KR20080006452A - Coloring resin composition and color filter for liquid crystal display device - Google Patents

Abstract

A colorant resin composition useful for fabricating a color filter for a liquid crystal display device is provided to inhibit a drop in voltage maintenance in displaying images, to realize excellent shelf stability with time, and to accomplish stable image display with a good image reproducibility. A colorant resin composition comprises: a colorant having an average particle diameter of 200 nm or less; and an alkali soluble resin having at least one of carboxyl and phosphate groups and a sulfonate group per molecule. The alkali soluble resin has a weight average molecular weight of 2,000-100,000 as measured by gel permeation chromatography using polystyrene standards. The colorant includes at least one red colorant having an average particle diameter of 150 nm or less in an amount of at least 20 wt% based on the total solid content.

Description

Color filter for colored resin composition and liquid crystal display element {COLORING RESIN COMPOSITION AND COLOR FILTER FOR LIQUID CRYSTAL DISPLAY DEVICE}

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing for demonstrating the structure of the liquid crystal cell used for the measurement of VHR.

The present invention relates to a colored resin composition and a color filter for a liquid crystal display device, and more particularly, to a colored resin composition suitable for forming a colored image constituting a color filter used for a liquid crystal display device and the like and a color filter for a liquid crystal display device using the same. It is about.

The color filter constituting the liquid crystal display device (LCD) is coated with a photosensitive colored resin composition containing a pigment or the like on a substrate, dried, and then exposed to a dry coating film in a desired pattern. It can be produced by forming a.

Various studies have been made on a colored composition having photosensitivity, and a copolymer containing an acidic group such as, for example, a COOH group, a PO ₃ H ₂ group, or a -SO ₃ H group is contained together with the pigment. A composition using a star polymer in which a composition, a monomer having a sulfonic acid group, or the like is used as a monomer component and the polymer chain is elongated in a branched state, and the like are known (for example, Japanese Patent Application Laid-Open No. 9-146272, Japanese Patent Publication 2003). -222717 publication).

On the other hand, one of the characteristics that affect the display performance of the liquid crystal display device (LCD) is the voltage retention (VHR). And the color filter which comprises LCD is one cause which influences this voltage retention. For example, when a small liquid crystal cell is knitted and a voltage is applied, a small amount of polar compounds such as surface modifiers and dispersants of pigments remaining in the color filter composition is eluted in the liquid crystal cell, and the voltage between the electrodes is not constant.

This voltage fluctuation is thought to cause a drop in voltage because a substance which becomes a carrier of electric charges is exuded from the color filter to the liquid crystal cell (liquid crystal layer), but more than that, in fact, the polarization by voltage application is also highly dependent. do.

In connection with the above, the composition used as a coloring agent is disperse | distributed to the dispersing agent which has a urethane bond, and the composition whose voltage retention is 80% or more is disclosed (for example, refer Unexamined-Japanese-Patent No. 2002-365795). There is also a disclosure of a composition containing a nitrogen atom-containing resin or a dispersant and a composition containing a pigment having a voltage retention of 80% or more by improving the voltage retention by setting the residual ratio of the total nitrogen amount to 60% by mass or less (for example, , Japanese Patent Laid-Open No. 2004-325968, and Japanese Patent Laid-Open No. 2000-329929).

However, the problem associated with the above-mentioned voltage retention (VHR) tends to occur as the particle size of the colorant becomes smaller and the surface area thereof becomes larger, and as the content rate of the colorant in each pixel of the color filter increases.

In recent years, TV use has become widespread as a use of LCD, and further improvement of contrast and color purity is required in TV use beyond conventional monitors, and it is inevitable to reduce the particle size of the colorant and to increase the content of the colorant in the pixel. There is a situation.

The present invention has been made in view of the above situation, and the drop in voltage retention during image display is suppressed, and even when the colorant particles are fine, the storage stability is excellent over time, the image reproducibility of the display image is good, and stable image display can be performed. The colored resin composition and the color filter for liquid crystal display elements are provided.

The specific means for achieving the said subject is as follows.

