used. By using a dioxazine pigment in combination with the blue coloring composition of the present invention, it is possible to obtain a stable and high-quality blue coloring composition which is further excellent in heat resistance, light resistance and solvent resistance.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. 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. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

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.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate. The ink jet method is a method for printing and producing a filter segment by an ink jet method.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”.

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

  First, acrylic resin solutions, refined pigments, salt-forming compounds (A), xanthene-based compounds, pigment dispersions, salt-forming compound-containing resin solutions, xanthene-based compound-containing resin solutions, blue resist materials used in Examples and Comparative Examples The method for producing a green resist material will be described.

<Method for producing acrylic resin solutions 1 to 4>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2,2'-
A mixture of 0.4 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 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. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by addition.

(Preparation of acrylic resin solution 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 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 2 was obtained. Prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of acrylic resin solution 3)
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 Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 1.33 of 2,2′-azobisisobutyronitrile Part 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, after cooling to room temperature, 6.5 parts of 2-methacryloyloxyl ethyl isocyanate, A mixture of 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 3 was obtained. Prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of acrylic resin solution 4)
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 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an acrylic resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Production method of fine pigment>
(Preparation of red fine pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 1 were obtained. The specific surface area of the red fine pigment 1 was 70 m ² / g.

(Preparation of red fine pigment 2)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthalred A2B” manufactured by Ciba Japan Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 2 were obtained. The specific surface area of the red fine pigment 2 was 80 m ² / g.

(Preparation of red fine pigment 3)
Red pigment C.I. I. 200 parts of Pigment Red 242 (“NOVOPERM SCARLET 4RF” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 3 were obtained.

(Preparation of red fine pigment 4)
Red pigment C.I. I. 200 parts of CI Pigment Orange 38 (“NOVOPERM RED HFG” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigment 4 were obtained.

(Preparation of red fine pigment 5)
Red pigment C.I. I. 200 parts of Pigment Red 166 (“Chromophthal Scallet RN” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 5 were obtained.

(Preparation of red fine pigment 6)
Red pigment C.I. I. 200 parts of Pigment Red 220 (“Chromophthal Red G” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red pigment 6 were obtained.

(Preparation of red fine pigment 7)
Red pigment C.I. I. Pigment Red 48: 1 (“LIONOL RED TT-4801G” manufactured by Toyo Ink Manufacturing Co., Ltd.), 200 parts of sodium chloride, 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and 6 at 80 ° C. Kneaded for hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 7 were obtained.

(Preparation of yellow fine pigment 1)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a yellow fine pigment 1 were obtained. The specific surface area of the yellow fine pigment 1 was 65 m ² / g.

(Preparation of blue fine pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Co., Ltd., specific surface area 60 m ² / g), 200 parts of sodium chloride, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho). And kneading at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue fine pigment 1 were obtained. The specific surface area of the blue fine pigment 1 was 80 m ² / g.

(Preparation of purple fine pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of purple fine pigment 1 were obtained. The specific surface area of the purple fine pigment 1 was 95 m ² / g.

(Preparation of green fine pigment 1)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of green fine pigment 1 were obtained. The specific surface area of the green fine pigment 1 was 75 m ² / g.

<Method for preparing resin having cationic group in side chain>
(Preparation of resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged 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 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in the side chain of 47% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

  Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value of the resin having a cationic group in the side chain was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent amount of potassium hydroxide. It indicates the ammonium salt value of the solid content.

(Preparation of resin 2 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 2,2′-azobis (2,4-dimethylvaleronitrile 5.7) and 15.6 parts of methyl ethyl ketone were made uniform, 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 45 mgKOH / g.

(Preparation of resin 3 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 27.5 parts of isopropyl methacrylate, 25.0 parts of benzyl methacrylate, 27.5 parts of 2-ethylhexyl acrylate, 20.0 parts of N, N-dimethylaminomethylstyrene, 2,2′-azobis (2,4-dimethyl) 6.7 parts of valeronitrile) and 25.1 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6770, and the mixture was cooled to 50 ° C. To this, 15.7 parts of benzyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 3 having a cationic group in the side chain of 50% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 60 mgKOH / g.

