JP5625542B2 - Coloring composition for color filter, and color filter - Google Patents

Description

  The present invention relates to a colored 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. is there.

  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.

In addition, a color image pickup device represented by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. has a red filter layer (R) on the light receiving element. In general, color filters each including a primary color filter segment of an additive mixture of a green filter layer (G) and a blue filter layer (B) are disposed and separated. 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.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. 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.

  For example, as a colorant conventionally used for forming a blue filter segment (pixel) or a cyan filter segment (pixel), a phthalocyanine pigment generally excellent in durability and color tone is often used. Phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type, and each has excellent properties such as clearness and high coloring power. It is suitable. As this phthalocyanine pigment, those having various central metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among these, copper phthalocyanine pigments are widely used because they have the clearest color tone. In addition, metal phthalocyanine pigments such as metal-free phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, and cobalt phthalocyanine pigments have been put into practical use.

  In a display device such as a liquid crystal display device using a conventional cold cathode tube type backlight, a combination of a copper phthalocyanine pigment and a dioxazine pigment is combined with a blue filter segment or a cyan filter segment to achieve high brightness and wide color. The display area could be achieved. 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).
In addition, an ink for a color filter containing a phthalocyanine dye and a xanthene dye has been studied. In particular, it was a combination of a direct dye and an acid dye, but although the color developability was good, it was inferior in heat resistance and light resistance and was not satisfactory. (For example, see Patent Document 2)

  Further, it has been proposed to use a triphenylmethane dye and a xanthene dye together as a blue pixel for a color filter. However, as described above, since the dye has inferior weather resistance compared to the pigment, sufficient weather resistance cannot be obtained by simply mixing the dyes, leaving room for improvement. . (For example, see Patent Document 3)

  It has also been proposed to use amine salts such as copper phthalocyanine acid dyes and sulfonamide compounds of copper phthalocyanine acid dyes as colorants for color filters. However, the salt-forming compound disclosed here has poor solvent solubility and does not have sufficient heat resistance and light resistance. (For example, see Patent Documents 4 and 5)

JP-A-6-75375 JP-A-8-327811 Japanese Patent Laid-Open No. 11-223720 Japanese Patent Laid-Open No. 6-194828 JP-A-6-51115

  The object of the present invention is to provide a color composition for a color filter that is excellent in color characteristics, heat resistance, light resistance, solvent resistance, does not generate foreign matter on the coating film, and has good color characteristics and heat resistance. It is to provide a color filter having excellent properties, light resistance and solvent resistance.

  As a result of intensive studies to solve the above problems, the present inventors have made it possible to achieve high brightness and a wide color reproduction region by using the coloring composition for color filters of the present invention. The present invention has been made based on this finding, and it has been found that there is no generation of foreign matter on the surface and excellent resistance.

The present invention is a color filter coloring composition comprising a colorant, a resin, and an organic solvent.
The colorant contains a salt-forming compound (A) comprising an acidic dye and a quaternary ammonium salt compound having a molecular weight of the cationic moiety in the range of 190 to 900,
The organic solvent has a boiling point at 760 mmHg of 120 to 210 ° C. and a solubility parameter (= SP value) of 8.8 (cal / cm ³ ) ^1/2 or more and less than 13.0 (cal / cm ³ ) ^1/2 Organic solvent (S)
The present invention relates to a coloring composition for a color filter, wherein the content of the organic solvent (S) based on the total amount of the solvent is 5 to 100% by weight.

The organic solvent (S) contains an organic solvent (S1) having a solubility parameter (= SP value) of 8.8 (cal / cm ³ ) ^1/2 or more and less than 9.7 (cal / cm ³ ) ^1/2. The coloring composition for a color filter as described above.

The organic solvent (S) includes an organic solvent (S2) having a solubility parameter (= SP value) of 9.7 (cal / cm ³ ) ^1/2 or more and less than 13.0 (cal / cm ³ ) ^1/2 ,
Content of the organic solvent (S2) when it is based on the total amount of the solvent is 5 to 50% by weight.

Moreover, this invention relates to the said coloring composition for color filters characterized by the quaternary ammonium salt compound whose molecular weight of a cation part is the range of 190-900 represented by following General formula (1).
General formula (1)
[In General Formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ and R ₄ are The number of C is 5-20. Y ^- is representative of an inorganic or organic anion. ]

  The present invention also relates to the colored composition for a color filter, wherein the resin contains a resin having an ethylenically unsaturated double bond in a side chain.

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to the color composition for color filters, wherein the colorant further contains a phthalocyanine pigment and / or a triarylmethane lake pigment.

  The present invention also relates to a color filter comprising a filter segment formed on a base plate using the coloring composition for a color filter.

  In the present invention, a colorant, a resin, and a specific solvent containing a salt-forming compound (A) comprising an acidic dye and a quaternary ammonium salt compound (counter component thereof) having a molecular weight of a cationic moiety in the range of 190 to 900 By using a color filter formed from a coloring composition for a color filter using a high brightness and a wide color reproduction region, it is excellent in resistance by using a salt-forming compound, and by using a specific solvent Thus, it is possible to obtain a color filter that does not generate foreign matter.

