KR102051933B1 - Color composition for color filter and color filter - Google Patents

Abstract

[일반식(1) 중, R₁, R₂ 및 R₃는 각각 독립적으로 하기 일반식(2)~(6)으로 표시되는 기인데, 적어도 1개는 일반식(2)~(4)으로 표시되는 기의 어느 하나이다]
일반식(2):

일반식(3):

일반식(4):

일반식(5):

일반식(6):

[일반식(2)~(6) 중, R₄, R₅ 및 R₆는 각각 독립적으로 H 또는 CH₃의 어느 하나이다. n은 0~10의 정수이다. m은 각각 독립적으로 1~20의 정수이다. l은 1~5의 정수이다.]The coloring composition for color filters which is hard to produce the fall of the brightness by heat processing of 180 degreeC or more, especially 230 degreeC, and the color filter formed using this color filter coloring composition are provided. The coloring composition for color filters of this invention contains a coloring agent [A], resin [B], and a monomer [C], a coloring agent [A] contains dye, and this monomer [C] is following General formula (1) Isocyanurate frame | skeleton containing monomer [C1] represented by the following.
Formula (1):

[In General formula (1), although R <_1> , R <_2> and R <_3> are group represented by following General formula (2)-(6) each independently, at least 1 is general formula (2)-(4) Is one of the groups displayed]
Formula (2):

Formula (3):

Formula (4):

Formula (5):

Formula (6):

[Formula (2) to (6) of, R _4, R ₅ and R ₆ are each independently selected from any one of H or CH _3. n is an integer of 0-10. m is an integer of 1-20 each independently. l is an integer from 1 to 5.]

Description

Color composition and color filter for color filters {COLOR COMPOSITION FOR COLOR FILTER AND COLOR FILTER}

The present invention relates to a color filter comprising a coloring composition for color filters used in the production of color filters contained in a color liquid crystal display device, a color imaging element, and the like, and a filter segment and / or a black matrix formed using the same. .

The liquid crystal display device has a structure in which a liquid crystal substance and many pixels are interposed between two polarizing plates. In the liquid crystal display device, a voltage is applied to each pixel to change the alignment state of the liquid crystal material, change the degree of polarization of light passing through the first polarizing plate, and control the transmitted light passing through the second polarizing plate to display an image.

By providing a color filter between these two polarizing plates, a liquid crystal display device can be used for color display and is used in television receivers, personal computers, monitors and the like.

The color filter is a glass plate that is formed of a black matrix (hereinafter referred to as BM), which is a grid-shaped light shielding film for preventing mixed color of transmitted light and increasing display contrast, and a filter segment of a plurality of colors (usually red, green, blue) arranged in correspondence to pixels. It has a structure provided on a transparent substrate, such as a back. The filter segments are fine, from a few microns to several hundred microns. The arrangement of the filter segments includes arrangement of two or more different colors in a fine stripe (stripe) shape (stripe arrangement), arrangement of horizontal and constant arrangements (delta arrangement), and the like. The filter segment and the BM are formed by applying a coloring composition and drying at a high temperature of generally at least 180 ° C., preferably at 230 ° C.

In a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and the alignment film for orientating a liquid crystal in a fixed direction is formed on it. In order to fully acquire the performance of these transparent electrodes and an oriented film, the formation must generally be performed at high temperature 180 degreeC or more, Preferably it is 230 degreeC or more. For this reason, as a manufacturing method of a color filter, the method called the pigment dispersion method which uses the pigment excellent in light resistance and heat resistance as a coloring agent is mainstream.

Examples of the quality required for the color liquid crystal display include high quality, low power consumption, and the like, and high brightness, high contrast, and high resolution color filters are required to achieve them.

In particular, in terms of power consumption, high brightness of color filters has become a trend.

When the color filter with high brightness is used, since the light transmittance is high, the number of backlight which is a light source can be reduced and power consumption can be suppressed.

Conventional color filters combine diketopyrrolopyrrole pigments and anthraquinone pigments in the red filter segment, copper or zinc phthalocyanine pigments and nickel azo complex pigments in the green filter segment. By combining copper phthalocyanine pigment, dioxazine pigment, etc., high brightness and a wide color display area were achieved. However, as described above, further high brightness is required for the color filter.

In recent years, further high brightness is required, and attention is being paid to the dye-based color material. Among them, xanthene-based dyes such as rhodamine dyes and eosin dyes, and triarylmethane-based dyes such as triphenylmethane have excellent color characteristics, and thus are expected as materials for achieving high brightness (for example, patents). See Documents 1 and 2).

However, when the pixel containing the said pigment | dye was produced and chromaticity was measured, after high temperature drying at 230 degreeC at the time of pixel formation, the brightness fell compared with before high temperature drying. The dye-based colorant has a problem in that it is not possible to obtain sufficiently high brightness by heat treatment because the heat resistance is worse than that of the pigments conventionally used. This suggests that there is room for further improvement in brightness if the decrease in brightness due to heat treatment can be suppressed.

Japanese Unexamined Patent Publication No. 2009-265641 Japanese Unexamined Patent Publication No. 2010-32999

The objective of this invention is providing the coloring composition for color filters which is hard to produce the fall of the brightness by heat processing of 180 degreeC or more, especially 230 degreeC, and the color filter formed using this color filter coloring composition.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, and, as a result, the outstanding spectral characteristics of the triphenylmethane type, quinoline type, thiazine type, thiazole type, and xanthene type pigment | dye and the high density of the isocyanurate compound have By paying attention to the crosslinking performance and the rigid skeleton, the present invention can be achieved by combining them.

That is, according to the first aspect of the present invention,

As a coloring composition for color filters containing a coloring agent [A], resin [B], and monomer [C],

The colorant [A] comprises a dye,

This monomer [C] contains the isocyanurate skeleton containing monomer [C1] represented by following General formula (1), The coloring composition for color filters is provided.

Formula (1):

[In General formula (1), although R <_1> , R <_2> and R <_3> are group represented by following General formula (2)-(6) each independently, at least 1 is general formula (2)-(4) Is one of the groups displayed]

Formula (2):

Formula (3):

Formula (4):

Formula (5):

Formula (6):

[Formula (2) to (6) of, R _4, R ₅ and R ₆ are each independently selected from any one of H or CH _3. n is an integer of 0-10. m is an integer of 1-20 each independently. l is an integer from 1 to 5.]

According to the second aspect of the present invention, the dye is a quinophthalone dye, an anthraquinone dye, an oxazine dye, a phthalocyanine dye, an azo dye, an indigoid dye, a triphenylmethane dye, a quinoline dye, a thia At least 1 sort (s) of pigment | dye [A1] chosen from the group which consists of a true dye, a thiazole dye, and a xanthene type pigment is provided, The coloring composition for color filters which concerns on 1st aspect is provided.

According to the 3rd aspect of this invention, the coloring composition for color filters which concerns on the 2nd aspect characterized by the xanthene type pigment | dye being a salt salt compound of a xanthene type | system | group acidic dye, and / or a sulfonamide compound of a xanthene type | system | group dye.

According to the 4th aspect of this invention, the coloring composition for color filters in any one of the 1st-3rd aspect characterized by the coloring agent [A] further including a pigment.

According to a fifth aspect of the present invention, the epoxy compound [P] (except for the case of isocyanurate skeleton-containing monomer [C1]) is further contained, according to any one of the first to fourth aspects. A coloring composition for color filters is provided.

According to the 6th aspect of this invention, the coloring composition for color filters in any one of the 1st-5th aspect characterized by further containing a photoinitiator [D] is provided.

According to the 7th aspect of this invention, the color filter formed from the coloring composition for color filters in any one of the 1st-6th aspect is provided.

According to this invention, the fall of the brightness by heat processing of 180 degreeC or more, especially 230 degreeC can be suppressed and a high brightness filter segment, for example, a red filter segment, a green filter segment, and a blue filter segment can be formed. have. By using a color filter including such a filter segment, a low power consumption color liquid crystal display device can be realized.

First, various structural components of the coloring composition for color filters which concern on embodiment of this invention are demonstrated.

In addition, when it is described as "(meth) acrylate", "(meth) acrylic acid", or "(meth) acrylamide", unless otherwise indicated, "acrylate and / or methacrylate", " Acrylic acid and / or methacrylic acid ”or“ acrylamide and / or methacrylamide ”.

In addition, "C.I." shown below means a color index (C.I.).

<Colorant [A]>

The coloring composition for color filters which concerns on embodiment of this invention contains dye as a coloring agent.

As the dye, any one pigment selected from the group consisting of quinophthalone series, anthraquinone series, oxazine series, phthalocyanine series, azo series, indigoid series, triphenylmethane series, quinoline series, thiazine series, thiazole series, and xanthene series It is preferable to contain [A1].

<Quinophthalone pigment | dye [A1]>

It does not specifically limit as a quinophthalone type dye, A well-known substance can be used. For example, the quinophthalone dyes described in Unexamined-Japanese-Patent No. 5-39269, Unexamined-Japanese-Patent No. 6-220339, Unexamined-Japanese-Patent No. 8-171201, etc. are mentioned, Specifically, C.I. Solvent Yellow 33, C.I. Disperse Yellow 54, C.I. The compound represented by the disperse yellow 64, etc. are mentioned.

<Anthraquinone Dye [A1]>

As an anthraquinone type dye, it is C.I. Direct blue 77 is mentioned.

<Oxane system pigment [A1]>

Examples of the oxazine dyes include C.I. Direct blue 97, 99, 106, 107, 108, 109, 190, 293 and the like.

<Phthalocyanine-based pigment [A1]>

Phthalocyanine dyes, which are direct dyes, include C.I. Direct Blue 86, 87, 189, 199, etc. are mentioned.

As phthalocyanine dye which is an acid dye, it is C.I. And acid blue 249.

<Azo dyes [A1]>

As an azo dye, for example, as a direct dye,

C.I. Direct yellow 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95, 98, 102, 109, 129, 136, 141;

C.I. 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;

C.I. 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;

C.I. Direct Green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82

Etc. can be mentioned.

As the same acid dye, for example,

C.I. 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;

C.I. Acid orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;

C.I. Acid violet 11, 56, 58;

C.I. Acid yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;

C.I. Acid brown 2, 4, 13, 248;

C.I. Acid Blue 92, 102, 113, 117

Can be mentioned.

<Indigoid dyes [A1]>

Examples of indigoid dyes include C.I. And acid blue 74.

<Triphenylmethane Dye [A1]>

(Form as Acid Dye of Triphenylmethane Dye)

Acidic dyes of triphenylmethane dyes include edible blue 101 (CI acid blue 1), acid pure blue (CI acid blue 3), lake blue I (CI acid blue 5), and lake blue II (CI acid blue 7). Blue 1 (CI acid blue 9), CI Acid blue 22, C.I. Acid blue 83, C.I. Acid blue 90, C.I. Acid blue 93, C.I. Acid blue 100, C.I. Acid blue 103, C.I. Acid blue 104, C.I. Preference is given to using acid blue 109.

(Form as Basic Dye of Triphenylmethane Dye)

Triphenylmethane-based basic dyes develop by taking a quinone structure by oxidation of NH ₂ or OH groups in the position of para with respect to the central carbon.

The triphenylmethane-based basic dyes are divided into the following three types by the number of NH ₂ and OH groups, and among them, the triphenylmethane-based basic dyes are preferably in the form of triaminotriphenylmethane-based basic dyes. will be.

a) diaminotriphenylmethane basic dyes

b) triaminotriphenylmethane basic dyes

c) rosolic acid basic dyes having an OH group

Triamino triphenylmethane-based basic dyes and diaminotriphenylmethane-based basic dyes are preferred because they have a clear color tone and excellent light fastness than others. Moreover, triphenylmethane basic dye is preferable.

Specifically, C.I. Basic Blue 1 (Basic Cyanine 6G), Copper 5 (Basic Cyanine EX), Copper 7 (Victoria Pure Blue BO), Copper 25 (Basic Blue GO), Copper 26 (Victoria Blue B conc.) And the like.

C.I. Basic green 1 (brilliant green GX), copper 4 (malachite green), etc. are mentioned.

C.I. Basic violet 1 (methyl violet), copper 3 (crystal violet), copper 14 (Magenta), etc. are mentioned.

(Form as Lake Pigment of Triphenylmethane Dye)

As triarylmethane-based lake pigments, specifically C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 62, C.I. Pigment violet 3, C.I. Pigment Violet 27, C.I. Pigment violet 39, and the like.