<1> It is a coloring resin composition containing the coloring agent whose average particle diameter is 200 nm or less, and alkali-soluble resin which has at least 1 of a carboxyl group and a phosphoric acid group, and a sulfonic acid group in 1 molecule.

<2> The said alkali-soluble resin is resin obtained by copolymerizing using 1 or more types of compounds chosen from the following compounds D-1 to D-9, It is colored resin composition as described in said <1> characterized by the above-mentioned.

Wherein, Q ₂ denotes a -H or -CH _3, j is an integer of 2 ~ 18, l represents an integer of 1 to 4, m is an integer of 1-12.

<3> The said alkali-soluble resin is resin obtained by copolymerizing using the 1 or more types of compound chosen from the following compound D-10-D-16, The colored resin composition as described in said <1> or <2> characterized by the above-mentioned. .

In the formula, Q ₂ represents -H or -CH ₃ , j represents an integer of 2 to 18, and m represents an integer of 1 to 12.

The weight average molecular weight (polystyrene conversion value measured by GPC method) of <4> above-mentioned alkali-soluble resin is 2,000-100,000, It is the colored resin composition in any one of said <1>-<3> characterized by the above-mentioned.

<5> At least 1 type of the said coloring agent is a coloring agent for red, the said coloring agent for red is an average particle diameter of 150 nm or less, and the content rate with respect to the total solid of the said coloring agent for red is 20 mass% or more, The said < It is colored resin composition in any one of 1>-<4>.

<6> At least 1 type of the said coloring agent is a green coloring agent, The said green coloring agent has an average particle diameter of 200 nm or less, and the content rate with respect to the total solid of the said green coloring agent is 35 mass% or more, The said < It is the colored resin composition in any one of 1>-<4>.

<7> At least 1 type of the said coloring agent is a blue coloring agent, the said blue coloring agent is 150 nm or less in average particle diameter, and the content rate with respect to the total solid of the said blue coloring agent is 15 mass% or more, The said < It is the colored resin composition in any one of 1>-<4>.

<8> Photopolymerizable compound and a photoinitiator are further contained, The colored resin composition in any one of said <1>-<7> characterized by the above-mentioned.

<9> The said coloring agent is an organic pigment of 10-100 nm of average particle diameters, It is a colored resin composition in any one of said <1>-<8> characterized by the above-mentioned.

The <10> red coloring agent has an average particle diameter of 10-100 nm, and the content rate with respect to the total solid of the said red coloring agent is 25-50 mass%, any one of said <5>-<9> characterized by the above-mentioned. It is colored resin composition of description.

The <11> above-mentioned green coloring agent has an average particle diameter of 10-100 nm, The content rate with respect to the total solid of the said green coloring agent is 45-60 mass%, any one of said <6>-<10> characterized by the above-mentioned. It is colored resin composition of description.

The <12> above-mentioned blue coloring agent has an average particle diameter of 10-100 nm, The content rate with respect to the total solid of the said blue coloring agent is 25-50 mass%, Any one of said <7>-<11> characterized by the above-mentioned. It is colored resin composition of one.

Content of the <13> above-mentioned alkali-soluble resin is 0.5-150 mass% with respect to the mass of the said coloring agent, It is the colored resin composition in any one of said <1>-<12> characterized by the above-mentioned.

<14> The said photopolymerizable compound is a tetrafunctional or more acrylate compound, It is colored resin composition in any one of said <8>-<13> characterized by the above-mentioned.

<15> It is a color filter for liquid crystal display elements formed using the colored resin composition in any one of said <1>-<14>.

<16> voltage retention is 85% or more, It is a color filter for liquid crystal display elements as described in said <15> characterized by the above-mentioned.

Hereinafter, the colored resin composition of this invention is demonstrated in detail, and the color filter for liquid crystal display elements of this invention produced using a colored resin composition is explained in full detail.

The coloring resin composition of this invention contains a coloring agent and alkali-soluble resin at least, The average particle diameter of the said coloring agent is 200 nm or less, and the said alkali-soluble resin is one or more of a carboxyl group and a phosphoric acid group, and a sulfonic acid group in 1 molecule. It was set as having a configuration. Moreover, Preferably it consists of containing a photopolymerizable compound, a photoinitiator, and a solvent, and can be comprised using another component as needed.