  For example, when used as a blue coloring composition, the transmittance spectrum of a coloring composition for a color filter that combines a conventional copper phthalocyanine blue pigment and a dioxazine pigment, etc., has a peak position near 450 nm and a short wavelength side of 450 nm or less. Then, the transmittance is drastically decreasing. On the other hand, the blue coloring composition for a color filter of the present invention comprises a salt-forming compound (A) comprising an acidic dye and a quaternary ammonium salt compound (counter component thereof) having a molecular weight of 190 to 900 as a colorant. By containing, compared with a copper phthalocyanine blue pigment, the high transmittance | permeability is maintained also at the short wavelength side of 450 nm or less. Therefore, it effectively acts on a peak in the vicinity of 425 to 500 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 coloring composition for a color filter of the present invention comprises a colorant containing a salt-forming compound (A) comprising an acidic dye and a quaternary ammonium salt compound having a cation moiety molecular weight in the range of 190 to 900, a resin, and 760 mmHg. An organic solvent having a boiling point of 120 to 210 ° C. and a solubility parameter (= SP value) of 8.8 (cal / cm ³ ) ^1/2 or more and less than 13.0 (cal / cm ³ ) ^1/2 It is characterized by that.

<Colorant>
Examples of the colorant include an acidic dye and a quaternary ammonium salt compound (A) having a molecular weight of 190 to 900 in the cation portion. For example, when used as a blue coloring composition, the salt-forming compound (A) and blue A pigment can be used in combination or mixed. This makes it possible to have a high transmittance around 425 to 500 nm, which has the characteristic peak of many backlights as described above, and is a color combining conventional copper phthalocyanine pigments and dioxazine pigments. High brightness and wide color reproducibility can be obtained from the filter. Furthermore, by chlorinating a quaternary ammonium salt compound in which the molecular weight of the acidic dye and cation moiety is in the range of 190 to 900, it can have high heat resistance, light resistance and solvent resistance.

(Salt-forming compound (A))
The salt-forming compound (A) is formed by salt formation and modification with an acid dye (including a direct dye) and a quaternary ammonium salt compound in which the molecular weight of the cation moiety which is a counter component serving as a counter ion is in the range of 190 to 900. It belongs to salt dyes.

[Acid dyes]
An acid dye is a water-soluble dye having an acid group such as a sulfonic acid group or a carboxyl group in the pigment molecule, or a salt structure thereof, and is a protein fiber such as wool, silk, or nylon, leather or paper.・ It is widely used as ink and food coloring.

  Some acid dyes are classified as direct dyes, and the direct dye is a general term for those excellent in dyeability of cellulosic fibers.

As the direct dye, azo dyes, thiazole dyes, anthraquinone dyes, oxazine dyes, phthalocyanine dyes, and the like can be used. In the following, usable dyes are exemplified by color index (CI) numbers.
Examples of the azo dye include CI Direct Yellow 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95, 98, 102, 109, 129, 136, 141;
CI Direct Orange 41, 46, 56, 61, 64, 70, 96, 97, 106, 107;
C.I. Direct Red 79, 82, 83, 84, 97, 98, 99, 106, 107, 172, 173, 176, 177, 179, 181, 182, 204, 207, 211, 213, 218, 221 222, 232, 233, 243, 246, 250;
CI Direct Violet 47, 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C.I. Direct Blue 51, 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101, 113, 149, 150, 153, 160, 162, 163, 164, 166 167, 170, 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275;
CI direct green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82 and the like. Examples of thiazole dyes include CI Direct Yellow 54.
Examples of dioxazine dyes include CI Direct Blue 97, 99, 106, 107, 108, 109, 190, 293 and the like.
An example of an anthraquinone dye is CI Direct Blue 77.
Examples of the phthalocyanine dye include CI Direct Blue 86, 87, 189, 199 and the like.
Other direct dyes include C.I. Direct Yellow 38, 43, 47, 58, 68, 108, 138; C.I. Direct Orange 34, 39, 50, 52, 57, 65, 68; C.I. Direct Red 91, 92, 96, 105, 184, 220, 234, 241; CI Direct Violet 59; CI Direct Blue 80, 114, 115, 117, 119, 137, 155, 156, 158 , 159, 161, 171, 173; CI Direct Green 25, 31, 32, 63, 66, and the like.

As acidic dyes other than direct dyes, azo dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, quinoline dyes, azine dyes, indigoid dyes, and the like can be used.
As the azo dye, for example, CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;
CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
CI Acid Violet 11, 56, 58;
CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
CI Acid Brown 2, 4, 13, 248;
CI Acid Blue 92, 102, 113, 117 and the like.
Examples of the phthalocyanine dyes include CI Acid Blue 249.
Examples of quinoline dyes include CI Acid Yellow 3.
Examples of azine dyes include CI Acid Blue 59,102.
Examples of indigoid dyes include CI Acid Blue 74.
Other dyes include CI Acid Violet 49; CI Acid Brown 19; CI Acid Blue 7, 9, 74, 112, 126, 167; CI Acid Green 9; I. Food green 3 etc. are mentioned.

Examples 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 (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. Acid Violet 9, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30 etc. are mentioned.
Examples of the anthraquinone dyes include CI Acid Red 82 and 92; CI Acid Violet 41, 42 and 43; CI Acid Blue 14, 22, 25, 40, 45, 78, 80 and 127: 1, 129, 145, 167, 230; CI Acid Green 25, 27, and the like.