If more specifically indicate that

C.I. Pigment Blue 1.

C.I. Basic Blue 26, C.I. Basic blue 7 is rakes in phosphotungsten molybdate.

C.I. Pigment Violet 3.

C.I. Basic violet 1 is rakes with phosphotungsten molybdate.

C.I. Pigment Violet 39.

C.I. Basic Violet 3 (Crystal Violet) is rakes with phosphotungsten molybdate.

Among them, C.I. Preference is given to using Pigment Blue 1.

<Quinoline pigments [A1]>

As quinoline dyes, C.I. Solvent Yellow 33, C.I. Solvent Yellow 98, C.I. The dye marketed by the color index, such as solvent yellow 157, disperse yellow 54, disperse yellow 160, and acid yellow 3, is mentioned.

<Thiazine-based pigment [A1]>

Examples of thiazine dyes include Lauth's Violet, methylene blue, methylene green B, and C.I. obtained by oxidizing P-phenylenediamine under FeCl2 in the presence of hydrogen sulfide. Basic Blue 9, 17, 24, 25, Solvent Blue 8, C.I. Basic Green 5, C.I. Direct red 70, and the like.

<Thirazole-based pigment [A1]>

As the thiazole dye, a dye having a thiazole ring is used as a thiazole dye. Specifically, C.I. Basic Yellow 1, C.I. Basic Violet 44, 46, C.I. Basic Blue 116, C.I. Acid yellow 186, copper direct yellow 7, 8, 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, C.I. Direct Orange 18, C.I. Direct red 11;

<Xanthene-based dye [A1]>

The xanthene-based dye [A1] which can be preferably used in the embodiment of the present invention is red or purple, and preferably has the form of a dye, and any of oil-soluble dyes, acid dyes, direct dyes and basic dyes. It is preferable to have the form of. Moreover, the form of the lake pigment which laked these dyes may be sufficient.

Among these, xanthene-based oil-soluble dyes and xanthene-based acid dyes are preferable because of their excellent color.

As xanthene type pigment | dye [A1] which can be used in embodiment of this invention, C.I. Solvent Red, C.I. Oil-soluble dyes such as solvent violet, C.I. Basic Red, C.I. Basic dyes such as basic violet, and C.I. Acid Red, C.I. Acid dyes such as acid violet, C.I. Direct Red, C.I. The thing belonging to direct dyes, such as direct violet, etc. are mentioned.

Here, the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in the structure, and in the embodiment of the present invention, the direct dye is regarded as an xanthene acid dye.

The xanthene-based pigment [A1] used in the embodiment of the present invention has a transmittance of 90% or more in the region of 650 nm in the transmission spectrum, a transmittance of 75% or more in the region of 600 nm, and a transmittance of 5% in the region of 500 to 550 nm. Hereinafter, it is preferable that the transmittance | permeability is 70% or more in the 400 nm area | region. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500-550 nm, and the transmittance is 75% or more in the region of 400 nm.

Among these, xanthene-based basic dyes and xanthene-based dyes have spectroscopic characteristics having high transmittances in the range of 400 to 450 nm, but have problems in light resistance and heat resistance and are used in image display apparatuses using color filters requiring high reliability. In order to do this, the characteristic may not be sufficient.

Therefore, in order to improve such a fault, it is preferable to use the xanthene type basic dye by salt-forming using organic acid or perchloric acid. It is preferable to use organic sulfonic acid and organic carboxylic acid as an organic acid. Among them, naphthalene sulfonic acid and perchloric acid, such as tobias acid, are preferable in terms of resistance.

In addition, the xanthene acid dye is salt-forming using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound and the like, and a resin component having these functional groups to be used as a salt forming compound, or It is preferable in terms of resistance to sulfonamide and use as a sulfonamide compound.

Among these, quaternary ammonium salts, which are counter salts, in which the salt salt compounds of xanthene acid dyes and / or sulfonamide compounds of xanthene acid dyes are excellent in color and resistance, and also serve as counter ions for xanthene acid dyes to function as counter ions. It is more preferable to use the compound salt-formed using the compound and the sulfonamide compound which sulfonated the xanthene acid dye.

Among the xanthene dyes [A1], rhodamine dyes are preferred because they are excellent in color development and resistance.

Hereinafter, the form of the xanthene type pigment | dye [A1] used for embodiment of this invention is explained in full detail.

(Xanthene-based oil-soluble dye)

As xanthene oil soluble dye, C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 42, C.I. Solvent Red 43, C.I. Solvent Red 44, C.I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, C.I. Solvent Red 109, C.I. Solvent Red 140, C.I. Solvent Red 141, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent Violet 2, C.I. Solvent violet 10 and the like.

Among them, C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 49, C.I. Solvent Red 109, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent violet 2 is more preferred.

(Xanthene-based basic dye)

As xanthene basic dye, C.I. Basic Red 1 (Rhodamine 6GCP), 8 (Rhodamine G), C.I. Basic violet 10 (Rhodamine B) etc. are mentioned. Among them, C.I. Basic Red 1, C.I. Preference is given to using basic violet 10.

(Xanthene acid dyes)

As xanthene acid dyes, C.I. Acid red 51 (erythrosin (edible red No. 3)), C.I. Acid red 52 (acid rhodamine), C.I. Acid red 87 (Eosin G (edible red No. 103)), C.I. Acid red 92 (acid phloxine PB (edible red 104)), C.I. Acid red 289, C.I. Acid red 388, rose bengal B (edible red No. 5), acid rhodamine G, C.I. Preference is given to using acid violet 9.

Among them, in terms of heat resistance and light resistance, C.I. Acid red 87, C.I. Acid red 92, C.I. Acid red 388, or C.I. Acid red 52 (acid rhodamine), C.I. Acid red 289, acid rhodamine G, C.I. More preferably, acid violet 9 is used.

Among them, C.I., which is a rhodamine-based acid dye, is particularly excellent in color development, heat resistance, and light resistance. Acid red 52, C.I. Most preferably, acid red 289 is used.

(Salt salt compounds of xanthene acid dyes and / or sulfonamide compounds of xanthene acid dyes)

The xanthene acid dye in the embodiment of the present invention is co-salted using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound and the like, and a resin component having these functional groups, Since it is possible to impart high heat resistance, light resistance and solvent resistance, it is preferable to use a salt salt compound of a ten acidic dye or to sulfonamide to form a sulfonamide compound.

Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine ), Aliphatic unsaturations such as tridodecylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, Uji alkylamine, hardened Uji alkylamine, allylamine, etc. Primary amine, aniline, benzylamine, etc. are mentioned.

As the secondary amine compound, aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, Diphenylamine, dicoalkylalkylamine, dicured tallow alkylamine, distearylamine, and the like.

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

The xanthene-based dyes [A1] used in the embodiment of the present invention are particularly preferably salted xanthene-based dyes with quaternary ammonium salts or sulfonated with xanthene-based acid dyes. Two forms are explained in full detail below.

(Basic salt compound consisting of xanthene acid dye and quaternary ammonium salt compound)

It is most preferable to use the xanthene type pigment | dye [A1] used for embodiment of this invention as a salt forming compound which consists of the xanthene type | system | group acidic dye mentioned above and a quaternary ammonium salt compound from a viewpoint of heat resistance, light resistance, and solvent resistance.

(Quaternary ammonium salt compound)

The quaternary ammonium salt compound has an amino group so that the cation moiety becomes a counter of the xanthene acid dye.

The preferred form of the quaternary ammonium salt compound which is the counter component of the salt forming compound is colorless or white. Here, colorless or white means what is called a transparent state, and is defined as the state in which the transmittance | permeability is 95% or more, Preferably it is 98% or more in the 400-700 nm full-wavelength region of visible region. That is, it is necessary that it does not inhibit the color development of the dye component and does not cause discoloration.

It is preferable that the molecular weight of the cation part used as the counter of a quaternary ammonium salt compound is the range of 190-900. The cationic portion corresponds to the portion of (NR ₇ R ₈ R ₉ R ₁₀ ) ^{+ in} the following general formula (7). When molecular weight is less than 190, light resistance and heat resistance may fall, and the solubility to a solvent may fall. Moreover, when molecular weight becomes larger than 900, since the ratio of the color development component in a molecule | numerator falls, color development property may fall and brightness may fall. More preferably, the molecular weight of the cationic moiety is in the range of 240 to 850, and particularly preferably in the range of 350 to 800.

The molecular weight was calculated based on the structural formula, and the atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

Moreover, the compound represented by following General formula (7) can be used as a quaternary ammonium salt compound.

Formula (7):

[In General Formula (7), R <_7> -R <_10> represents a C1-C20 alkyl group or benzyl group each independently, and two or more of R <_7> , R <_8> , R <_9> , and R <_10> are C atoms of 5; It is ~ 20. Y ⁻ represents an inorganic or organic anion.]

When the number of C atoms of two or more side chains of R ₇ to R ₁₀ is 5 to 20, solubility in a solvent is good. When three or more alkyl groups whose number of C atoms is less than 5 in R <_7> -R <_10> become three or more, solubility to a solvent will worsen and a coating foreign material will arise easily. Moreover, when the alkyl group in which the number of C atoms exceeds 20 exists in a side chain, the coloring property of a salt-forming compound may be impaired.

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

Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (the molecular weight of the cation moiety is 74), tetraethylammonium chloride (the molecular weight of the cation moiety is 122), monostearyltrimethylammonium chloride (the molecular weight of the cation moiety is 312), Distearyldimethylammonium chloride (molecular weight of cation moiety 550), tristearyl monomethylammonium chloride (molecular weight of cation moiety 788), cetyltrimethylammonium chloride (molecular weight of cation moiety 284), trioctylmethylammonium chloride ( Cation moiety 368), dioctyldimethylammonium chloride (cationic moiety 270), monolauryltrimethylammonium chloride (cationic moiety 228), dilauryldimethylammonium chloride (cationic moiety 382) , Trilaurylmethylammonium chloride (cationic mole of molecular weight of 536 ), Triamylbenzylammonium chloride (molecular weight of cation moiety 318), trihexylbenzylammonium chloride (molecular weight of cation moiety 360), trioctylbenzylammonium chloride (molecular weight of cation moiety 444), trilaurylbenzylammonium chloride (Molecular weight of the cation moiety is 612), benzyldimethylstearylammonium chloride (the cation moiety has a molecular weight of 388), and benzyldimethyloctylammonium chloride (the cation moiety has a molecular weight of 248), or dialkyl (alkyl is C14 to C18) dimethyl It is preferable to use ammonium chloride (cured tallow) (molecular weight of cation part is 438-550) and the like.

As a product, Quartamine 24P, Quartamine 86P Conk, Quartamine 60W, Qutamine 86W, Quartamine D86P, Sanizol C, Sanizol B-50, etc., are made by Lion Corporation's AQUAD 210-80E, 2C-75, 2HT-75, 2HT flake, 2O-75I, 2HP-75, or 2HP flake, and the like, and among them, quartamine D86P (distearyldimethylammonium chloride) or aquad 2HT-75 (dialkyl (alkyl is C14-C18) dimethylammonium chloride) etc. are preferable.

The quaternary ammonium salt compound may be in the form of a resin having a cationic group, especially an amino group and an ammonium group in the side chain, and reacting with a xanthene acid dye to form a quaternary ammonium salt structure (see Reference 1).

(Reference Document 1) JP 2011-242752

(Resin Having Cationic Group in Side Chain)

Resin which has a cationic group in a side chain is an alkali resin containing the structural unit represented by following General formula (8). A salt-forming compound can be obtained by salt-forming the anionic group of xanthene type acid dye in general formula (8).

Formula (8):

[In General formula (8), R <_11> represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₁₂ to R ₁₄ each independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted, and two of R ₁₂ to R ₁₄ may be bonded to each other to form a ring. . Q represents an alkylene group, an arylene _{group, -CONH-R 15 -, -COO} -R 15 - represents the, R ₁₅ represents an alkylene group. Y ⁻ represents an inorganic or organic anion.]

(Method for Producing a Salt-Containing Compound)

The salt forming compound of a xanthene acid dye and a quaternary ammonium salt compound can be manufactured by a conventionally known method. Japanese Patent Laid-Open No. 11-72969 and the like have disclosed a specific technique.

For example, the xanthene acid dye may be dissolved in water, followed by a crude salt treatment while adding and stirring a quaternary ammonium salt compound. Here, xanthan a salt forming compound is obtained which combines part of the acid dye butene sulfonic acid group (-SO ₃ H) or a sulfonate group (-SO ₃ Na) portion and a quaternary ammonium group of the ammonium salt compound (NH ₄ ⁺⁾ in the. In addition, methanol and ethanol are solvents which can be used at the time of salting instead of water.