(Preparation of resin 4 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 25.0 parts of methyl methacrylate, 25.0 parts of stearyl methacrylate, 20.0 parts of cyclohexyl methacrylate, 15.0 parts of Bremer PE90 (manufactured by NOF Corporation, diethylene glycol monomethacrylate), 20.0 parts of N-vinylpyrrolidone, After homogenizing 4.7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 15.6 parts of isopropyl alcohol, the mixture was charged into a dropping funnel and attached to a four-necked separable flask for 2 hours. It was dripped over. 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 7550, and the mixture was cooled to 50 ° C. To this, 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thereafter, 50 parts of isopropyl alcohol was added to obtain a resin 4 having a cationic group in the side chain of 44% by weight of the resin component. The ammonium salt value of the obtained resin was 92 mgKOH / g.

(Preparation of resin 5 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 82.0 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 23.5 parts of ethyl methacrylate, 26.0 parts of t-butyl methacrylate, 25.0 parts of lauryl methacrylate, Kayamer PM-21 (manufactured by Nippon Kayaku Co., Ltd., 1 mol of ε-caprolaclone 1-hydroxyethyl methacrylate phosphate ester) ) 10.0 parts, diethylaminopropyl methacrylate 17.5 parts, 2,2′-azobis (2,4-dimethylvaleronitrile) 6.0 parts, and methyl ethyl ketone 25.6 parts, and then a dropping funnel Was 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 7010, and the mixture was cooled to 50 ° C. In this way, Resin 5 having a cationic group in the side chain of which the resin component was 48% by weight was obtained. The amine salt value of the obtained resin was 49 mgKOH / g. Here, the amine value of the resin having a cationic group in the side chain was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent amount of potassium hydroxide.

<Method for Producing Salt-Forming Compound (A)>
(Salt-forming compound (A2-1))
In the following procedure, C.I. I. A salt-forming compound (A2-1) composed of Acid Red 52 and Resin 1 having a cationic group in the side chain was produced.
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, it is 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 is dissolved is prepared and added 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 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 salt-forming compound (A2-1) between Acid Red 52 and Resin 1 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-2))
In the following procedure, C.I. I. A salt-forming compound (A2-2) consisting of Acid Red 52 and Resin 2 having a cationic group in the side chain was produced. 88 parts of the resin 2 having a cationic group in the side chain is added to 2000 parts of a 10% aqueous methanol solution, and after sufficient 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. An aqueous solution in which Acid Red 52 is dissolved is prepared and added 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. I. A salt-forming compound (A2-2) between Acid Red 52 and Resin 2 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-3))
In the following procedure, C.I. I. A salt-forming compound (A2-3) comprising Acid Red 52 and Resin 3 having a cationic group in the side chain was produced. 42,000 parts of the resin 3 having a cationic group in the side chain is added to 2000 parts of a 10% N, N-dimethylformamide aqueous solution, and the mixture is sufficiently stirred and mixed, and then heated to 70 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 is dissolved is prepared and added dropwise to the resin solution. After dropping, the mixture is stirred at 70 ° 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 29 parts of C.I. I. A salt-forming compound (A2-3) between Acid Red 52 and Resin 3 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-4))
In the following procedure, C.I. I. A salt-forming compound (A2-4) comprising Acid Red 52 and Resin 4 having a cationic group in the side chain was produced. A solution in which resin 4 having a cationic group in 20.0 parts of the side chain is dissolved in 1000 parts of water is prepared, sufficiently stirred and mixed, and then heated to 70 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 is dissolved is prepared and added 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 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 19 parts of C.I. I. A salt-forming compound (A2-4) between Acid Red 52 and resin 4 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-5))
In the following procedure, C.I. I. A salt-forming compound (A2-5) comprising Acid Red 52 and Resin 5 having a cationic group in the side chain was produced. The resin 5 having a cationic group in the side chain of 63.2 parts is added to 2000 parts of 20% acetic acid, and after sufficiently stirring and mixing, the mixture is heated to 60 ° C. and ammonium chloride of the tertiary amino group in the side chain is added. I do. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 is dissolved is prepared and added dropwise little by little to the ammonium chloride 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. I. A salt-forming compound (A2-5) between Acid Red 52 and resin 5 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-6))
In the following procedure, C.I. I. A salt-forming compound (A2-6) consisting of Acid Red 52 and Disperbyk-2000 (manufactured by Big Chemie Japan, modified acrylic block copolymer, ammonium salt value 61 mg KOH / g) was produced. Add 50.9 parts Disperbyk-2000 to 2000 parts water, stir and mix thoroughly, and then heat 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 is dissolved is prepared and added 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 31 parts of C.I. I. A salt-forming compound (A2-6) of Acid Red 52 and Disperbyk-2000 was obtained.