Among these, preferred examples include xanthene acid dyes and anthraquinone acid dyes from the viewpoint of color developability.
The xanthene-based acid dye has a red or purple color and has a dye form.
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.
Among the above, C.I. I. It is preferable to use Acid Red 52, 87, 92, 289, 388.

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

  As the anthraquinone acid dye, an anthraquinone acid dye which is diaminoanthraquinone sulfonic acid is preferable in that it has heat resistance and light resistance while exhibiting color developability, color reproducibility and high brightness. The reason why these are excellent in heat resistance and light resistance is presumed that the structure is stabilized by bonding the carbonyl group part of the anthraquinone skeleton and the amino group part with a hydrogen bond.

  Especially, since the anthraquinone type acidic dye represented by following General formula (2) is excellent in the heat resistance of the coloring composition for color filters, and light resistance, it is preferable.

General formula (2)
[In general formula (2),
R ₅ and R ₆ each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alicyclic group that may have a substituent, or a substituent. Or an alkynyl group which may have a substituent, or an alkoxyl group which may have a substituent.
R _{7 to} R ₁₂ are each independently a hydrogen atom or a SO ₃ M group.
In addition, at least one of R _{5 to} R ₁₂ is an SO ₃ M group, or an alkyl group, an aryl group, an alicyclic group, an alkenyl group, an alkynyl group, or an alkoxyl group that is substituted with an SO ₃ M group. Either.
M represents a hydrogen ion or a sodium ion. ]

As R ₆ and R ₈ in the general formula (2), specific examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec -Butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, chloromethyl, bromomethyl, hydroxymethyl, cyanomethyl, nitromethyl, methoxymethyl, aminomethyl Group, dimethylaminomethyl group, acetonyl group, ethoxycarbonylmethyl group, diethylaminocarboxymethyl group, p-hydroxyphenylmethyl group, methylthiomethyl group, ethylthiomethyl group, butylthiomethyl group, phenylthiomethyl group, methylsulfinylmethyl group , Methylsulfonylmethyl group, ethyl Examples thereof include a sulfonylmethyl group, a benzenesulfonylmethyl group, a p-toluenesulfonylmethyl group, a salicyl group, an anisyl group, and the aryl group which may have a substituent includes a phenyl group, a p-tolyl group, a xylyl group, and a mesityl group. Group, cumenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, chlorophenyl group, bromophenyl group, fluorophenyl group and the like, and the alicyclic group which may have a substituent includes cyclohexyl group, cyclopentyl Group, cyclohexenyl group, norbornyl group, bornyl group, menthyl group, pinanyl group, adamantyl group and the like, and examples of the alkenyl group which may have a substituent include a vinyl group, a 2-propenyl group, an isopropenyl group, Butenyl, styryl group, cinnamyl group, etc. Suitable alkynyl groups include ethynyl groups, propynyl groups, and the like, and alkoxy groups that may have substituents include methoxy groups, tert-butoxy groups, benzyloxy groups, and the like. Examples of the aryloxy group that may be used include a phenoxy group, a p-tolyloxy group, a p-fluorophenoxy group, and a p-nitrophenoxy group.

Examples of the substituent include alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, sulfonic acid group, carboxyl group, halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxy group, cyano group, amino group Groups and the like.
Moreover, in this invention, a sulfonate group is also synonymous with a sulfonic acid group.

Also, if at least one of R ₅ to R ₁₂ is SO ₃ M group, a substituted SO ₃ M alkyl group substituted with a group, SO ₃ M aryl group substituted with a group, with SO ₃ M group has been being alicyclic group, or a alkenyl group, SO ₃ M alkynyl group substituted with a group or SO ₃ M alkoxyl group substituted with a group, which is substituted by SO ₃ M group.

  Specific structural formulas of preferable anthraquinone acid dyes are shown below, but are not limited thereto.

C. I. Acid Blue 112

C. I. Acid Blue 62

C. I. Acid Blue 138

  The anthraquinone acid dye used in the present invention exceeds 80% in the 440 nm region in the transmission spectrum, has a transmittance of 75% or more in the 450 nm region, and has a transmittance of 10% or less in the 550 nm region. Is preferred.

[Quaternary ammonium salt compound in which the molecular weight of the cation moiety is in the range of 190 to 900]
Next, the quaternary ammonium salt compound as the counter component of the acid dye will be described. In the quaternary ammonium salt compound in the present invention, the molecular weight of the cation moiety is in the range of 190 to 900.

A preferred form of the quaternary ammonium salt compound which is a counter 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.

Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (1). The molecular weight of the counter portion of the present invention is in the range of 190-900, preferably in the range of 240-850, particularly preferably in the range of 350-800. When the molecular weight is smaller than 190, the solubility in a solvent is lowered, and as a result, foreign matter is generated, which is not preferable. On the other hand, if the molecular weight is larger than 900, the ratio of the coloring component in the molecule is reduced, and the function as a coloring material cannot be sufficiently exhibited, and the fine pattern is peeled off in the resist patterning step, which is not preferable.
Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

  Moreover, what is represented by following General formula (1) is used as a quaternary ammonium salt compound.