Moreover, the salt-forming compound used for embodiment of this invention stirs or vibrates the aqueous solution which melt | dissolved resin which has cationic group in the side chain represented by General formula (8), and xanthene type acid dye, or General formula (8 It can be easily obtained by mixing an aqueous solution of a resin having a cationic group and an aqueous solution of xanthene acid dye under side chains represented by) under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the xanthene acid dye are ionized, and they are ionically bonded, and this ion-bonded portion becomes water insoluble and precipitates. On the contrary, since the salt consisting of the large anion of the resin and the ocean ion of the xanthene acid dye is water-soluble, it can be removed by washing with water or the like. Resin and xanthene acid dye which have a cationic group in a side chain may respectively use only single type, and may use multiple types from which a structure differs.

As the salt forming compound, in particular, C.I. Acid red 289 or C.I. By using the salt forming compound of the acid red 52 and the quaternary ammonium salt compound whose molecular weight of the cation part used as a counter is 350-800, it is excellent in solvent solubility, and when used together with the pigment mentioned later, it is excellent in heat resistance, light resistance, and solvent resistance. It becomes an excellent thing by this. Moreover, it is guessed that what becomes a favorable thing by using a salt-forming compound together with a pigment is to adsorb | suck to a pigment, dissolving and disperse | distributing in a solvent. At this time, it is suitable that the primary particle diameter of a pigment is 20-100 nm.

Although the coloring composition which concerns on embodiment of this invention is mentioned later, the form of the blue coloring composition used together with a blue pigment, or the red coloring composition used together with a red pigment is preferable.

(Sulfonic acid amide compound of xanthene acid dye)

The sulfonamide compounds of the xanthene acid dyes which can be preferably used for the xanthene dyes [A1] according to the embodiment of the present invention are prepared by chlorination of a xanthene acid dye having -SO ₃ H or -SO ₃ Na by a conventional method. , -SO ₃ H can be prepared by -SO ₂ Cl, and the compound is reacted with an amine having a -NH ₂ group.

Moreover, as an amine compound which can be preferably used in sulfonamide, it is specifically 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3- Preference is given to using ethoxypropylamine, cyclohexylamine and the like.

For example, C.I. In the case of obtaining the sulfonic acid amide compound obtained by modifying acid red 289 using 3- (2-ethylhexyloxy) propylamine, C.I. Acid red 289 was sulfonylated and then reacted with the theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. The sulfonic acid amide compound of the acid red 289 may be obtained.

In addition, C.I. In the case where the acid red 52 is modified with 3- (2-ethylhexyloxy) propylamine to obtain a sulfonamide compound, C.I. Acid red 52 was sulfonylated and then reacted with the theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. The sulfonic acid amide compound of the acid red 52 may be obtained.

<Pigment>

The coloring agent [A] of the coloring composition for color filters which concerns on embodiment of this invention may further contain the pigment.

<Red Pigment [A2]>

As a coloring agent [A] of the coloring composition for color filters which concerns on embodiment of this invention, when using the said pigment [A1] and red pigment [A2] together, around 560-650 nm which light emission spectrum of many backlights has a characteristic peak. In this case, it is possible to have a high transmittance of the spectral spectrum, and higher brightness can be obtained as a red filter segment than a colorant in which a red pigment [A2] and the following other pigments conventionally used are combined.

Moreover, in embodiment of this invention, the specific example of the pigment which can be used as a coloring agent [A] when forming the pixel of a color filter is shown.

As red pigment [A2], it is C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48 , 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53 : 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81 : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254 , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like.

As an orange pigment which acts similarly to a red pigment, it is C.I. Pigment Orange Orange pigments, such as 36, 38, 43, 51, 55, 59, 61, can be used.

Among them, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. Pigment Red 254, C.I. Pigment Red 177, C.I. Particular preference is given to using Pigment Red 242.

<Green Pigment [A3]>

As a coloring agent [A] of the coloring composition for color filters which concerns on embodiment of this invention, when using the said pigment [A1] and green pigment [A3] together, 500-590 nm vicinity whose emission spectrum of many backlights has a characteristic peak. In this case, it becomes possible for the spectral spectrum to have a high transmittance, and higher brightness can be obtained as a green filter segment than a colorant combining a conventional green pigment and the following other pigments.

As green pigment [A3], it is C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among them, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. Pigment green 7, 36 or 58.

<Blue pigment [A4]>

As a coloring agent [A] of the coloring composition for color filters which concerns on embodiment of this invention, when using the said pigment [A1] and blue pigment [A4] together, the emission spectrum of many backlights is about 425-500 nm which has a characteristic peak. In this case, the spectral spectrum can have a high transmittance, and higher brightness can be obtained as a blue filter segment than a colorant in which a conventional blue pigment and the following other pigments are combined.

As blue pigment [A4], it is C.I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33 , 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among them, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, more preferably C.I. Pigment Blue 15: 6.

<Other pigments>

As a yellow pigment, it is C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36 : 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94 , 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139 , 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174 , 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207, 208 and the like. Among them, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185, more preferably C.I. Pigment yellow 83, 138, 139, 150, or 180.

As a purple pigment, it is C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50 and the like. Among them, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. Pigment violet 19, or 23, more preferably C.I. Pigment Violet 23.

<Pigmentation>

The pigment used in embodiment of this invention can be refine | miniaturized by performing a salt milling process etc. It is preferable that the primary particle diameter of a pigment is 20 nm or more from the point which the dispersion | distribution to a pigment carrier is favorable. Moreover, it is preferable that it is 100 nm or less from the point which can form the filter segment with high contrast ratio. Especially preferable range is the range of 25-85 nm. In addition, the primary particle diameter of a pigment has the method of measuring the size of a primary particle directly from the electron microscope photograph by the TEM (transmission electron microscope) of a pigment, for example. Specifically, for example, assume that a sphere having a particle diameter obtained by measuring the minor axis diameter and major axis diameter of the primary particles of each pigment in nm units, the average of which is the primary particle diameter of the pigment particles, and then obtained. There is a method of calculating the volume average particle diameter by calculating the volume of the particles, performing this operation on 100 pigment particles, and calculating the particle size and volume based on each particle.

Salt milling treatment is performed by kneading a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, and mechanically kneading with water. It removes a water-soluble inorganic salt and a water-soluble organic solvent by the process. The water-soluble inorganic salt acts as a crushing aid, and during salt milling, the pigment is crushed using the height of the hardness of the inorganic salt. By optimizing the conditions at the time of salt milling the pigment, it is possible to obtain a pigment having a very small primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but it is preferable to use sodium chloride (salt) from the viewpoint of price. It is preferable to use 50-2000 mass parts with respect to 100 mass parts of pigments, and, as for a water-soluble inorganic salt, from both surfaces of processing efficiency and production efficiency, it is most preferable to use 300-1000 mass parts.

The water-soluble organic solvent acts 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, since the temperature rises at the time of salt milling and a solvent becomes easy to evaporate, the high boiling point solvent of 120 degreeC or more of boiling point is preferable at the point of safety. 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, etc. are used. It is preferable to use 5-1000 mass parts with respect to 100 mass parts of pigments, and, as for a water-soluble organic solvent, it is most preferable to use 50-500 mass parts.

When salt milling a pigment, you may add resin as needed. The kind of resin used is not specifically limited, A natural resin, a modified natural resin, a synthetic resin, the synthetic resin modified with the natural resin, etc. can be used. Resin used is solid at room temperature, it is preferable that it is water-insoluble, and it is more preferable that it is partially soluble in the said organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

When producing a pigment dispersion, it is preferable to add a pigment derivative in order to prevent aggregation of a pigment, to keep the pigment finely dispersed, and to manufacture a color filter with high color purity with high brightness and high contrast ratio. Content of a pigment derivative becomes like this. Preferably it is 0.5 mass part or more, More preferably, it is 1 mass part or more, Most preferably, it is 3 mass parts or more with respect to 100 mass parts of pigments. Moreover, from a heat resistant and light resistant viewpoint, content of a pigment derivative becomes like this. Preferably it is 40 mass parts or less, Most preferably, it is 35 mass parts or less with respect to 100 mass parts of pigments.

Pigment derivatives are compounds in which a basic or acidic substituent is introduced into an organic dye. Organic dyes also include light yellow aromatic polycyclic compounds which are not generally called dyes, such as naphthalene, anthraquinone, acridon, and the like. As a pigment derivative, Unexamined-Japanese-Patent No. 63-305173, Unexamined-Japanese-Patent No. 57-15620, Unexamined-Japanese-Patent No. 59-40172, Unexamined-Japanese-Patent No. 63-17102, Unexamined-Japanese-Patent No. 5-5 9469, Unexamined-Japanese-Patent No. 9-176511, etc. can be used, These can be used individually or in mixture of 2 or more types.

The resin type dispersing agent which is excellent in pigment dispersibility and big in preventing the reaggregation of the pigment after dispersion can be added to the coloring composition for color filters which concerns on embodiment of this invention. The resin type dispersant is preferably 0.1 to 40 parts by mass, and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment.

The resinous dispersant is preferably a polymer having an acidic group or a basic group in view of adsorbing on the surface of the pigment using an acidic group or a basic group as an anchor, and effectively exhibiting a resilient stability by acting as a repelling effect of the polymer. As an acidic group, a sulfone group is preferable at the point which is excellent in adsorption characteristic, and an amino group is preferable at the point which is excellent in adsorption characteristic as a basic group. Moreover, the combination of the pigment derivative which has an acidic group and the resin type dispersing agent which has a basic group, or the combination of the pigment derivative which has a basic group and a resin type dispersing agent which has an acidic group is preferable because of its good compatibility with resin.

As a resin type dispersing agent which has an acidic group or a basic group, the comb polymer of the structure in which the branched polymer part was graft-bonded to the stem polymer part which has an acidic group or a basic group is preferable because it has organic solvent solubility more from the steric repulsion effect excellent in the branched polymer part. Moreover, the comb-type polymer which has the molecular structure which graft-bonded the branched polymer of 2 or more molecules to 1 molecule of a stem polymer is more preferable from the said reason.

Commercially available resin type dispersants include DisPerByk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, manufactured by BIC Chemistry Co., Ltd. 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-TerrA-U, 203, 204, or BYK-P104, P104S, 220S, or LACtimon, LACtimon-WS or Bykumen, etc. Brisol's SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120 , 150, 1501, 1502, 1503 and the like.

<Other colorants>

In the coloring composition for color filters which concerns on embodiment of this invention, you may use together dye other than xanthene dye as other coloring agent.

<Resin [B]>

It is preferable that the coloring composition for color filters which concerns on embodiment of this invention contains resin [B] further. Dispersion stability of a coloring composition becomes more favorable by containing resin [B], and when the colored pixel layer of a color filter is formed using this coloring filter composition for coloring, there are few pigment aggregates, and developability and pattern shape are also favorable coloring. A pixel layer can be obtained.

Resin [B] is a resin having a spectral transmittance of preferably 80% or more, and more preferably 95% or more in the full-wavelength region of 400 to 700 nm in the visible light region.

Moreover, a thermoplastic resin is preferable and when using in the form of an alkali developing type coloring resist material, it is preferable to use alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. Moreover, in order to improve light sensitivity, active energy ray curable resin which has an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali developing type colored resist material, the photocuring density is increased by three-dimensional crosslinking of the resin when exposing with an active energy ray to form a coating film, It is more preferable because it leads to improvement of resistance as a result.

Examples of the thermoplastic resin include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, and polyester resins. , Vinyl-based resins, alkyd resins, polystyrene resins, polyamide resins, rubber-based resins, cyclized rubber-based resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Especially, it is preferable to use an acrylic resin.

As alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example.

Specifically as alkali-soluble resin, acrylic resin which has an acidic group, (alpha) -olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer, or isobutylene / (anhydride) male Acid copolymers, etc. Among these, acrylic resins having acidic groups and at least one resin selected from styrene / styrenesulfonic acid copolymers, particularly acrylic resins having acidic groups, are suitably used because of their high heat resistance and transparency. .

As active energy ray curable resin which has an ethylenically unsaturated double bond, resin which introduce | transduced ethylenically unsaturated double bond by the method (i) or (ii) shown below is mentioned, for example.