In the present invention, in the case of using a coloring agent having a small particle size of 200 nm or less in average particle diameter, a voltage is obtained by using a resin component in which a sulfonic acid group (preferably in a molecular side chain) is introduced into a molecule having an alkali solubilizing group of a carboxyl group or a phosphoric acid group. Since the fall of a retention rate can be suppressed and voltage can be kept high, image display at the time of making a liquid crystal panel and displaying an image can be performed stably.

Here, the voltage retention VHR is obtained from a value obtained by measuring a cell voltage after a predetermined time is applied by applying a voltage of 5 V between the electrodes of the liquid crystal cell for a predetermined time, and then stopping the application of the voltage. . In addition, the measurement was performed by wiring between the ITO films (transparent electrodes) formed on two substrates sandwiching the liquid crystal of the liquid crystal cell, and applying the voltage 5V repeatedly by inverting the polarity, and averaging the measured values as the cell voltage. do.

Voltage retention (%) = (cell voltage / 5) x 100

As shown in FIG. 1, the liquid crystal cell is a color filter substrate having an ITO electrode and a color filter film on a glass substrate, and an opposing substrate having an ITO electrode prepared separately from this, such that the color filter film and the ITO electrode of the opposing substrate face each other. It can arrange | position with a desired cell gap, and can adhere | attach between board | substrates with a sealing compound, inject | pour a liquid crystal, and heat and bond with an oven etc., and can produce it.

-coloring agent-

The colored resin composition of this invention contains 1 or more types of coloring agents whose average particle diameter is 200 nm or less. Since a colorant with a small particle size with an average particle diameter of 200 nm or less is selected, an image having high contrast and high transmittance and high color purity with high color purity can be obtained when the display panel is configured and the image is displayed. In addition, by using a colorant having a small particle size (that is, having a large specific surface area), a decrease in voltage retention (VHR) when a liquid crystal display panel is formed and an image is displayed, tends to deteriorate image display performance. By using alkali-soluble resin which concerns on this invention mentioned later, the fall of VHR can be suppressed effectively, and image display performance is favorable and a stable image can be obtained.

In addition, it is generally difficult to use a colorant having a small particle size, whether inorganic particles or organic pigment particles, to maintain a dispersed state without agglomerating fine particles. If the particles dispersed in fine particles are aggregated, the color filter may have low contrast and transmittance, and foreign matter may be easily generated in the manufacturing process, or even a uniform film thickness may not be applied onto the substrate. . By using the alkali-soluble resin according to the present invention, agglomeration of the pigment is prevented to obtain a dispersion having good storage properties, and even when a colored resin composition is obtained, the storage properties are good and a homogeneous coating film can be formed. As a result, a display device with good image display can be obtained.

Here, an average particle diameter means the particle diameter (for example, pigment) which averaged the primary particle diameter at the time of preparing the coloring resin composition containing a coloring agent (for example, in the case of a pigment, the dispersion composition which a pigment is disperse | distributing). And the like, in the case of dispersing, etc., the average primary particle diameter of the pigment dispersed in the dispersion composition), and immediately after the dispersion treatment, a transmission electron microscope [TEM; For example, it is measured using SEM S-4800, Hitachi Seisakusho Co., Ltd. which has a TEM function.

There is no restriction | limiting in particular other than an average particle diameter as a coloring agent, It can select from 1 type (s) or 2 or more types from various conventionally well-known dyes and pigments, and can use it in the range which the average particle diameter in a dispersion state becomes 200 nm or less.

As said average particle diameter, when it is preferable that an inorganic pigment or an organic pigment has high transmittance, it is preferable to select a thing as fine as possible. As average particle diameter, 200 nm or less is preferable, More preferably, it is 150 nm or less, Most preferably, it is 100 nm or less. And as a minimum of an average particle diameter, it is 10 nm. Moreover, the inside of the said range is preferable also from a handling point.