(Salt-forming compound (A2-7))
In the following procedure, C.I. I. A salt-forming compound (A2-7) comprising Acid Red 289 and Resin 1 having a cationic group in the side chain was produced. 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, it is 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 is dissolved is prepared and added dropwise little by little to the previous 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 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 salt-forming compound (A2-7) between Acid Red 289 and Resin 1 having a cationic group in the side chain was obtained.

(Salt Forming Compound (A2-8))
In the following procedure, C.I. I. A salt-forming compound (A2-8) comprising Acid Red 388 and Resin 1 having a cationic group in the side chain was produced. 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, it is 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 388 is dissolved is prepared and added dropwise little by little to the previous 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 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 salt-forming compound (A2-8) between Acid Red 388 and Resin 1 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-9))
In the following procedure, C.I. I. A salt-forming compound (A2-9) comprising Acid Red 87 and Resin 1 having a cationic group in the side chain was produced. 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, it is 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 87 is dissolved is prepared and added dropwise to the previous resin solution little by little. 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 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 salt-forming compound (A2-9) between Acid Red 87 and Resin 1 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-10))
In the following procedure, C.I. I. A salt-forming compound (A2-10) comprising Acid Red 92 and Resin 1 having a cationic group in the side chain was produced. 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, it is 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 92 is dissolved is prepared and added 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 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 salt-forming compound (A2-10) between Acid Red 92 and Resin 1 having a cationic group in the side chain was obtained.

(Salt-forming compound (A2-11))
In the following procedure, C.I. I. A salt-forming compound (A2-11) consisting of Acid Red 289 and Resin 5 having a cationic group in the side chain was produced. The resin 5 having a cationic group in the side chain of 63.2 parts is added to 2000 parts of 20% acetic acid, and after sufficiently stirring and mixing, the mixture is heated to 60 ° C. and ammonium chloride of the tertiary amino group in the side chain is added. I do. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise little by little to the ammonium chloride 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. I. A salt-forming compound (A2-11) between Acid Red 289 and resin 5 having a cationic group in the side chain was obtained.

<Method for producing xanthene compound>
(Xanthene compound (C-1))
C. I. Acid Red 52 was converted to a sulfonyl chloride by a conventional method and then reacted with a theoretical equivalent of dodecylamine in dioxane to obtain C.I. I. A sulfonamide compound of Acid Red 52 and a xanthene compound (C-1) were obtained. (Based on the description of JP-A-6-194828)

(Xanthene compound (C-2))
C. I. Acid Red 289 was converted to a sulfonyl chloride by a conventional method and then reacted with a theoretical equivalent of dodecylamine in dioxane to obtain C.I. I. A sulfonamide compound of Acid Red 289 and a xanthene compound (C-2) were obtained. (Based on the description of JP-A-6-194828)

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

Red fine pigment 1 (CI Pigment Red 254): 11.0 parts acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (manufactured by Ciba Japan) "EFKA4300"): 1.0 part

Hereinafter, pigment dispersions (DP-2 to 13) were prepared in the same manner as the pigment dispersion (DP-1) except that the pigments and resins shown in Table 1 were changed.

<Method for producing salt-forming compound-containing resin solution and xanthene-based compound-containing resin solution>
(Preparation of salt-forming compound-containing resin solution (DA2-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (DA2-1).

Salt-forming compound (A2-1): 11.0 parts acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts (salt-forming compound-containing resin solution (DA2-2 to 11), Xanthene compound-containing resin solution

(Production of DC-1, 2)
Hereinafter, the salt-forming compound-containing resin solution (DA2-2 to 11) is the same as the salt-forming compound-containing resin solution (DA-1) except that the salt-forming compound and acrylic resin solution shown in Table 2 are changed. A xanthene compound-containing resin solution (DC-1, 2) was prepared.

<Method for producing blue and green resist materials>
(Preparation of blue resist material)
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
A blue resist material was obtained.
Pigment dispersion (DP-4): 50.0 parts Pigment dispersion (DP-5): 10.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
A green resist material was obtained.
Pigment dispersion (DP-6): 45.0 parts Pigment dispersion (DP-3): 15.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 1 to 11, Comparative Examples 1 and 2]
(Example 1; Production of colored composition (DB2-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a mixed colored composition.
Salt-forming compound-containing resin solution (DA2-1): 5.0 parts Pigment dispersion (DP-1): 6.0 parts Acrylic resin solution 1: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 Part

(Examples 2 to 11, Comparative Examples 1 and 2; Colored composition (DB2-2 to 13))
Hereinafter, except changing the salt-forming compound-containing resin solution (DA2-1) to the salt-forming compound-containing resin solution or xanthene-based compound-containing resin solution shown in Table 3, in the same manner as the colored composition (DB2-1), Coloring compositions (DB2-2 to 13) were produced. However, the pigment dispersion (DP-1) was used in the same manner as in Example 1 in Examples 2 to 11 and Comparative Examples 1 and 2.