(Method (i))

As the method (i), for example, an carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to the side chain epoxy group of the copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers. Moreover, there exists a method of making a polybasic acid anhydride react with the produced hydroxyl group, and introducing an ethylenically unsaturated double bond and a carboxyl group.

As ethylenically unsaturated monomer which has an epoxy group, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxy ethyl (meth) acrylate, 3,4 epoxy butyl (meth), for example Acrylate and 3, 4 epoxycyclohexyl (meth) acrylate are mentioned, These may be used independently and may use two or more types together. From the viewpoint of reactivity with unsaturated monobasic acid of the next step, glycidyl (meth) acrylate is preferred.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-position haloalkyl, alkoxyl, halogen, nitro and cyano substituents of (meth) acrylic acid. These may be used, These may be used independently and may use two or more types together.

Examples of the polybasic acid anhydride include tetrahydro phthalic anhydride, phthalic anhydride, hexahydro phthalic anhydride, succinic anhydride and maleic anhydride. These may be used alone or in combination of two or more kinds. If necessary, the remaining anhydride groups may be hydrolyzed using tricarboxylic anhydrides such as trimellitic anhydride, or tetracarboxylic dianhydrides such as pyromellitic dianhydride, such as increasing the number of carboxyl groups. It may be. Moreover, when tetrahydro phthalic anhydride or maleic anhydride which has an ethylenically unsaturated double bond is used as a polybasic acid anhydride, an ethylenically unsaturated double bond can be extended further.

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

(Method (ii))

As the method (ii), an isocyanate of an ethylenically unsaturated monomer having an isocyanate group is used in a side chain hydroxyl group of an unsaturated monobasic acid monomer having another carboxyl group and copolymerization of another monomer using an ethylenically unsaturated monomer having a hydroxyl group. There is a way to react groups.

As ethylenically unsaturated monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates, such as glycerol (meth) acrylate or cyclohexane dimethanol mono (meth) acrylate, are mentioned, These may be used independently and may use two or more types together. Moreover, polyether mono (meth) acrylate which addition-polymerized ethylene oxide, propylene oxide, and / or butylene oxide, etc. to the said hydroxyalkyl (meth) acrylate, (poly) (gamma) -valerolactone, ( (Poly) ester mono (meth) acrylate which added poly) (epsilon) -caprolactone, and / or (poly) 12-hydroxystearic acid, etc. can also be used. 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from a viewpoint of coating film foreign material suppression.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. You can use together more than a kind.

In order for the weight average molecular weight (Mw) of resin [B] to disperse | distribute a coloring agent [A] preferably, the range of 10,000-100,000 is preferable, More preferably, it is the range of 10,000-80,000. Moreover, the range of 5,000-50,000 is preferable, and, as for number average molecular weight (Mn), it is preferable that the value of Mw / Mn is 10 or less.

When using resin [B] as the photosensitive coloring composition for color filters, it is preferable to use resin of acid value 20-300 mgKOH / g from a viewpoint of the dispersibility, permeability, developability, and tolerance of a pigment. If the acid value is less than 20 mgKOH / g, solubility in the developer is poor, and it is difficult to form a fine pattern. If the acid value exceeds 300 mgKOH / g, no fine pattern remains.

Since resin [B] is favorable in film-forming property and agent resistance, it is preferable to use it in the quantity of 20 mass parts or more with respect to 100 mass parts of coloring agents [A], a high coloring agent density | concentration, and the point which can express favorable color characteristic. Is preferably used in an amount of 1000 parts by mass or less.

Moreover, the coloring composition for color filters which concerns on embodiment of this invention may contain the hardening | curing agent, a hardening accelerator, etc. as needed. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective. However, the curing agent is not particularly limited, and any curing agent may be used as long as it can react with the thermosetting compound. As said curing accelerator, for example, an amine compound (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, triethylbenzyl ammonium chloride, etc.), block isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amides Dine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimida Sol, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compound (for example, triphenylphosphine, etc.) ), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2 -Vinyl-4,6-diamino-S-triazine isocyanuric acid Adducts, 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts) and the like can be used. These may be used individually by 1 type and may use 2 or more types together. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of isocyanurate compounds [C].

Monomer [C]

<Isocyanurate skeleton containing monomer [C1]>

The coloring composition for color filters which concerns on embodiment of this invention contains the isocyanurate skeleton containing monomer [C1] represented by following General formula (1) as a monomer.

Formula (1):

[In General formula (1), although R <_1> , R <_2> and R <_3> are group represented by following General formula (2)-(6) each independently, at least 1 is general formula (2)-(4) Is one of the groups displayed]

Formula (2):

Formula (3):

Formula (4):

Formula (5):

Formula (6):

[Formula (2) to (6) of, R _4, R ₅ and R ₆ are each independently selected from any one of H or CH _3. n is an integer of 0-10. m is an integer of 1-20 each independently. l is an integer from 1 to 5.]

Heat resistance is greatly improved by firm crosslinking by isocyanurate skeleton containing monomer [C1].

As a result, the fall of the brightness after heat processing is suppressed, and the brightness improves as a color filter.

Content of isocyanurate frame | skeleton containing monomer [C1] is 1-300 mass parts with respect to 100 mass parts of coloring agents [A] in the coloring composition for color filters, for example, Preferably it is 10-250 mass parts. When isocyanurate frame | skeleton containing monomer [C1] exceeds 300 mass parts, addition amount of resin, a photoinitiator, etc. is restrict | limited and sufficient developability and sensitivity may not be ensured, and dispersion stability may become a problem. have. On the contrary, when an isocyanurate skeleton containing monomer [C1] is contained less than 1 mass part, heat resistance may become inadequate.

<Other monomers [C2]>

Other monomers include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyl Oxypropyl succinic acid, 2-methacryloyloxypropyl succinic acid, methoxy ethylene glycol acrylate, methoxy ethylene glycol methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylic Latex, methoxy triethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, 2-hydroxy-3-phenoxy 2-acryloyl as a propyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, or a commercial item Oxyethyl succinic acid (brand name M-5300), polyethylene glycol di (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol Adi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, di Ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, dipentaerythritol penta (meth) acrylate , Caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane Lee monomer, or a portion having a (meth) acrylic acid esters, and various kinds of methacrylic acid esters such as acrylate, the acid groups and the like photo-polymerization monomer that is polymerizable by the radical organic.

(Monomer having an acid group)

Examples of the monomer having an acidic group include esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohols and (meth) acrylic acid and dicarboxylic acids; polyhydric carboxylic acids and monohydroxyalkyl (meth) acrylates. And esterified products thereof. Specific examples include trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and the like. Free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tri Carboxylic acid (tricarvallylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene Tricarboxylic acids such as -1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl meth Mono acrylates Oligonucleotide-containing de-hydroxy monoacrylate or monohydroxy free carboxyl groups of the mono and methacrylates may be mentioned the esterified product and the like.

Moreover, the compound represented by following General formula (10) can also be used preferably.

Formula (10):

(H ₂ C = C (R ₁₆ ) COO) _m -X- (OCOCH (R ₁₆ ) CH ₂ S (R ₁₇ ) COOH) _n

[In General Formula (10), R <_16> is a hydrogen atom or a methyl group, R <_17> is a C1-C12 hydrocarbon group, X is a (m + n) valence C3-60 organic group, m is an integer of 2-18. , n represents an integer of 1 to 3.]

Here, the compound represented by following General formula (10) can be easily obtained by the following method, for example.

(1) The method of adding the mercapto compound to the obtained compound after esterifying and acrylating the compound which gives the organic group represented by X with acrylic acid.

(2) A method in which a mercapto compound is added to the obtained compound after the compound giving the organic group represented by X is modified with a polyisocyanate compound and then acrylated with an acrylate compound having a hydroxyl group.

(3) A method in which a compound giving an organic group represented by X is esterified with acrylic acid to be acrylated, modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

Examples of the compound imparting the organic group represented by X include pentaerythritol, caprolactone modified substance of pentaerythritol, polyisocyanate modified substance of pentaerythritol, dipentaerythritol, caprolactone modified substance of dipentaerythritol, and dipenta Polyisocyanate modified substance of erythritol is mentioned.

As a mercapto compound, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, a mercaptosuccinic acid, etc. are mentioned, for example.

It is preferable that it is 5-400 mass parts with respect to 100 mass parts of coloring agents [A], and, as for content of monomer [C], it is more preferable that it is 10-300 mass parts from a viewpoint of photocurability and developability.

<Epoxy compound [P]>

The epoxy compound in this invention points out the compound which has an epoxy group. The epoxy compound may be a low molecular compound or a high molecular weight compound such as a resin.

Preferable in this invention is an epoxy equivalent in the range of 100-500, More preferably, it is the range of 100-250. When epoxy equivalent is less than 100, sclerosis | hardenability is high, the crosslinking density of a film becomes high too much, shrinkage at the time of hardening becomes large, and flatness of a film is not obtained. When epoxy equivalent exceeds 500, sclerosis | hardenability will run short and the effect of suppression of a contrast ratio fall and NMP resistance improvement by a heat processing process will become small. The epoxy equivalent in this invention points out the value defined by "molecular weight ÷ epoxy group: unit g / eq" calculated | required by calculation from the chemical formula of an epoxy compound, ie, the molecular weight per one epoxy group.

Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl Substituted dihydroxybenzene, dihydroxy naphthalene, etc.) and various aldehydes (formaldehyde, acetoaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutalaldehyde, phthalaldehyde, cintonaldehyde, croton Polycondensates with aldehydes, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, di Polymers with isopropenyl biphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl iso portion) Polycondensates with ketones, acetophenones, benzophenones, etc., phenols and aromatic dimethanols (benzenedimethanol, α, α, α ', α'-benzenedimethanol, biphenyldimethanol, α, α, α', polycondensates of α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as α, α'-dichloroxylene, bischloromethylbiphenyl), polycondensates of bisphenols and various aldehydes, alcohols Glycidyl ether epoxy compound, an alicyclic epoxy compound, a glycidyl amine epoxy compound, glycidyl ester epoxy compound etc. which glycidylated etc. are mentioned, It is limited to these if it is an epoxy compound normally used. It is not. These may be used independently and may use 2 or more types.

As a commercial item, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above brand name; Yuka Shell Epoxy Co., Ltd. product), Epicoat 1004 , Epicoat 1256 (more than brand name; product made in Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (brand name; product made by Mitsui Kagaku Co., Ltd.), EPPN-501H, 502H (brand name; Nihon Kayaku Co., Ltd.), JER 1032H60 (Brand name; Japan epoxy resin Co., Ltd.), JER 157S65, 157S70 (brand name; Japan epoxy resin Co., Ltd.), EPPN-201 (brand name; Nihon Kayaku Co., Ltd.), JER152, JER154 (above brand name; Japan epoxy resin Co., Ltd., EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (more brand name; Nihon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (more brand name; Daiselka Gakuko Bridge Co., Ltd., Denacall EX-810, EX-830, EX-851, EX-611, EX-512, EX-421, EX-313, EX-201, EX-111 (more brand names; Nagase Chemtex Co., Ltd. etc. are mentioned, It is not limited to these.

Among them, the epicoat 807, the epicoat 815, the epicoat 825, the epicoat 827, the epicoat 828, the epicoat 190P, and the epicoat 191P whose epoxy equivalents are in the range of 100-250 (above brand names; Yuka Shell Epoxy Co., Ltd. product) , TECHMORE VG3101L (brand name; product made by Mitsui Kagaku Co., Ltd.), EPPN-501H, 502H (brand name; product made by Nihon Kayaku Co., Ltd.), JER 1032H60 (brand name; product made in Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (Brand name; product made in Japan Epoxy Resin Co., Ltd.), EPPN-201 (product name; product made in Nihon Kayaku Co., Ltd.), JER152, JER154 (more brand name; product made in Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S , EOCN-104S, EOCN-1020 (above brand name; product made in Nihon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (more brand name; Daiselka Chemical Co., Ltd. product), Denacol EX-810, EX- 851, EX-611, EX-512, EX-421, EX-313, EX-201, and EX-111 (above trade names; manufactured by Nagase Chemtex Co., Ltd.) and the like are preferable in terms of flatness and curability of the film.

Photoinitiator [D]

Examples of the photopolymerization initiator [D] include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholi Acetophenone compounds such as nil) phenyl] -1-butanone, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, Methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t-butylperoxycar Benzophenone compounds such as carbonyl) benzophenone, thioxanthone, 2- Thioxanthone type compounds, such as chlor thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2, 4- diethyl thioxanthone, 2,4,6 -Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine , 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine compounds such as 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O -Benzoyl oxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxya Phosphine compounds such as oxime ester compounds, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4', 5, Imidazole compounds such as 5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-methylphenyl) biimidazole, 9, Quinone compounds, such as 10-phenanthrene quinone, camphor quinone, and ethyl anthraquinone, a borate type compound, a carbazole type compound, a titanocene type compound, etc. are used.