General formula (1)

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

R ₁ to R ₄ in by the a 5 to 20 the number of at least two and C, solubility in solvents is improved. When the number of alkyl groups having a C number of less than 5 is 3 or more, solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if there is an alkyl group in which the number of C exceeds 20, the color forming property of the salt-forming compound (A) is impaired, and fine pattern peeling occurs in the resist patterning step, which is not preferable.

Specifically, monostearyl trimethyl ammonium chloride (cation portion molecular weight 312), distearyl dimethyl ammonium chloride (cation portion molecular weight 550), tristearyl monomethyl ammonium chloride (cation portion molecular weight 788), cetyltrimethyl ammonium Chloride (cation part molecular weight 284), trioctylmethylammonium chloride (cation part molecular weight 368), dioctyldimethylammonium chloride (cation part molecular weight 270), monolauryltrimethylammonium chloride (cation part molecular weight 228) , Dilauryldimethylammonium chloride (cation part molecular weight 382), trilaurylmethylammonium chloride The molecular weight of the cation moiety is 536), triamylbenzylammonium chloride (the molecular weight of the cation moiety is 318), trihexylbenzylammonium chloride (the molecular weight of the cation moiety is 360), trioctylbenzylammonium chloride (the molecular weight of the cation moiety is 444), trilauryl benzyl ammonium chloride (molecular weight of the cationic portion 612), benzyl dimethyl stearyl ammonium chloride (molecular weight 388 of the cation portion), and benzyl dimethyl octyl ammonium chloride (molecular weight of the cationic portion 248), dialkyl (alkyl C ₁₄ ~ C ₁₈ ) dimethylammonium chloride (cured beef tallow) (the molecular weight of the cation moiety is preferably 438 to 550) or the like is preferably used.

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

Specific examples of the quaternary ammonium salt compound products include Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50, etc. manufactured by Lion Corp. , 2C-75,2HT-75,2HT flakes, 2O-75I, 2HP-75,2HP flakes and the like, among others QUARTAMIN D86P (distearyldimethylammonium chloride), Arquad 2HT-75 (di (alkyl C ₁₄ ~ _C18 ) dimethylammonium chloride) is preferred.

[Chlorination]
A salt-forming compound of an acid dye and a quaternary ammonium salt compound can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, after the xanthene acid dye is dissolved in water, the quaternary ammonium salt compound is added and the chlorination treatment may be performed while stirring. Here, a salt-forming compound is obtained in which the sulfonic acid group (—SO ₃ H) moiety in the xanthene acid dye and the ammonium group (NH ₄ +) moiety of the quaternary ammonium salt compound are bonded. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

  The salt-forming compound (A) is particularly preferably C.I. I. Acid Red 289 or C.I. I. By setting the molecular weight of Acid Blue 112 and the counter, which is a cation component of the quaternary ammonium salt compound, to 350 to 800, a composition having excellent solvent solubility is obtained, and when used in combination with a blue pigment, It is excellent in light resistance and solvent resistance. Moreover, what becomes favorable when the salt-forming compound (A) is used in combination with the blue pigment is that the salt-forming compound (A) is adsorbed on the blue pigment while being dissolved and dispersed in the solvent.

(Other colorants)
In addition, an organic pigment can be added to the colored composition of the present invention as long as the effect is not hindered.

  Examples of the colorant used in the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 166, 168, 169, 176, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, Red pigments such as 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Further, basic dyes exhibiting red color, acidic dyes, and salt-forming compounds of these dyes can also be used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like and / or 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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Further, basic dyes exhibiting orange and / or yellow, acid dyes, and salt-forming compounds of these dyes can also be used.

Examples of the colorant used in the green coloring composition include C.I. I. Pigment green 7, 10, 36, 37, 58 and the like.
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, basic dyes exhibiting yellow, acidic dyes and salt-forming compounds of these dyes can be used in combination.

For example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, or 64 can be used as the colorant used in the blue coloring composition. . Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 can be used in combination with the blue coloring composition.
Of these, phthalocyanine pigments and / or triarylmethane lake pigments are preferable as blue pigments, and copper phthalocyanine blue pigments are preferable as phthalocyanine pigments.

  When using as a blue coloring composition, the salt-forming compound (A) is preferably used in an amount of 1 to 80 parts by weight with respect to 100 parts by weight of the blue 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. Regarding the mixing ratio, the mixing ratio can be arbitrarily changed in order to achieve a desired hue.

  When using as a green coloring composition, as for the usage-amount of a green pigment and salt-forming compound (A), 1-80 weight part of salt-forming compounds (A) are preferable with respect to 100 weight part of green pigments. 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 greatly, which is not preferable.

  When used as a red coloring composition, 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 greatly, which is not preferable.

[Miniaturization of pigment]
The pigment used in combination with the colored composition of the present invention can be 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, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to 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 parts by weight and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the total weight of the pigment from the viewpoint of both processing efficiency and production efficiency.

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

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

<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, 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.

  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.