(Coating foreign material test method)
The evaluation was performed by preparing a test substrate and counting the number of particles. The coloring composition was applied onto the transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes to obtain a test substrate. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification was 500 times, and the number of particles that were observable in arbitrary 5 fields of view through transmission was counted.
In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness (spots) due to foreign matters.
未 満: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more The results are shown in Table 3 below.

  When the red pigment and the salt-forming compound (A) are used, in the substrate evaluation, there are few foreign matters (undissolved foreign matter). When the xanthene compounds (C-1 and 2) are used, the foreign matters are very There were many results. From this, the resin salt-forming compound having a cationic group in the side chain was superior to those obtained by organically converting the substituents.

[Examples 12 to 24, Comparative Examples 3 to 5]
(Example 12: Resist material (R2-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (R2-1).
Colorant dispersion (60 parts in total)
Salt-forming compound-containing resin solution (DA2-1): 21.0 parts Pigment dispersion (DP-1): 39.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (new "NK ESTER ATMPT" manufactured by Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

(Examples 13-24, Comparative Examples 3-5; Resist material (R2-2-16))
Hereinafter, the resist material (R2-1) except that the colorant dispersion was changed to the type and blending amount of the colorant dispersion (pigment dispersion or salt-forming compound-containing resin solution or xanthene compound-containing resin solution) shown in Table 4. ) To obtain an alkali developing resist material (R2-2 to 16). In the resist material, a colorant dispersion (a pigment dispersion or a salt-forming compound-containing resin solution or a xanthene compound-containing resin solution) is used in combination, but the total amount of the colorant dispersion is 60 parts in all resist materials.

(Examples 25-30, resist material (R2-17-22))
Alkali developing resist materials R2-17, 18, and 19 were obtained in the same manner as in the resist material (R2-10), except that the acrylic resin solution 1 of Example 21 was replaced with the acrylic resin solutions 2, 3, and 4.
Furthermore, the acrylic resin solution 1 of Example 22 was replaced with the acrylic resin solutions 2, 3, and 4, and alkali developing resist materials R 2-20, 21, and 22 were obtained in the same manner as the resist material (R 2-11).

(Evaluation of resist material)
Each test of the chromaticity, foreign matter, heat resistance, light resistance, and solvent resistance of the coating film of the obtained resist material (R2-1 to 22) was performed by the following methods. The test results are shown in Table 5.

(Coating foreign material test method)
A resist material was applied on the transparent substrate so that the dried coating film had a thickness of about 2.5 μm, and the entire surface was exposed to ultraviolet light. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification is 500 times, and the number of particles that can be confirmed in any five visual fields through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness due to the foreign matters.
A: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or less, Table 5 shows the results.

(Evaluation of color characteristics)
A resist material was applied on a glass substrate so that x = 0.640 and y = 0.315 with a C light source, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
The results are shown in Table 5 below.

(Method of coating heat resistance test)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and after UV exposure through a mask having a predetermined pattern, an alkali developer is sprayed to remove uncured parts. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 20 minutes and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source is microspectrophotometric. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
The results are shown in Table 5 below.

Using the measured color difference value, the color difference ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
：: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 2.5 Δ: ΔEab * is 2.5 or more and less than 5.0 ×: ΔEab * is 5.0 or more, Table 5 The results are shown in.

(Method of coating light resistance test)
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optics) It measured using "OSP-SP200" by a company. Thereafter, the substrate was placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI) and left for 500 hours. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the light resistance of the coating film was evaluated according to the same criteria as heat resistance.
The results are shown in Table 5 below.

(Method of coating solvent resistance test)
A test substrate is prepared in the same procedure as the heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd.) It measured using "OSP-SP200"). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the heat resistance.
The results are shown in Table 5 below.

  The resist materials (R2-1 to 13, 17 to 22) of Examples 12 to 30 had good light resistance. On the other hand, the resist materials (R2-14 and 15) of Comparative Examples 3 and 4 have many foreign matters and are difficult to use. The resist material (R2-16) of Comparative Example 5 had a lower brightness (Y) than Examples 12-30.