These photoinitiators [D] can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

Among these, it is more preferable to contain an acetophenone type compound or an oxime ester type compound as a photoinitiator [D]. Since acetophenone type compound and an oxime ester type compound are very sensitive, content of a photoinitiator [D] can be made small. As a result, the brightness as a color filter can be improved, which is preferable.

It is preferable that these photoinitiators [D] are 5-200 mass parts with respect to 100 mass parts of coloring agents [A] in the coloring composition for color filters, and it is more preferable that they are 10-150 mass parts from a viewpoint of photocurability and developability.

<Sensitizer [E]>

Moreover, the sensitizer can be contained in the coloring composition for color filters which concerns on embodiment of this invention.

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Polymethine pigments such as acidene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, Thiazine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporpyrazine derivatives, Phthalocyanine derivatives, tetraazaporpyrazine derivatives, tetraquinoxalinoporpyrazine derivatives, naph Rocyanine derivatives, subphthalocyanine derivatives, pyryllium derivatives, thiopyryllium derivatives, tetrapyrine derivatives, arnylene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospyropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketones Derivatives; and the like.

These sensitizers can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

Also specifically, Makoto Okawara, "Painted Handbook" (Godansha, 1986), Makoto Okawara, "Chemical of Functional Pigments" (CMC, 1981), Ikemori Chuzaburo, "Special Features" Sensitizers described in "Material" (CMC, 1986), but the present invention is not limited thereto. Moreover, the sensitizer which shows absorption with respect to the light from ultraviolet to a near-infrared region can also be contained.

Particularly suitable sensitizers in the above sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 1-chloro- 4-propoxycyxanthone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N -Ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole and the like are used.

It is preferable that it is 3-60 mass parts with respect to 100 mass parts of photoinitiators [D] contained in a coloring composition, and, as for content of a sensitizer, it is more preferable that it is 5-50 mass parts from a viewpoint of photocurability and developability.

<Solvent>

In the coloring composition for color filters which concerns on embodiment of this invention, a solvent disperse | distributes a coloring agent [A] fully in pigment carriers, such as resin [B] and a monomer [C], and dried film on transparent substrates, such as a glass substrate, It is used in order to make it easy to form a filter segment or a black matrix by apply | coating so that thickness may be 0.2-10 micrometers.

As the solvent, for example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone , 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-methoxybutanol, 3-methoxybutylacetate, 4-heptanone, m -Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetoamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, N-methylpyrroli Don, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, iso Butyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether , Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene Glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, di Propylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol Diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. have.

These solvents can be used individually or in mixture of 2 or more types in arbitrary ratios as needed.

A solvent is 100-10000 mass parts with respect to 100 mass parts of pigments in a coloring composition, Preferably it can be used in the quantity of 500-5000 mass parts.

<Multifunctional thiol>

The coloring composition for color filters which concerns on embodiment of this invention can contain a polyfunctional thiol. Multifunctional thiols are compounds having two or more thiol (SH) groups.

By using the polyfunctional thiol together with the above-mentioned photoinitiator [D], it acts as a chain transfer agent in the radical polymerization process after light irradiation, and since the tiradal which does not receive polymerization inhibition by oxygen generate | occur | produces, coloring for the color filter obtained The composition is highly sensitive. In particular, the polyfunctional aliphatic thiol which SH group couple | bonded with aliphatic groups, such as methylene and ethylene group, is preferable.

Examples of the polyfunctional thiols include hexanedithiol, decandithiol, 1,4-butanediolbisthiopropionate, 1,4-butanediolbisthioglycolate, ethylene glycolbisthioglycolate, ethylene glycol bisthiopropionate , Trimethylolpropane tristhioglycolate, trimethylolpropane tristyopiothionate, trimethylol ethane tris (3-mercaptobutylate), trimethylol propane tris (3-mercapto butyrate), trimethylol propane tris (3 Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakistiopionionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3 Mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2, 4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, etc. are mentioned.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

As for content of a polyfunctional thiol, 0.05-100 mass parts is preferable with respect to 100 mass parts of coloring agents [A], More preferably, it is 1.0-50.0 mass parts.

By using 0.05 mass part or more of polyfunctional thiols, better image development resistance can be obtained. When a thiol (SH) group uses one monofunctional thiol, such improvement in development resistance is not obtained.

<Leveling agent>

In order to improve the leveling property of the composition on a transparent substrate, it is preferable to add a leveling agent to the coloring composition which concerns on embodiment of this invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. As a specific example of the dimethylsiloxane which has a polyether structure in a principal chain, FZ-2122 by Toray Dow Corning Corporation, BYK-333 by Big Chem Corporation, etc. are mentioned. Specific examples of the dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BIC Chem. Dimethylsiloxane which has a polyether structure in a principal chain, and dimethylsiloxane which has a polyester structure in a principal chain can also be used together. It is preferable to use content of a leveling agent normally 0.003-1.0 mass part with respect to 100 mass parts of total weight of a coloring composition.

As a leveling agent, it is a kind of so-called surfactant which has a hydrophobic group and a hydrophilic group in a molecule | numerator, It has the characteristic that the solubility to water is small while it has a hydrophilic group, and when added to a coloring composition, its surface tension lowering ability is low, and surface tension decreases It is useful to have good wettability with respect to a glass plate in spite of low performance, and it can use suitably what can fully suppress chargeability in the addition amount which the defect of the coating film by bubble formation does not appear. As a leveling agent having such a property, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. As a polyalkylene oxide unit, there exist a polyethylene oxide unit and a polypropylene oxide unit, and dimethyl polysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

Moreover, the bond form of the polyalkylene oxide unit with the dimethyl polysiloxane has the pendant form which the polyalkylene oxide unit couple | bonded in the repeating unit of a dimethyl polysiloxane, the terminal modification type couple | bonded with the terminal of the dimethyl polysiloxane, and the linear chain alternately repeating with dimethyl polysiloxane. The block copolymer type of may be either. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Torre Dow Corning, Inc., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, Although FZ-2207 is mentioned, it is not limited to these.

It is also possible to add anionic, cationic, nonionic, or amphoteric surfactants to the leveling agent in an auxiliary manner. You may use surfactant in mixture of 2 or more types.

Anionic surfactants added auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, and lauryl Monoethanolamine sulfate, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Can be.

Examples of the cationic surfactant added to the leveling agent auxiliary include alkyl quaternary ammonium salts and their ethylene oxide adducts. As nonionic surfactant added to a leveling agent auxiliary, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene Glycol monolaurate and the like; Amphoteric surfactants, such as alkylbetaines, such as alkyldimethylamino acetate betaine, and alkyl imidazoline, and fluorine-type and silicone type surfactants are mentioned.

<Ultraviolet absorber, polymerization inhibitor>

The coloring composition for color filters which concerns on embodiment of this invention may contain a ultraviolet absorber or a polymerization inhibitor. By containing a ultraviolet absorber or a polymerization inhibitor, the shape and resolution of a pattern can be controlled.

As the ultraviolet absorber, for example, 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1, Hydroxyphenyltriazines such as 3,5-triazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis Benzotriazoles such as (1-methyl-1-phenylethyl) phenol and 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-dihydroxy Benzophenones such as benzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, p-tert-butylphenyl salicylate Cyanoacrylates such as salicylates, ethyl-2-cyano-3,3'-diphenyl acrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl ( Triacetone-amine-N-oxyl), bis (2,2,6,6- Tramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] [ And hindered amines such as (2,2,6,6-tetramethyl-4-piperidinyl) imino].

These ultraviolet absorbers can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

As a polymerization inhibitor, for example, methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, t Hydroquinone derivatives such as butylcatechol and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine and 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate Copper and manganese salt compounds such as diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, 4-nitrosophenol, N-nitrosodiphenylamine, and N- Nitroso compounds, such as nitrosocyclohexyl hydroxylamine and N-nitrosophenyl hydroxylamine, its ammonium salt, or aluminum salt, etc. are mentioned.

These polymerization inhibitors can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

A ultraviolet absorber and a polymerization inhibitor can be used in 0.01-20 mass parts with respect to 100 mass parts of coloring agents [A] in a coloring composition, Preferably it is the quantity of 0.05-10 mass parts.

Better resolution can be obtained by using 0.01 part by mass or more of the ultraviolet absorber or the polymerization inhibitor.

Antioxidant

The coloring composition for color filters which concerns on embodiment of this invention can contain antioxidant in order to raise the transmittance | permeability of a coating film. Antioxidant prevents resin [B], a photoinitiator [D], etc. which are contained in the coloring composition for color filters oxidizing and yellowing by the thermal process at the time of thermosetting or ITO annealing. Therefore, the transmittance | permeability of a high coating film can be obtained by including antioxidant.

Preferred antioxidants include hindered phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfide antioxidants. More preferably, it is a hindered phenolic antioxidant, a hindered amine antioxidant, or phosphorus antioxidant.

These antioxidant can be used individually by 1 type or in mixture of 2 or more types in arbitrary ratio as needed.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3 , 5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, etc. Can be mentioned.

In hindered amine antioxidants, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperi) Dill) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6 , 6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl -4-piperidyl) (1,2,3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-tri Azine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl ) Imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) No} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2, Polycondensates with 6,6-tetramethylpiperidine, N, N'-4,7-te Thrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl ] 4,7- diazadecan-1, 10- diamine etc. are mentioned.

Examples of phosphorus antioxidants include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6-yl. ] Oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-2-yl) oxy ] Ethyl] amine and ethyl bisphosphite (2, 4- ditert- butyl- 6-methylphenyl) are mentioned.

Examples of sulfide antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) Methyl] -o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, and the like.

It is preferable to use content of antioxidant in the quantity of 0.1-5 weight% in 100 weight% of total of solid content of the coloring composition for color filters.

When the antioxidant is less than 0.1% by weight, the effect of increasing the transmittance is small, and when it is more than 5% by weight, the hardness is greatly lowered, and the sensitivity of the color composition for color filter is greatly reduced.

<Other Ingredients>

In order to improve adhesiveness with a transparent substrate, the coloring composition for color filters which concerns on embodiment of this invention can be made to contain adhesion promoters, such as a silane coupling agent, an amine compound etc. which have a function which reduces the dissolved oxygen.

As a silane coupling agent, (meth), such as vinylsilanes, such as vinyl tris ((beta) -methoxyethoxy) silane, vinylethoxysilane, and vinyl trimethoxysilane, (gamma)-methacryloxypropyl trimethoxysilane, for example. Acrylsilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) methyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl Epoxy silanes such as triethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N -β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltri Ethoxy amino silanes, γ- mercaptopropyltrimethoxysilane, γ- mercaptopropyl tree, such as silane, and the like thio silanes such as silane.

A silane coupling agent can be used in 0.01-10 mass parts with respect to 100 mass parts of coloring agents [A] in a coloring composition, Preferably it is 0.05-5 mass parts.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic isoamyl acid, benzoic acid 2-dimethylaminoethyl and 4-dimethylamino Benzoic acid 2-ethylhexyl, N, N- dimethyl paratoluidine, etc. are mentioned.

<The manufacturing method of the coloring composition for color filters>

The coloring composition for color filters which concerns on embodiment of this invention disperse | distributes various coloring agents [A], such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, in a pigment carrier and / or a solvent, such as resin [B]. Finely dispersed by means of the above to prepare a pigment dispersion, in which the resin [B], isocyanurate skeleton-containing monomer [C1], other monomers [C2], photopolymerization initiator [D], Therefore, it can manufacture by mixing and stirring a sensitizer [E], a polyfunctional thiol, a ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, a solvent, and other components. Moreover, the coloring composition for color filters containing 2 or more types of pigments mixes what disperse | distributed finely each pigment dispersion in a pigment carrier and / or a solvent separately, and also contains monomer [C], a photoinitiator [D], etc. You may manufacture by mixing and stirring. The isocyanurate frame | skeleton containing monomer [C1] can obtain the same effect, even if it uses at the time of manufacturing a pigment dispersion, or adds it later to a pigment dispersion.