  The resin is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the colorant because the film formability and various resistances are good, and since the colorant concentration is high and good color characteristics can be expressed. It is preferably used in an amount of 500 parts 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 resin having an ethylenically unsaturated double bond in the side chain include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).
By using a resin having an ethylenically unsaturated double bond in the side chain for an alkali developing resist for color filters, no coating film foreign matter is generated after applying the salt-forming compound (A), and salt formation in the resist The stability of the compound (A) 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 are likely to aggregate and precipitate, but by using a resin having an ethylenically unsaturated double bond in the side chain, the dye can easily be trapped in the resin-dye mixed liquid. In addition, the dye component is fixed by three-dimensional cross-linking of the resin when it is cured by ultraviolet rays or the like to form a film, and even if the solvent is removed in the subsequent development process, the dye component is aggregated and It is estimated that it becomes difficult to precipitate.

[Method (a)]
As the method (a), for example, the 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 similar method 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.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation.
The organic solvent in the present invention has a boiling point of 120 to 210 ° C. at 760 mmHg and a solubility parameter (= SP value) of 8.8 (cal / cm ³ ) ^1/2 or more 13.0 (cal / cm ³ ) ^{1 / It} contains less than ² organic solvent (S).

  Here, the solubility parameter (= SP value) is an index indicating the ease of dissolution of the non-electrolyte with respect to the organic solvent, such as Daicel Chemical Industries, Ltd. “Solvent Handling Product List” (2009.9.730 revised edition) catalog, etc. The value described in is used.

(Organic solvent (S))
The organic solvent used in the present invention has a boiling point of 120 to 210 ° C. at 760 mmHg and a solubility parameter (= SP value) of 8.8 (cal / cm ³ ) ^1/2 or more and 13.0 (cal / cm ³ ) ^1. The organic solvent (S) is less than ^{/ 2, and the} content of the organic solvent (S) with respect to the total amount of the solvent is 5 to 100% by weight. By using an organic solvent having this specific boiling point and SP value, the compatibility with the dye contained in the colorant is improved, and since the compatibility with the resin is also high, the generation of foreign matters can be suppressed, and coloring The composition can exhibit high brightness and a wide color reproduction region. Further, when a pigment is used in combination, it is preferable because the dispersion stability of the pigment is increased.

Further, when an organic solvent having a boiling point of less than 120 ° C. is used, the drying property becomes too high, and the composition ratio of the solvent and the non-volatile content are changed during production, storage, and use, which is not preferable.
When an organic solvent having a boiling point higher than 210 ° C. is used, it is difficult to dry when forming a thin film of the colored composition. Therefore, when applying the coating liquid by the spin coat method, a liquid swell is formed at the edge of the substrate, and the swelled liquid is smoothed from the edge of the substrate toward the center in the drying process from the end of the spin. As a result, a frame-like color unevenness (film thickness unevenness) is formed. Also in the die coating method, a portion where the liquid swells is formed at the application boundary, and smoothing proceeds from the boundary toward the center, resulting in the formation of a frame-like color unevenness (film thickness unevenness). .

  The content of the organic solvent (S) in the present invention is 5 to 100% by weight based on the total solvent amount (100% by weight). When the content of the organic solvent (S) is less than 5%, generation of foreign matters cannot be suppressed.

The organic solvent (S) is described together with <boiling point (° C.) / SP value (cal / cm ³ ) ^1/2 >.
Ethylene glycol monobutyl ether acetate <188 / 8.9>, ethylene glycol monomethyl ether acetate <145 / 9.0>, cyclohexanol acetate <173 / 9.2>, cyclohexanone <155 / 9.4>, propylene glycol Diacetate <190 / 9.6>, propylene glycol monomethyl ether <121 / 10.2>, 3-methoxybutanol <161 / 10.9>, diethylene glycol monoethyl ether <202 / 10.9>, γ-butyrolactone < 204 / 12.9> and the like.

[Organic solvent (S1)]
Among them, an organic compound having a boiling point at 760 mmHg of 120 to 210 ° C. and a solubility parameter (= SP value) of 8.8 (cal / cm ³ ) ^1/2 or more and less than 9.7 (cal / cm ³ ) ^1/2 When the solvent (S1) is used, the polarity of the organic solvent is increased, and the dye used in the present invention can be dissolved more preferably, so that the generation of foreign matter is suppressed, and further, when the filter segment is used as an optical filter The performance can be exhibited more preferably.

  Examples of the organic solvent (S1) include ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, cyclohexanol acetate, cyclohexanone, propylene glycol diacetate and the like.

[Organic solvent (S2)]
In particular, the SP has a boiling point at 760 mmHg of 120 to 210 ° C. and a solubility parameter (= SP value) of 9.7 (cal / cm ³ ) ^1/2 or more and less than 13.0 (cal / cm ³ ) ^1/2. When the organic solvent (S2) having a high value is used, the polarity of the organic solvent is further increased, and the dye used in the present invention can be dissolved more preferably, so that the generation of foreign matters is suppressed, and further, the filter segment is used. The optical performance can be more preferably exhibited.
When using an organic solvent (S2), it is preferable that it is 5 to 50 weight% on the basis of the whole quantity of coloring composition. The organic solvent (S2) has a higher SP value than the organic solvent (S1), and the boiling point is higher than that of the organic solvent (S1). However, when it is within the range of the above SP value, 5 to 50% by weight is preferable based on the total amount of the coloring composition.

  Examples of the organic solvent (S2) include propylene glycol monomethyl ether, 3-methoxybutanol, diethylene glycol monoethyl ether, and γ-butyrolactone.