  Moreover, as can be seen from the results of Examples 25 to 30 resist materials (R-17 to 22), the use of an active energy ray-curable resin having an ethylenically unsaturated double bond can further reduce coating film foreign matter. Recognize.

[Examples 31-49, Comparative Examples 6-8]
(Example 31; color filter (CF2-1))
A black matrix is patterned on a glass substrate, and a red resist material (R2-1) is applied on the substrate with a spin coater to a thickness such that x = 0.640 and y = 0.315, and a colored film is formed. Formed. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. Using the same method, the green resist material is formed to have a film thickness of x = 0.300 and y = 0.600, and the blue resist material is used to form a film having x = 0.150 and y = 0.060. Each was applied to a thickness to form a green filter segment and a blue filter segment to obtain a color filter (CF2-1).

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A polarizing plate was formed on the other surface of this glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

(Examples 32-49, Comparative Examples 6-8)
Thereafter, in the same manner as in Example 31, the color filters (CF2-2 to 22) and color display devices of Examples 32-49 and Comparative Examples 6-8 were prepared in combination with the resist material shown in Table 6 and a three-wavelength CCFL light source. Was made.
Thereafter, in the obtained color display device, a light source was emitted to display a color image, and the brightness of each color filter segment portion was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 6.

  When Examples 31-49 and Comparative Example 8 (color filter (CF2-16)) were compared, they were formed from a resist material containing a conventionally used diketopyrrolopyrrole pigment and anthraquinone pigment in white display. Compared to a color filter (color filter (CF2-22)), a color filter (color filter (CF2-1 to 19)) formed from the resist material of the present invention containing a red pigment and a salt-forming compound (A). High brightness is obtained. Although Comparative Examples 6 and 7 (color filters (CF2-20, 21)) have high brightness, a large amount of foreign matter is generated as described above, so that it is difficult to use practically.

(Example 51)
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to prepare a red colored resin composition.

Pigment dispersion (DP-7): 7.2 parts Salt-forming compound-containing resin solution (DA2-1): 3.8 parts Acrylic resin solution 1: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 Part

(Example 52)
The ratio of the pigment dispersion and the salt-forming compound-containing resin solution so that the same chromaticity as Example 51 was obtained by changing the salt-forming compound-containing resin solution (DA2-1) to the salt-forming compound-containing resin solution (DA2-9). A red colored resin composition was obtained in the same manner as in Example 51 except that was adjusted.
(Example 53)
The ratio of the pigment dispersion and the salt-forming compound-containing resin solution so that the same chromaticity as Example 51 was obtained by changing the salt-forming compound-containing resin solution (DA2-1) to the salt-forming compound-containing resin solution (DA2-10). A red colored resin composition was obtained in the same manner as in Example 51 except that was adjusted.
(Example 54)
The ratio of the pigment dispersion and the salt-forming compound-containing resin solution so that the same chromaticity as Example 51 was obtained by changing the salt-forming compound-containing resin solution (DA2-1) to the salt-forming compound-containing resin solution (DA2-7). A red colored resin composition was obtained in the same manner as in Example 51 except that was adjusted.
(Example 55)
The ratio of the pigment dispersion and the salt-forming compound-containing resin solution so that the same chromaticity as Example 51 is obtained by changing the salt-forming compound-containing resin solution (DA2-1) to the salt-forming compound-containing resin solution (DA2-8). A red colored resin composition was obtained in the same manner as in Example 51 except that was adjusted.

(Comparative Example 12)
The pigment dispersion (DP-7) is changed to the pigment dispersion (DP-1), and the salt-forming compound-containing resin solution (DA2-1) is changed to the pigment dispersion (DP-2). A red colored resin composition was obtained in the same manner as in Example 51 except that the ratio of the pigment dispersion was adjusted.
(Comparative Example 13)
The same as in Example 51 except that the salt-forming compound-containing resin solution (DA2-1) was changed to the pigment dispersion (DP-2) and the ratio of the pigment dispersion was adjusted so as to have the same chromaticity as in Example 51. Thus, a red colored resin composition was obtained.
(Comparative Example 14)
By changing the pigment dispersion (DP-7) to the pigment dispersion (DP-8) and the salt-forming compound-containing resin solution (DA2-1) to the pigment dispersion (DP-2), the same chromaticity as in Example 51 was obtained. A red colored resin composition was obtained in the same manner as in Example 51 except that the ratio of the pigment dispersion was adjusted.