When disperse | distributing a coloring agent [A] in resin [B] and / or a solvent, dispersion adjuvant, such as a resin pigment dispersing agent, surfactant, a pigment derivative, can be contained suitably. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-agglomeration of the pigment after dispersion, transparency is used when the coloring composition for color filters formed by dispersing the pigment in a resin and / or a solvent using the dispersion aid. This excellent color filter is obtained.

Dispersion adjuvant can be used in 0.1-40 mass parts with respect to 100 mass parts of pigments in a coloring agent [A], Preferably it is 0.1-30 mass parts.

The color composition for color filters is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more of coarse particles and mixed dust by means of centrifugation, sintering filter, membrane filter, or the like. Do.

<Color filter>

Next, the color filter which concerns on embodiment of this invention is demonstrated.

The color filter which concerns on embodiment of this invention is equipped with the filter segment and / or black matrix formed from the coloring composition for color filters which concerns on embodiment of this invention on a transparent substrate. This color filter typically has a black matrix, at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or a black matrix, at least one magenta filter segment, at least one A cyan filter segment and at least one yellow filter segment.

As a transparent substrate, glass plates, such as a soda-lime glass, a low alkali borosilicate glass, an alkali-free alumino borosilicate glass, and resin plates, such as polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, are used. Moreover, the transparent electrode which consists of indium oxide, a tin oxide, etc. may be formed in the surface of a glass plate or a resin plate for liquid crystal drive after panelization.

If the black matrix is formed before the filter segment is formed on the transparent substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, inorganic films such as chromium, chromium / chromium oxide, inorganic films such as titanium nitride, and resin films in which light-shielding agents are dispersed are used, but not limited to these, and are formed from the color filter coloring composition according to the embodiment of the present invention. The black matrix which consists of these is preferable. In addition, the thin film transistor TFT may be previously formed on the above-mentioned transparent substrate or a reflective substrate, and a filter segment may be formed after that. By forming filter segments and / or black matrices on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the brightness can be improved.

It is preferable that the dry film thickness of a filter segment and a black matrix is 0.2-10 micrometers, More preferably, it is 0.2-5 micrometers. When drying a coating film, you may use a pressure reduction dryer, a convection oven, an IR oven, a hotplate, etc.

Formation of each color filter segment and black matrix by the photolithography method is performed by the following method. That is, a dry film thickness is 0.2 by coating methods, such as a spray coat, a spin coat, a slit coat, and a roll coat, on the transparent substrate for the coloring composition for color filters prepared as the coloring composition for solvent image development type or alkali image development type color filter. Apply to ˜10 μm. Ultraviolet exposure is performed through the film which dried as needed through the mask which has a predetermined | prescribed pattern provided in the contact or non-contact state with this film.

Thereafter, the developer may be immersed in a solvent or an alkaline developer, or sprayed with a spray or the like to remove the uncured portion to form a desired pattern to form a filter segment and a black matrix. Moreover, in order to promote superposition | polymerization of the filter segment and black matrix formed by image development, you may heat as needed. According to the photolithography method, it is possible to form a filter segment and a black matrix having higher precision than the printing method.

At the time of image development, aqueous solution, such as sodium carbonate and sodium hydroxide, is used as alkaline developing solution, Organic alkali, such as dimethylbenzylamine and triethanolamine, can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

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

In addition, in order to increase the ultraviolet exposure sensitivity, after coating and drying the coloring composition for color filters, water-soluble or alkali-soluble resins such as polyvinyl alcohol or water-soluble acrylic resins are applied and dried to prevent polymerization inhibition by oxygen. After forming a film, ultraviolet light exposure may be performed.

On the color filter, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, etc. are formed as needed.

Using a sealing agent, the color filter substrate and the counter substrate are bonded together to form a cell, the liquid crystal is injected into the cell from an injection hole provided in the seal portion, and then the injection hole is sealed, and then a polarizing film or a retardation film is used as necessary. By affixing on the outer side of the liquid crystal display panel, a liquid crystal display panel is manufactured.

Such liquid crystal display panels are twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optically-compensated bend (OCB). It can be used for the liquid crystal display mode which colorizes using color filters, such as these.

(Example)

EMBODIMENT OF THE INVENTION Although this invention is demonstrated based on an Example below, this invention is not limited by this. In addition, "part" and "%" represent a "mass part" and the "mass%" in an Example, respectively. Moreover, the measuring method of the ammonium salt price of resin which has a cationic group in the side chain represented by the weight average molecular weight (Mw) of resin and General formula (8) is as follows.

<Measurement method>

(Polymerization average molecular weight (Mw) of resin)

The polymerization average molecular weight (Mw) of the resin is a GPC (manufactured by Tosoh Corporation, HPC-8120GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation), and the weight of polystyrene conversion measured using THF as the developing solvent. Average molecular weight (Mw).

(Ammonium salt of resin having cationic group in side chain)

The ammonium salt value of the resin having a cationic group in the side chain represented by the general formula (8) is a value calculated by converting it to the equivalent of potassium hydroxide after titrating with 0.1% aqueous solution of potassium nitrate as an indicator. Ammonium salts are shown.

<Method for producing acrylic resin solution>

(Acrylic Resin Solution (B-1))

Into a detachable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, 70.0 parts of propylene glycol monoethyl ether acetate was introduced, the temperature was raised to 80 ° C, and the reaction vessel was replaced with nitrogen. N-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" by Toagosei Corporation) from a dripping pipe ) 7.4 parts and 0.4 part of 2,2'- azobisisobutyronitrile were dripped over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a solid content of 30% by weight and a weight average molecular weight of 26000.

After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monoethyl ether acetate was added so that the nonvolatile content was 20% by weight to the previously synthesized resin solution. Acrylic resin solution (B-1) which is alkali-soluble resin was obtained.

(Acrylic Resin Solution (B-2))

In a detachable four-necked flask, 100 parts of propylene glycol monomethyl ether acetate were placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and heated to 120 ° C while injecting nitrogen gas into the vessel, and at the same temperature. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from the dropping tube over 2.5 hours to conduct a polymerization reaction.

Subsequently, the flask was air-substituted, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours to terminate the reaction when the solid acid value was 0.8. And the resin solution whose weight average molecular weight was about 12000 (measurement by GPC) were obtained.

Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 DEG C for 4 hours. Propylene glycol monomethyl ether acetate was added so as to have a nonvolatile content of 20%, and an energy ray-curable resin having an ethylenically unsaturated active double bond. Phosphorus acrylic resin solution (B-2) was obtained.

<Preparation method of resin which has a cationic group in the side chain represented by General formula (8)>

(Preparation of Resin 1 Having Cationic Group in the Side Chain)

75.1 parts of isopropyl alcohol were introduce | transduced into the four neck detachable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Separately, 15.7 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethylmethyl chloride methacrylate, 15.0 parts of hydroxyethyl methacrylate, methacryl After 2.5 parts of acid and 15.6 parts of methyl ethyl ketone were made uniform, it was introduce | transduced into the dropping funnel, it attached to the four neck detachable flask, and was dripped over 2 hours. After 2 hours of completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content, the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol were added to obtain a resin 2 having a cationic group in a 40% by weight side chain. Ammonium salt value of obtained resin was 33 mgKOH / g.

(Production of Resin 2 Having Cationic Group in the Side Chain)

75.1 parts of isopropyl alcohol were introduce | transduced into the four neck detachable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Separately, after equalizing 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethylmethyl chloride salt and 15.6 parts of methyl ethyl ketone, It was introduce | transduced into the dropping funnel, it attached to the four neck detachable flask, and dripped over 2 hours. After 2 hours of completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content, the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin 1 having a cationic group in a 40% by weight side chain. Ammonium salt value of obtained resin was 33 mgKOH / g.

<Method for Preparing Epoxy Compound Solution>

(Preparation method of epoxy compound solution (P-1))

Sorbitol polyglycidyl ether ("EX-611" manufactured by Nagase ChemteX Co., Ltd .: glycidyl ether-based epoxy compound) and ethylene glycol monomethyl ether acetate were used to prepare a 50% by weight solution of a non-volatile content. The compound solution (P-1) was obtained.

(Preparation method of epoxy compound solution (P-2))

Poly [(2-oxylanyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propanediol ether (made by Daicel Kagaku Kogyo Co., Ltd. "EHPE-3150 ”: Alicyclic epoxy compound) and ethylene glycol monomethyl ether acetate were used to prepare a 50% by weight nonvolatile content solution to obtain an epoxy compound solution (P-2).

<Method for Producing Color [A1]>

(Xanthene dye (A1-1): Rhodamine salt forming compound)

C.I. The salt formation compound (A1-1) which consists of acid red 52 and resin 1 which has a cationic group in a side chain was produced.

51 parts of vinyl-type resin 1 were added to 2000 parts of water, and after stirring and mixing enough, it heated at 60 degreeC. On the other hand, 10 parts of C.I. The aqueous solution which melt | dissolved acid red 52 was prepared, and it was dripped little by little with the preceding resin solution. After dripping, it stirred at 60 degreeC for 120 minutes, and fully reacted. As confirmation of the end point of reaction, the reaction liquid was dripped at the filter paper, and it was judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with a dryer, and 32 parts of C.I. The salt formation compound (A1-1) of resin 1 which has an acid red 52 and a cationic group in a side chain was obtained. At this time, C.I. in salt forming compound (A1-1). Content of the active pigment component derived from acid red 52 was 25 weight%.

(Xanthene dye (A1-2): Rhodamine salt forming compound)

C.I. The salt formation compound (A1-2) which consists of acid red 52 and resin 2 which has a cationic group in a side chain was produced.

Resin 2 which has 51 parts of cationic groups was added to 2000 parts of water, and after fully stirring and mixing, it heated at 60 degreeC. On the other hand, 10 parts of C.I. The aqueous solution which melt | dissolved acid red 52 was prepared, and it was dripped little by little with the preceding resin solution. After dripping, it stirred at 60 degreeC for 120 minutes, and fully reacted. As confirmation of the end point of reaction, the reaction liquid was dripped at the filter paper, and it was judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with a dryer, and 32 parts of C.I. The salt formation compound (A1-2) of resin 1 which has an acid red 52 and a cationic group in a side chain was obtained. At this time, C.I. in salt forming compounds (A1-2). Content of the active pigment component derived from acid red 52 was 25 weight%.

(Xanthene dye (A1-3): Rhodamine salt forming compound)

C.I. The salt-forming compound (A1-3) which consists of acid red 289 and resin 1 which has a cationic group in a side chain was produced.

Resin 1 having a cationic group was added to 88 parts of side chains in 2000 parts of 10% aqueous methanol solution, and after fully stirring and mixing, it heated at 60 degreeC. On the other hand, 10 parts of C.I. The aqueous solution which melt | dissolved acid red 289 was prepared, and it was dripped little by little with the preceding resin solution. After dripping, it stirred at 60 degreeC for 120 minutes, and fully reacted. As confirmation of the end point of reaction, the reaction liquid was dripped at the filter paper, and it was judged that the salt forming compound was obtained by making into the end point the time when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with a dryer, and 43 parts of C.I. The salt formation compound (A1-3) of resin 1 which has an acid red 289 and a cationic group in a side chain was obtained. At this time, C.I. in salt forming compounds (A1-3). Content of the effective pigment component derived from acid red 289 was 25 weight%.

(Xanthene dye (A1-4): Rhodamine salt forming compound)

C.I. The salt-forming compound (A1-4) which consists of acid red 52 and distearyl dimethylammonium chloride (quatamine D86P) (molecular weight of cation part is 550) was produced.

In 7-15 mol% sodium hydroxide solution, C.I. Acid red 52 is melt | dissolved, it fully mixes and stirs, after heating at 70-90 degreeC, the quartamine D86P is dripped gradually. Qutamine D86P may be dissolved in water and used as an aqueous solution. After dropping quarteramine D86P, the mixture is stirred at 70 to 90 ° C for 60 minutes to sufficiently react. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with a drier, and dried under C.I. A salt forming compound (A1-4) of acid red 52 and distearyl dimethylammonium chloride was obtained. At this time, C.I. in salt forming compound (A1-4). Content of the active pigment component derived from acid red 52 was 25 weight%.

(Xanthene dye (A1-5): Rhodamine salt forming compound)

C.I. The salt-forming compound (A1-5) which consists of acid red 52 and dialkyl (alkyl is C14-C18) dimethylammonium chloride (aquad 2HT-75) (molecular weight of cation part is 438-550) was produced.