(Other organic solvents)
In the present invention, as the organic solvent other than the organic solvent (S) and the organic solvent (S), the following can be used.
For example, propylene glycol monomethyl ether acetate <146 / 8.7>, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol di Acetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 3,5,5-trimethyl-2-cyclohexen-1-one 3,3,5-trimethylcyclohexanone, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 4-heptanone, m-xylene , M-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n Propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diisobutyl ketone, 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, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol mono Propyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol model Ether, propylene glycol monopropyl ether, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl acetate, isobutyl, propyl acetate, may also be used organic solvents such as dibasic esters.
These organic solvents are preferably 60 to 95% by weight based on the total amount of the colored composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a colorant comprising an acid dye and a salt-forming compound (A) comprising a quaternary ammonium salt compound (counter component thereof) having a molecular weight of a cationic moiety of 190 to 900, the resin, In a colorant carrier comprising a solvent, if necessary, preferably 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. It can be manufactured with fine dispersion. In addition, when the solubility of the salt forming compound (A) of the acid dye is high, specifically, the solubility in the solvent to be used is high. There is no need to manufacture it in a dispersed manner.
The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds (A), and other colorants separately 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 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 (3).
P-Ln Formula (3)
(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, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex 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 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

  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; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

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

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

<Photopolymerizable monomer>
The photopolymerizable monomer of the present invention includes a monomer or oligomer that forms a transparent resin by being cured by ultraviolet rays or heat, and these can be used alone or in admixture of two or more. The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

  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 coloring composition for a 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 add a solvent developing type or an alkali developing type coloring. It can be prepared in the form of a resist. The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the colorant, and 10 to 150 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

  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-methoxyphene) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -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- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime ester compounds; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.

<Sensitizer>
Furthermore, the 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 parts by weight with respect to 100 parts by weight of the total weight of the photopolymerization initiator contained in the colored composition, and is photocurable and developable. From the viewpoint, it is more preferably 5 to 50 parts 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 colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK 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. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 100% by weight of the coloring composition.

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

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

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

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

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- 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, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

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

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the colorant.

  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 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the colorant in the coloring composition.

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

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one filter segment uses the coloring composition for a color filter of the present invention. Formed.

<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 forming a filter segment by a photolithography method, a coating composition such as spray coating, spin coating, slit coating, roll coating, or the like is applied to the transparent composition on the transparent composition prepared as the solvent developing type or alkali developing type coloring resist. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. 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, 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 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, etc. 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.

  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. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

First, the acrylic resin solutions, refined pigments, salt-forming compounds (A), other salt-forming compounds, xanthene compounds, pigment dispersions, and pigment resist production methods used in Examples and Comparative Examples will be described.
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.
The specific surface area of the pigment particles was determined by the BET method using nitrogen adsorption. For the measurement, an automatic vapor adsorption amount measuring device (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) was used.

<Method for producing acrylic resin solution>
(Preparation of acrylic resin solution (RA-1))
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Thereafter, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 7 A mixture of 0.4 part and 0.4 part of 2,2′-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. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to obtain an acrylic resin solution (RA-1).

(Preparation of acrylic resin solution (RA-2))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 70.0 parts of cyclohexyl acetate, heated to 80 ° C., purged with nitrogen in the reaction vessel, and then dropped. N-Butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) from the tube A mixture of 0.4 part of 2,2′-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, sample approximately 2g of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add cyclohexyl acetate to the previously synthesized resin solution so that the nonvolatile content is 20 wt% As a result, an acrylic resin solution (RA-2) was obtained.

(Preparation of acrylic resin solution (RA-3))
A separable four-necked flask was charged with 207 parts of a cyclohexanol acetate 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 atmosphere in the flask was replaced with nitrogen. , 20 parts of methacrylic 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 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, 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 resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanol acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. (RA-3) was obtained. The weight average molecular weight (Mw) was 19000.

(Preparation of acrylic resin solution (RA-4))
A separable four-necked flask was charged with 370 parts of a cyclohexanol acetate 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 atmosphere in the flask was replaced with nitrogen. , 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2 0.0 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 and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanol acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution (RA-4). The weight average molecular weight (Mw) was 19000.

<Production method of fine pigment>
(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 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 yellow fine pigment 1)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 ("Irgafore Yellow 2R-CF" manufactured by Ciba Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 120 ° C for 8 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow fine pigment 1 were obtained. The specific surface area of the yellow fine pigment 1 was 70 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.

(Preparation of yellow fine pigment 2)
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, this 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 yellow fine pigment 2 were obtained. The specific surface area of the yellow fine pigment 2 was 65 m ² / g.

<Method for Producing Salt-Forming Compound (A)>
(Salt-forming compound (A-1))
In the following procedure, C.I. I. A salt-forming compound (A-1) composed of Acid Red 289 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety was 550) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 289 is dissolved, thoroughly mixed and stirred, heated to 70-90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of Acid Red 289 and distearyldimethylammonium chloride, a salt-forming compound (A-1) was obtained.

(Salt-forming compound (A-2))
In the following procedure, C.I. I. A salt-forming compound (A-2) composed of Acid Red 52 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety was 550) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 52 is dissolved, sufficiently mixed and stirred, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid red 52 and distearyldimethylammonium chloride, a salt-forming compound (A-2) was obtained.