(Comparative Example 15)
By changing the pigment dispersion (DP-7) to the pigment dispersion (DP-9) and the salt-forming compound-containing resin solution (DA2-1) to the pigment dispersion (DP-2), the same chromaticity as in Example 51 was obtained. A red colored resin composition was obtained in the same manner as in Example 51 except that the ratio of the pigment dispersion was adjusted.
(Comparative Example 16)
The pigment dispersion (DP-7) is changed to the pigment dispersion (DP-10), and the salt-forming compound-containing resin solution (DA2-1) is changed to the pigment dispersion (DP-2). A red colored resin composition was obtained in the same manner as in Example 51 except that the ratio of the pigment dispersion was adjusted.
(Comparative Example 17)
The pigment dispersion (DP-7) is changed to the pigment dispersion (DP-11), and the salt-forming compound-containing resin solution (DA2-1) is changed to the pigment dispersion (DP-2). A red colored resin composition was obtained in the same manner as in Example 51 except that the ratio of the pigment dispersion was adjusted.

After spin-coating the red colored resin compositions obtained in Examples 51 to 55 and Comparative Examples 12 to 17 to a film thickness of 2.0 μm on a transparent substrate and drying (prebaking) at 60 ° C. for 5 minutes. , And heated at 230 ° C. for 20 minutes (post-baking) to prepare a coated substrate.
The lightness (Y) of the prepared coating film substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
The results are shown in Table 7 below.

  As shown in Table 7, in the red colored resin compositions of Examples 51 to 55, a red coating film having a higher brightness than the red colored resin compositions of Comparative Examples 12 to 17 was obtained.

(Example 56)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a red alkali development resist material.

Colorant dispersion (60 parts in total)
Salt-forming compound-containing resin solution (DA2-1): 21.0 parts Pigment dispersion (DP-7): 39.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (new “NK ester ATMPT” manufactured by Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

(Comparative Example 18)
By changing the pigment dispersion (DP-7) and the salt-forming compound-containing resin solution (DA2-1) to the pigment dispersion (DP-1) and the pigment dispersion (DP-2), the same chromaticity as in Example 56 was obtained. A red alkali developing resist material was obtained in the same manner as in Example 56 except that the ratio of the pigment dispersion was adjusted.

The red alkali developing resist material obtained in Example 56 and Comparative Example 18 was spin-coated on a transparent substrate to a film thickness of 2.5 μm, dried at 60 ° C. for 5 minutes (prebaked), and then 230 ° C. Was heated (post-baked) for 20 minutes to prepare a coated substrate, and the brightness (Y) of the prepared coated substrate was measured as described above.
The results are shown in Table 8 below.

  As shown in Table 8, in the red coloring composition of Example 56, a red coating film having higher brightness than that of the red alkali development resist material of Comparative Example 18 was obtained.

Claims (8)

In a red coloring composition for a color filter comprising at least a colorant and a resin, the colorant comprises a salt-forming compound (A) comprising a xanthene acid dye and a resin having a cationic group in a side chain and a red pigment. ,
A red coloring composition for a color filter, wherein the resin having a cationic group in the side chain is a vinyl resin containing a structural unit represented by the following general formula (1-2).
General formula (1-2)

[In General Formula (1-2), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, or —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]   Xanthene acid dyes are C.I. I. It is classified into acid red, The red coloring composition for color filters of Claim 1 characterized by the above-mentioned.   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. 3. The red coloring composition for a color filter according to claim 1, wherein the composition is at least one selected from the group consisting of Acid Red 388. 4.   The red coloring composition for a color filter according to any one of claims 1 to 3, wherein the red pigment is a diketopyrrolopyrrole pigment and / or an anthraquinone pigment and / or a monoazo or disazo pigment. object. The red pigment is C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 166, C.I. I. Pigment red 220, C.I. I. Pigment red 242, and C.I. I. The red coloring composition for a color filter according to any one of claims 1 to 4, wherein the red coloring composition is any one selected from the group consisting of CI Pigment Orange 38.   The red coloring composition for a color filter according to any one of claims 1 to 5, wherein the colorant further contains a yellow pigment.   The red colored composition for a color filter according to any one of claims 1 to 6, further comprising a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein the at least one red filter segment is a red coloring composition for a color filter according to any one of claims 1 to 7. A color filter formed by objects.