In 7-15 mol% sodium hydroxide solution, C.I. Acid red 52 is melt | dissolved, it fully mixes and stirs, after heating at 70-90 degreeC, the aquad 2HT-75 is dripped gradually. Aqua 2HT-75 may be dissolved in water and used as an aqueous solution. After dripping AQUAD 2HT-75, it stirred at 70-90 degreeC for 60 minutes, and fully reacts. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with a drier, and dried under C.I. The salt formation compound (A1-5) of acid red 52 and dialkyl (alkyl is C14-C18) dimethylammonium chloride was obtained. At this time, C.I. in salt forming compounds (A1-5). Content of the active pigment component derived from acid red 52 was 25 weight%.

(Xanthene dye (A1-6): Rhodamine salt forming compound)

C.I. The salt-forming compound (A1-6) which consists of acid red 87 and distearyl dimethylammonium chloride (quatamine D86P) (molecular weight of cation part is 550) was produced.

In 7-15 mol% sodium hydroxide solution, C.I. Acid red 87 is melt | dissolved, it fully mixes and stirs, after heating to 70-90 degreeC, the quartamine D86P is dripped gradually. Qutamine D86P may be dissolved in water and used as an aqueous solution. After dropping quarteramine D86P, the mixture is stirred at 70 to 90 ° C for 60 minutes to sufficiently react. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with a drier, and dried under C.I. A salt forming compound (A1-6) of acid red 87 and distearyldimethylammonium chloride was obtained. At this time, C.I. in salt forming compounds (A1-6). Content of the active pigment component derived from acid red 87 was 25 weight%.

(Xanthene type dye (A1-7): Rhodamine type sulfonic acid amide compound)

C.I. Acid red 52 was sulfonylated according to the conventional method, followed by reaction with theoretical equivalents of 2-ethylhexylamine in dioxane to give C.I. The sulfonic acid amide compound (A1-7) of acid red 52 was obtained. (Based on description of Unexamined-Japanese-Patent No. 6-194828.) At this time, C.I. Content of the active pigment component derived from acid red 52 was 25 weight%.

(Xanthene dye (A1-8): Rhodamine salt forming compound)

Anthracene sulfonic acid (molecular weight 258) was added in a 7-15 mol% sodium hydroxide solution, and the sodium salt was obtained by fully stirring this liquid. After heating this aqueous solution of anthracene sulfonate salt at 70-90 degreeC, the rhodamine B dye (C.I. basic violet 10) was dripped gradually. Rhodamine B dye may be used as an aqueous solution. After completion of the dropwise addition of the rhodamine B dye, the solution was stirred at 70 to 90 ° C. over 40 to 60 minutes to sufficiently react. The end point of the reaction was a dropwise addition of the reaction liquid onto the filter paper, and the bleeding disappeared. That is, it was judged that the salt-forming compound was obtained when the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was performed and further water washing. After washing with water, water was removed from the salt forming compound remaining on the filter paper using a dryer to obtain a salt forming compound (A1-8) of rhodamine B dye and anthracene sulfonic acid. At this time, C.I. in salt forming compounds (A1-8). Content of the effective pigment component derived from basic violet 10 was 25 weight%.

(Xanthene dye (A1-9): Rhodamine salt forming compound)

C.I. The salt-forming compound (A1-9) which consists of basic red 1 and 2-amino-1- naphthalene sulfonic acid (tobias acid) (molecular weight 223) was produced.

2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) is dissolved in 9 mol% of sodium hydroxide solution, sufficiently mixed and stirred to obtain the sodium salt. After heating this aqueous 2-amino-1-naphthalenesulfonic acid (tobias) sodium salt solution at 85 degreeC, rhodamine 6GCP dye (C.I. basic red 1) is dripped little by little. Rhodamine 6GCP dye may be dissolved in water and used as an aqueous solution. After adding rhodamine 6GCP dye, it stirred at 85 degreeC for 55 minutes and fully reacts. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed to wash with water. After washing with water, the salt-containing compound remaining on the filter paper was dried by removing water with a dryer to obtain a salt-forming compound (A1-9) of rhodamine 6GCP dye and 2-amino-1-naphthalenesulfonic acid (tobias acid). At this time, C.I. in salt forming compounds (A1-9). Content of the effective pigment component derived from basic red 1 was 25 weight%.

(Quinoline Dye (A1-10))

Quinoline pigment | dye (A1-10) was obtained in the following procedure.

Quinoline dyes (A1-10):

2.3 parts of 6-iso-propyl-2-methylquinoline, 2.5 parts of naphthalenedicarboxylic anhydrides, and 30 parts of benzoic acid were mixed, and it stirred at 200 degreeC for 7 hours. After cooling, 100 parts of methanol was added and the mixture was stirred for 1 hour. And the solid precipitated was collected by suction filtration. In addition, the solid was put in 200 parts of methanol, and after stirring for 1 hour, the solid was collected by suction filtration. It dried with the vacuum dryer (40 degreeC) overnight, and obtained the product of 3.1 parts. Yield 67%. The product identified the compound by the mass spectrometer (TOF-MS: Bruker Daltonics make autoflexII). It confirmed that it was a target object in m / z = 366 (molecular weight 365.4).

(Thiazole type dye (A1-11): thiazole salt forming compound)

C.I. The thiazole type pigment | dye (A1-11) which consists of direct yellow 8 and distearyl dimethylammonium chloride (quatamine D86P) (molecular weight of cation part is 550) was produced.

In 7-15 mol% sodium hydroxide solution, C.I. Direct yellow 8 is dissolved, sufficiently mixed and stirred, and heated to 70 to 90 ° C, followed by dropwise dropping of quartamine D86P. Qutamine D86P may be dissolved in water and used as an aqueous solution. After dropping quarteramine D86P, the mixture is stirred at 70 to 90 ° C for 60 minutes to sufficiently react. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-containing compound remaining on the filter paper was removed by drying with a drier, and dried under C.I. Thiazole pigment | dye (A1-11) which is a salt-forming compound of direct yellow 8 and distearyl dimethylammonium chloride was obtained. At this time, C.I. Content of the effective pigment component derived from direct yellow 8 was 25 weight%.

(Triphenylmethane dye (A1-12): triphenylmethane salt forming compound)

C.I. A triphenylmethane dye (A1-12) consisting of basic blue 7 and 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) was produced.

2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) is dissolved in 9 mol% of sodium hydroxide solution, sufficiently mixed and stirred to obtain the sodium salt. This 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) sodium salt aqueous solution is heated to 85 degreeC, and Victoria pure blue dye (C.I. basic blue 7) is dripped gradually. Victoria pure blue dye may be dissolved in water and used as an aqueous solution. After the Victoria pure blue dye was dripped, it stirred at 85 degreeC for 55 minutes, and fully reacts. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed to wash with water. After washing with water, the salt-containing compound remaining on the filter paper was dried by removing water with a dryer, and the salt-containing compound and triarylmethane salt-containing compound (A1-12) of Victoria pure blue dye and 2-amino-1-naphthalenesulfonic acid (tobias acid). ) At this time, C.I. in triarylmethane salt forming compound (A1-12). Content of the effective pigment component derived from basic blue 7 was 25 weight%.

(Triphenylmethane dye (A1-13): triphenylmethane salt forming compound)

C.I. A triphenylmethane dye (A1-13) consisting of basic blue 7 and perchloric acid (molecular weight 100.5) was produced.

The perchloric acid (molecular weight 100.5) is dissolved in a 9 mol% sodium hydroxide solution, sufficiently mixed and stirred to obtain the sodium salt. After heating this aqueous sodium perchlorate salt at 85 degreeC, Victoria pure blue dye (C.I. basic blue 7) is dripped gradually. Victoria pure blue dye may be dissolved in water and used as an aqueous solution. After the Victoria pure blue dye was dripped, it stirred at 85 degreeC for 55 minutes, and fully reacts. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed to wash with water. After washing with water, the salt-containing compound remaining on the filter paper was dried by removing water with a drier to obtain a Victorian pure blue dye, a salt compound of perchloric acid, and a triarylmethane salt compound (A1-13). At this time, C.I. in triaryl methane salt forming compound (A1-13). Content of the effective pigment component derived from basic blue 7 was 25 weight%.

(Triphenylmethane Dye (A1-14); Triphenylmethane Dye Salting Compound)

The triphenylmethane salt salt compound obtained by the following method was used as (A1-14).

By the method disclosed in document BIOS 1157,53, 106 g (1 mol) of benzaldehyde is condensed with 508 g (2 mol) of N-benzyl-N-butyl-m-toluidine and sulfonated to introduce a trisulfonic acid group, which is introduced into manganese dioxide (MnO). After oxidizing with ₂ ), it was reacted with 137 g (1 mol) of p-phenetidine to obtain 500 g of the anion component represented by the general formula (9).

Formula (9):

91 g (0.1 mol) of the obtained component was dissolved in water at a water temperature of 60 ° C. to obtain an aqueous solution of 3%. This was prepared to pH7 and filtered. While stirring this filtrate, 22.5 g (0.12 mol) of acetic acid aqueous solution of 3- (2-ethylhexyloxy) propylamine of a cation component was dripped for 40 minutes. After the reaction at room temperature for 2 hours, the mixture was prepared at pH = 5 to 6, and then heated to 40 ° C to obtain crude particles. Then, it filtered and washed with water and dried, and 97 g of blue salt dyes were obtained. At this time, content of the effective pigment component derived from the compound represented by General formula (9) in a triaryl methane salt-forming compound (A1-14) was 25 weight%.

(Thiazine type dye (A1-15): thiazine type salt forming compound)

C.I. A thiazine dye (A1-15) consisting of basic blue 9 and 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) was produced.

In a 7-15 mol% sodium hydroxide solution, 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) is dissolved, sufficiently mixed and stirred to obtain the sodium salt. After heating this aqueous solution of 2,8-diamino-1-naphthol-5,7-disulfonate salt at 70 to 90 ° C, methylene blue FZ dye (C.I. basic blue 9) is added dropwise little by little. The methylene blue FZ dye may be dissolved in water and used as an aqueous solution. After dropping methylene blue FZ dye, the mixture is stirred at 70 to 90 ° C. for 40 to 60 minutes to sufficiently react. As confirmation of the end point of reaction, it can be judged that a salt-forming compound was obtained by making a reaction liquid dropwise into a filter paper, and making the end point the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration is performed to wash with water. After washing with water, the salt-containing compound remaining on the filter paper was dried by removing water with a dryer, and the salt-containing compound and thiazine-based salt compound of methylene blue FZ dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid ( A1-15) was obtained. At this time, C.I. in the thiazine salt forming compound (A1-15). Content of the effective pigment component derived from basic blue 9 was 25 weight%.

<Method for producing solution containing pigment [A1]>

(Preparation of xanthene dye-containing solution (DA-1))

After stirring and mixing the following mixture to make it uniform, it filtered by the 5.0 micrometer filter and produced the xanthene type pigment | dye containing solution (DA-1).

Xanthene dye (A1-1): 20.0 parts

Propylene Glycol Monomethyl Ether Acetate (PGMAC): 80.0 parts

(Production of Color [A1] Containing Solution (DA-2 to 15))

Hereinafter, except having changed the xanthene type pigment | dye (A1-1) into the pigment | dye (A1-2-15) shown in Table 1, it is similar to the pigment | dye containing solution (DA-1) mentioned above, and a dye [A1] containing solution (DA- 2-15).

The produced dye [A1] containing solution is put together in Table 1, and is shown.

<Preparation of Micronized Pigment>

(Red Refinement Pigment (PR254-1): Red Pigment [A2])

Red Pigment C.I. 152 parts of Pigment Red 254 (PR254) ("Sigapore Red B-CF" made by Chiba Japan), 8 parts of pigment derivatives of the general formula (10), 1600 parts of sodium chloride, and 190 parts of diethylene glycol, 1 gallon kneader made of stainless steel It was introduce | transduced into (the Inoue Seisakusho company make), and it knead | mixed at 60 degreeC for 10 hours. Next, the mixture was poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while heating to about 80 ° C. to a slurry state, filtered and washed repeatedly to remove sodium chloride and solvent, and then overnight at 80 ° C. It dried at daytime and obtained the red refined pigment (PR254-1).

Formula (10):

(Red Refinement Pigment (PR177-1): Red Pigment [A2])

Red Pigment C.I. 500 parts of pigment red 177 (PR177) ("Chromoma red A2B" made by Chiba Japan Corporation), 3500 parts of sodium chloride, and 250 parts of diethylene glycol are introduce | transduced into a stainless gallon kneader (made by Inoue Seisakusho), and it is 120 degreeC Kneaded for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C, and then slurryed. After filtration and washing with water, sodium chloride and diethylene glycol were removed, and dried overnight at 80 ° C. And red refinement | treatment pigment (PR177-1) were obtained.