(Salt-forming compound (A-3))
In the following procedure, C.I. I. A salt-forming compound (A-3) consisting of Acid Blue 112 and distearyldimethylammonium chloride (Coatamine D86P) (the molecular weight of the cation moiety was 550) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Blue 112 is dissolved, sufficiently mixed and stirred, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid blue 112 and distearyldimethylammonium chloride, a salt-forming compound (A-3) was obtained.

(Salt-forming compound (A-4))
In the following procedure, C.I. I. A salt-forming compound (A-4) composed of Acid Blue 140 and distearyldimethylammonium chloride (Cotamine D86P) (the molecular weight of the cation moiety was 550) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Blue 140 is dissolved and mixed and stirred thoroughly, heated to 70 to 90 ° C., and then Cotamine D86P is added dropwise little by little. Coatamine D86P may be dissolved in water and used as an aqueous solution. After adding Cotamine D86P dropwise, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid blue 140 and distearyldimethylammonium chloride, a salt-forming compound (A-4) was obtained.

<Methods for producing other salt-forming compounds>
(Salt Forming Compound (AC-1))
In the following procedure, C.I. I. A salt-forming compound (AC-1) composed of Acid Red 289 and tetraethylammonium chloride (the molecular weight of the cation moiety was 122) was produced.
In a 7-15 mol% sodium hydroxide solution, C.I. I. Acid Red 289 is dissolved, thoroughly mixed and stirred, heated to 70-90 ° C., and tetraethylammonium chloride is then added dropwise little by little. Tetraethylammonium chloride may be dissolved in water and used as an aqueous solution. After dropwise addition of tetraethylammonium chloride, the mixture is stirred at 70 to 90 ° C. for 60 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid red 289 and tetraethylammonium chloride, a salt-forming compound (AC-1) was obtained.

<Method for producing xanthene compound (C)>
(Xanthene compound (C-1))
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-1) were obtained. (Based on the description of JP-A-6-194828)

The solvents described in the following examples are abbreviated as follows.
<Boiling point (° C.) / SP value (cal / cm ³ ) ^1/2 >
Organic solvent (S) <120-210 / 8.8 or more and less than 13.0>

Organic solvent (S1) <120 to 210 / 8.8 or more and less than 9.7>
CHXA: cyclohexanol acetate <173 / 9.2>
ANO: cyclohexanone <155 / 9.4>

Organic solvent (S2) <120 to 210 / 9.7 or more and less than 13.0>
MB: 3-methoxybutanol <161 / 10.9>
γ-B: γ-butyrolactone <204 / 12.9>

Other solvents PGMAC: Propylene glycol monomethyl ether acetate <146 / 8.7>
EDGAC: Diethylene glycol monoethyl ether acetate <217 / 9.0>

<Method for producing pigment dispersion>
(Preparation of pigment dispersion (DP-1-7))
The following mixture was stirred and mixed in accordance with the combinations shown in Table 1 and then mixed with Eiger Mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. After time dispersion, the mixture was filtered through a 5.0 μm filter to prepare pigment dispersions (DP-1 to 7).
Colorant (pigment): 11.0 parts Acrylic resin solution: 40.0 parts Pigment dispersion diluent solvent: 48.0 parts Resin-type dispersant ("Solspers 20000" manufactured by Nippon Lubrizol): 1.0 part

<Method for producing pigment resist>
(Preparation of red resist)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a red resist.
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 Propylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist.
Pigment dispersion (DP-6): 45.0 parts Pigment dispersion (DP-7): 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 Propylene glycol monomethyl ether acetate: 23.2 parts

[Example 1]
(Preparation of dye solution (DA-1))
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to prepare a dye solution (DA-1).
Salt-forming compound (A-1): 11.0 parts Acrylic resin solution (RA-1): 40.0 parts Dye dilution solvent (CHXA): 49.0 parts

[Examples 2-8, Comparative Examples 1-4]
(Preparation of dye solution (DA-2 to 11))
Dye solutions (DA-2 to 11) were prepared in the same manner as in Example 1 (dye solution (DA-1)) except that the composition and blending ratio shown in Table 2 were changed.

The following evaluation was performed about dye solution (DA-2-12).
(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 is 500 times, and the number of particles that can be observed in any five fields of view 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 (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, Table 2 shows the results.

[Examples 9 to 21, Comparative Examples 5 to 8]
(Preparation of dye pigment mixed paste (DB-1 to 17))
According to the combinations shown in Table 3, the following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare dye pigment mixed pastes (DB-1 to 17).
Dye solution: 2.2 parts Pigment dispersion: 8.8 parts Acrylic resin solution: 40.0 parts Paste dilution solvent: 49.0 parts Note that the paste dilution solvent is used as necessary so that the solvent ratio shown in Table 3 is obtained. Two kinds of solvents were mixed.

The following evaluation was performed about the dye pigment mixed paste (DB-1 to 17).
(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 is 500 times, and the number of particles that can be observed in any five fields of view 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 (spots) due to foreign matters.
◎: Less than 5 ○: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or less, Table 3 shows the results.