(Red Refinement Pigment (PR242-1): Red Pigment [A2])

Red Pigment C.I. 200 parts of Pigment Red 242 ("NOVOPERM SCARLET 4RF" from Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were introduced into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a slurry state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. And red refinement | treatment pigment (PR242-1) were obtained.

(Green Refinement Pigment (PG58-1)) °

Phthalocyanine green pigment C.I. 200 parts of Pigment Green 58 ("FASTOGEN GREEN A110" made by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are introduced into a stainless gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. did. Next, this kneaded product was poured into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to a slurry state, filtration and washing were repeated to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C., Micronized green pigment (PG58-1) was obtained.

(Yellow Micronized Pigment (PY150-1))

Nickel Complex System Yellow Pigment C.I. 200 parts of pigment yellow 150 ("E-4GN" by LANXESS company), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were introduce | transduced into the stainless 1 gallon kneader (made by Inoue Seisakusho), and it knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product was poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to a slurry state, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried overnight at 85 ° C. And the refined yellow pigment (PY150-1) were obtained.

(Blue Refined Pigment (PB15: 6-1))

Blue pigment C.I. 500 parts of pigment blue 15: 6 (PB15: 6) (Toyo Inking Co., Ltd. "Lionol blue ES"), 2500 parts of sodium chloride, and 250 parts of diethylene glycol to stainless steel 1 gallon kneader (product made in Inoue Seisakusho) It introduce | transduced and knead | mixed at 120 degreeC for 12 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C, and then slurryed. After filtration and washing with water, sodium chloride and diethylene glycol were removed, and dried overnight at 80 ° C. And blue refinement | treatment pigment | dye (PB15: 6-1) were obtained.

(Purple Refinement Pigment (PV23-1))

Dioxazine violet pigment C.I. 500 parts of pigment violet 23 (PV23) ("Fast Violet RL" made by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (made by Tokyo Kasei Co., Ltd.) are introduced to a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), It knead | mixed for 12 hours at 120 degreeC. Next, the mixture was poured into about 5 liters of warm water, stirred at a high speed mixer for about 1 hour while heating to about 70 ° C, and then slurryed, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80 ° C. It dried overnight in the night, and obtained the purple refinement | treatment pigment (PV23-1).

<Method of adjusting pigment dispersant solution>

The pigment dispersant ("Azipa PB821" by Ajinomoto Fine Techno Co., Ltd.) was diluted with propylene glycol monomethyl ether acetate, and the non volatile matter adjusted the pigment dispersant solution of 30 weight%.

<Method for Producing Pigment Dispersion>

Pigment Dispersion (P-R1)

After uniformly stirring and mixing 12.0 parts of red fine treatment pigment (PR254-1), 32.5 parts of acrylic resin solution (B-1), 5 parts of pigment dispersant solutions, and 50.5 parts of ethylene glycol monomethyl ether acetate, zirconia of diameter 0.5mm After disperse | distributing with Eiger Mill ("Mini Model M-250 MKII" by Eiger Japan company) for 3 hours using the beads, it filtered with a 5 micrometer filter and obtained the pigment dispersion (P-R1) of PR254.

Pigment Dispersion (P-R2)

The pigment dispersion (P-R2) of PR177 was produced by the same manufacturing method as the pigment dispersion (P-R1) except having changed the red refinement pigment (PR254-1) into the red refinement pigment (PR177-1).

Pigment Dispersion (P-R3)

The pigment dispersion (P-R3) of PR242 was produced by the same manufacturing method as the pigment dispersion (P-R1) except having changed the red refinement pigment (PR254-1) into the red refinement pigment (PR242-1).

Pigment Dispersion (P-G1))

The pigment dispersion (P-G1) of PG58 was produced by the same manufacturing method as the pigment dispersion (P-R1) except having changed the red refinement pigment (PR254-1) into the green refinement pigment (PG58-1).

Pigment Dispersion (P-Y1)

The pigment dispersion (P-Y1) of PY150 was produced by the same manufacturing method as the pigment dispersion (P-R1) except having changed the red refinement pigment (PR254-1) into the yellow refinement pigment (PY150-1).

Pigment Dispersion (P-B1))

Pigment dispersion (P-B1) of PB15: 6 by the same manufacturing method as the pigment dispersion (P-R1) except that the red micro pigment (PR-1) was changed to the blue micro pigment (PB15: 6-1). Made.

Pigment Dispersion (P-V1)

The pigment dispersion (P-V1) of PV23 was produced by the same manufacturing method as the pigment dispersion (P-R1) except having changed the red refinement pigment (PR-1) into the purple refinement pigment (PV23-1).

The produced pigment dispersion is put together in Table 2, and is shown.

[Examples 1-57, Comparative Examples 1-20]

Various materials were mixed with the formulation of Tables 3-9, and the coloring composition was produced. In addition, the compound | combination shown by the mass part is shown to Tables 3-9.

Monomer (C1-1): Tris (2-acryloyloxyethyl) isocyanurate ("pancryl FA-731A" made by Hitachi Kasei Co., Ltd.)

Monomer (C1-2): CIC acid acrylate

Monomer (C1-3): diallyl monoglycidyl isocyanuric acid ("heat-resistant crosslinking agent DA-MGIC" made by Shikoku Chemical Co., Ltd.)

Monomer (C2-1): ("Aronix M-520" made by Toagosei Corporation)

Monomer (C2-2): Caprolactone modified dipentaerythritol hexaacrylate ("KAYARAD DPCA-60" made by Nippon Kayaku Co., Ltd.)

Photoinitiator (D-1): Ethan-1-one, 1- [9-ethyl-6- (2-methylbenzoi-9H-carbazol-3-yl], 1- (O-acetyloxime) (Chiba Japan company `` single cure OXE02 '')

Photopolymerization initiator (D-2): 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (made by Chiba Japan Corporation) `` Ulga Cure 379 '')

Sensitizer (E-1): 2, 4-diethyl thioxanthone ("kayakure DETX-S" made by Nippon Kayaku Co., Ltd.)

Solvent: Propylene Glycol Monomethyl Ether Acetate

Epoxy compound solution (P-1): Nagase Chemtex Co., Ltd. "EX-611" solution

Epoxy compound solution (P-2): Daisel Kagaku Kogyo Co., Ltd. "EHPE-3150" solution

<Evaluation method>

The red coloring composition was apply | coated on the glass substrate with the film thickness like x = 0.657 and y = 0.320 in C light source, and the ultraviolet exposure was performed through the mask which has a predetermined | prescribed pattern. Thereafter, the alkali developer was sprayed by spray to remove the uncured portion to form a desired pattern. About the obtained coating film, the brightness before and behind heat processing of 230 degreeC 60 minutes was measured in the oven with the brown rice spectrophotometer ("OSP-SP200" by Olympus Kogaku company).

The green coloring composition was apply | coated on the glass substrate with the film thickness like x = 0.290 and y = 0.600 in C light source, and the ultraviolet exposure was performed through the mask which has a predetermined | prescribed pattern. Thereafter, the alkali developer was sprayed by spray to remove the uncured portion to form a desired pattern. About the obtained coating film, the brightness before and behind heat processing of 230 degreeC 20 minutes was measured in the oven with the brown rice spectrophotometer ("OSP-SP200" by Olympus Kogaku company).

The blue coloring composition was apply | coated on the glass substrate with the film thickness like x = 0.141 and y = 0.084 in C light source, and the ultraviolet exposure was performed through the mask which has a predetermined | prescribed pattern. Thereafter, the alkali developer was sprayed by spray to remove the uncured portion to form a desired pattern. About the obtained coating film, the brightness before and behind heat processing of 230 degreeC 20 minutes was measured in the oven with the brown rice spectrophotometer ("OSP-SP200" by Olympus Kogaku company).

In addition, when chromaticity was deteriorated, the brightness | luminance in desired chromaticity was computed by creating the coloring composition which changed the ratio of a pigment dispersion and a pigment containing solution suitably, measuring chromaticity, and drawing a calibration curve.

The results are shown in Tables 10-12.

As shown in Tables 10-12, the coloring composition for color filters of Examples 1-57 had little brightness fall by heat processing, and the result of the high brightness was obtained.

Comparative Examples 1, 2, 8, 9, 12, and 13, in which only the pigments used were pigments, were inferior in brightness at the time point before the heat treatment.

Although all the comparative examples 3-7, 10-11, and 14-20 which do not contain the isocyanurate frame | skeleton containing monomer [C1] show high brightness at the time before heat processing, the brightness decreases by heat processing, The result was a fall.

(Production of color filter)

The black matrix was pattern-processed on the glass substrate, and the red coloring composition of Example 1 was apply | coated with this spin coater, and the coloring film was formed. The film was irradiated with ultraviolet light of 150 mJ / cm 2 using an ultrahigh pressure mercury lamp through a photomask. Next, after spray-developing with the alkaline developing solution which consists of 0.2 weight% sodium carbonate aqueous solution, the unexposed part was removed, it wash | cleaned with ion-exchange water, and this board | substrate was heated at 230 degreeC for 20 minutes, and the red filter segment was formed. Here, the red filter segment was made to match chromaticity of x = 0.657 and y = 0.320 in C light source (hereinafter also used for green and blue) after heat processing at 230 degreeC. In addition, by the same method, the green filter segment was made to match chromaticity of x = 0.290 and y = 0.600 using the green coloring composition of Example 22, and the blue filter segment was the blue coloring composition of Example 35 of this invention. Each filter segment was formed using the chromaticity of x = 0.141 and y = 0.084, and the color filter was obtained.

By using the coloring composition for color filters of this invention, it was able to withstand heat processing and the color filter of high brightness was obtained.

While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. These novel embodiments can be implemented in various other forms, and various omissions, substitutions, and changes can be made without departing from the spirit of the inventions. These embodiments and modifications thereof are included in the scope and spirit of the invention, and are included in the invention and equivalent scope of the claims.

Claims (7)

As a coloring composition for color filters containing a coloring agent [A], resin [B], and monomer [C],
The coloring agent [A] contains the dye containing a xanthene type pigment | dye, and a pigment,
This monomer [C] contains the isocyanurate skeleton containing monomer [C1] represented by following General formula (1),
Content of resin [B] is 20 mass parts or more and 1000 mass parts or less with respect to 100 mass parts of coloring agents [A],
Content of monomer [C1] is 1 mass part or more and 300 mass parts or less with respect to 100 mass parts of coloring agents [A], The coloring composition for color filters characterized by the above-mentioned.
Formula (1):

[In General formula (1), although R <_1> , R <_2> and R <_3> are group represented by following General formula (2)-(6) each independently, at least 1 is general formula (2)-(4) Is one of the groups displayed]
Formula (2):

Formula (3):

Formula (4):

Formula (5):

Formula (6):

[Formula (2) to (6) of, R _4, R ₅ and R ₆ are each independently selected from any one of H or CH _3. n is an integer of 0-10. m is an integer of 1-20 each independently. l is an integer from 1 to 5.] The dye according to claim 1, wherein the dye is a quinophthalone dye, an anthraquinone dye, an oxazine dye, a phthalocyanine dye, an azo dye, an indigoid dye, a triphenylmethane dye, a quinoline dye, a thiazine dye, And at least one pigment | dye [A1] selected from the group which consists of a thiazole type pigment | dye. The coloring composition for color filters characterized by the above-mentioned. The coloring composition for color filters according to claim 1, wherein the xanthene dye is at least one of a salt salt compound of a xanthene acid dye and a sulfonamide compound of a xanthene dye. The coloring composition for color filters of Claim 1 which further contains an epoxy compound [P] (except the case of isocyanurate frame | skeleton containing monomer [C1]). The epoxy compound [P] is a polycondensation product of bisphenols, phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensation products of phenols and ketones, and polycondensation of phenols and aromatic dimethanols. Polycondensates of a mixture, phenols and aromatic dichloromethyls, polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy compounds, alicyclic epoxy compounds, glycidylamine epoxy compounds, and glycidyl ester epoxys It is at least 1 sort (s) chosen from the group which consists of a compound, The coloring composition for color filters characterized by the above-mentioned. The coloring composition for color filters of Claim 1 which further contains a photoinitiator [D]. It is formed by the coloring composition for color filters in any one of Claims 1-6, The color filter characterized by the above-mentioned.