As in Comparative Example 5, the dye pigment colored paste using a salt-forming dye having a small cation portion molecular weight contains 5% or more of a solvent having an SP value of 8.8 or more. There was a foreign object.
When a salt-forming compound consisting of an acid dye and a quaternary ammonium salt compound is not used as in Comparative Example 6, even if the solvent contains an SP value of 8.8 or higher containing 5% or more of a solvent, Foreign matter was generated in the film.
Since the dye pigment colored pastes of Comparative Examples 7 and 8 did not contain 5% or more of a solvent having an SP value of 8.8 or more, foreign matter was generated in the coating film using the paste.
In Examples 9 to 21, the foreign matter evaluation was “◎” or “、”, and the coating film evaluation was good and at a level that could be used.

[Examples 22 to 36, Comparative Examples 9 to 12]
According to the combinations shown in Table 4, the mixture of DC-4 and 5 is prescription 2, and otherwise, the mixture of prescription 1 is stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter. (DC-1 to DC-19) were obtained.
(Prescription 1)
Dye solution: 12.0 parts Pigment dispersion: 48.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Resist diluent solvent: 23.2 parts (prescription) 2)
Dye solution: 30.0 parts Pigment dispersion: 30.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ("NK ester ATMPT" manufactured by Shin-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 Resist diluent solvent: 23.2 parts As the resist dilution solvent, two kinds of solvents were mixed as necessary so that the solvent ratios shown in Table 4 were obtained.

(Evaluation of dye pigment resist (DC-1 to DC-19))
Each test of the chromaticity, foreign matter, heat resistance, light resistance and solvent resistance of the coating film of the obtained dye pigment resist (DC-1 to DC-19) was conducted by the following methods. The test results are shown in Table 5.

(Coating foreign material test method)
A resist was applied on the transparent substrate so that the dried coating film was about 2.5 μm, and the entire surface was exposed to ultraviolet light, and then heated in an oven at 230 ° C. for 20 minutes and allowed to cool to obtain an evaluation substrate. 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.
: Less than 5 ○: 5 or more, less than 20 Δ: 20 or more, less than 100 ×: 100 or more

(Evaluation of color characteristics)
A resist was applied on a glass substrate so that x = 0.150 and y = 0.060 using a C light source, and this 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.).

(Method of coating heat resistance test)
A resist is applied on a transparent substrate so that the dried coating film 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. To form a desired pattern. 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.

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

(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.

(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.

As in Comparative Example 9, a dye pigment colored paste using a salt-forming dye having a small cation portion molecular weight contains 5% or more of a solvent having an SP value of 8.8 or more. There was a foreign object. In addition, the brightness was inferior.
When a salt-forming compound consisting of an acid dye and a quaternary ammonium salt compound is not used as in Comparative Example 10, even if the solvent contains an SP value of 8.8 or more in a solvent of 5% or more, Foreign matter was generated in the film. In addition, the brightness was inferior, and the heat resistance, light resistance and solvent resistance were slightly inferior.
Since the dye pigment colored pastes of Comparative Examples 11 and 12 did not contain 5% or more of the solvent having an SP value of 8.8 or more, foreign matter was generated in the coating film using the paste.
In Examples 22 to 36, the foreign matter evaluation was “◎” or “○”, which was a level that could be used.

[Examples 37 to 51, Comparative Examples 13 to 16]
A color filter was prepared and evaluated according to the combinations shown in Table 6 as follows. A black matrix was patterned on a glass substrate, and a red resist was applied on the substrate with a spin coater to a thickness such that x = 0.640 and y = 0.330 to form a colored coating. 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. By using the same method, the green resist is made to have a film thickness such that x = 0.300 and y = 0.600, and blue resist (R-1) is used so that x = 0.150 and y = 0.060. The green filter segment and the blue filter segment were formed by coating each with such a film thickness to obtain color filters (CF-1 to 17).

(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.

  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.

  In the white display, Comparative Examples 13 to 16 have a problem in coating properties as described above, and are difficult to use practically.

Claims (4)

In the color filter coloring composition containing a colorant, a resin, and an organic solvent,
The colorant contains a salt-forming compound (A) comprising an acidic dye and a quaternary ammonium salt compound having a molecular weight of the cationic moiety in the range of 190 to 900,
The organic solvent has a boiling point at 760 mmHg of 120 to 210 ° C. and a solubility parameter (= SP value) of 8.8 (cal / cm ³ ) ^1/2 or more and less than 13.0 (cal / cm ³ ) ^1/2 Organic solvent (S)
Organic solvent (S) is, cyclo hexanol acetate, Kisano down cyclohexane, 3 - include methoxy pig no Le, an organic solvent selected from the group consisting of contact and γ- butyrolactone,
A coloring composition for a color filter, wherein the content of the organic solvent (S) is 5 to 100% by weight based on the total amount of the solvent. The coloring composition for a color filter according to claim 1, wherein the quaternary ammonium salt compound having a molecular weight of the cation moiety in the range of 190 to 900 is represented by the following general formula (1).
General formula (1)
[In General Formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ and R ₄ are present. The number of C is 5-20. Y ^- is representative of an inorganic or organic anion. ] The coloring composition for a color filter according to claim 1 or 2 , wherein the colorant further contains a phthalocyanine pigment and / or a triarylmethane lake pigment. A color filter comprising a filter segment formed using the colored composition for a color filter according to any one of claims 1 to 3 on a substrate.