Examples of the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specific examples of the inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

As an organic pigment, for example,

C.I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C.I. Pigment Orange 36, 38, 43, 71;

C.I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment Violet 19, 23, 32, 39;

C.I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37;

C. I. Pigment Brown 25, 28;

C.I. Pigment Black 1;

Carbon black, titanium black, etc. are mentioned.

Among the above, the following can be used preferably. However, in this invention, it is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;

C. I. Pigment Orange 36, 71;

C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;

C.I. Pigment Violet 19, 23, 32;

C.I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37;

C.I. Pigment Black 1;

It is preferable that the colored resin composition in this invention contains green, red, or blue organic pigment as said organic pigment.

Organic pigments may be used alone or in combination of two or more in order to enhance color purity. The specific example of a combination is shown below.

Examples of the pigment for red include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or one or more of these, and disazo yellow pigments, isoindolin yellow pigments, or quinophthalone yellow pigments. Mixed pigments of one or more pigments, mixed pigments of anthraquinone pigments and diketopyrrolopyrrole pigments and the like can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, CI pigment red as a diketopyrrolopyrrole pigment. 254, and from the point of color reproducibility, 1 or more types of mixed pigment of CI pigment yellow 139 and the said red pigment is preferable.

Moreover, as for mass ratio of a red pigment and a yellow pigment, 100: 5-100: 75 are preferable. If it is in this range, light transmittance can be suppressed and color purity can be improved. As a more preferable mass ratio, it is 100: 10-100: 50.

When using the said organic pigment for red as one or more types of the said coloring agents, the pigment whose average primary particle diameter is 150 nm or less is preferable for the organic pigment for red, As a content rate, it is 20 mass with respect to the total solid of a colored resin composition. It is preferable that it is% or more. Moreover, 100 nm or less is more preferable and, as for the average primary particle diameter of the organic pigment for red, 80 nm or less is more preferable. The lower limit of the average primary particle diameter is preferably 10 nm. Moreover, content rate becomes like this. Preferably it is 25 mass% or more with respect to the total solid of a colored resin composition, More preferably, it is 30 mass% or more. It is preferable that the upper limit of the said content rate is 50 mass% of the total solid of a colored resin composition.

If the content rate of the red organic pigment is 20 mass% or more, the color reproduction required as an LCD (liquid crystal display device) can be implement | achieved even if the coating film of a color filter is a thin film.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture of this and a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment can be used. .

For example, CI pigment green 36 alone or CI pigment green 7, 36, 37 and CI pigment yellow 83, CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 150, CI pig Mixing with cement yellow 180 or CI pigment yellow 185 is preferred.

As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable.

When using the said organic pigment for green as one or more types of the said coloring agents, the pigment whose average primary particle diameter is 200 nm or less is preferable for the organic pigment for green, As a content rate, it is 35 mass with respect to the total solid of a colored resin composition. It is preferable that it is% or more. Moreover, 150 nm or less is more preferable, and, as for the average primary particle diameter of the organic pigment for green, 100 nm or less is more preferable. The lower limit of the average primary particle diameter is preferably 10 nm. Moreover, content rate becomes like this. Preferably it is 45 mass% or more with respect to the total solid of a colored resin composition, More preferably, it is 50 mass% or more. It is preferable that the upper limit of the said content rate is 60 mass% of the total solid of a colored resin composition.

When the content rate of the green organic pigment is in the range of 35% by mass or more, even if the coating film of the color filter is a thin film, color reproduction required as an LCD (liquid crystal display device) can be realized.

As a pigment for blue, a phthalocyanine type pigment can be used individually, or the mixture of this and a dioxazine type purple pigment can be used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 is preferred.

As for the mass ratio of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable.

When using the said organic pigment for blue as one or more types of the said coloring agents, the pigment whose average primary particle diameter is 150 nm or less is preferable for the organic pigment for blue, As a content rate, it is 15 mass with respect to the total solid of a colored resin composition. It is preferable that it is% or more. Moreover, 100 nm or less is more preferable, and, as for the average primary particle diameter of the organic pigment for blue, 70 nm or less is more preferable. The lower limit of the average primary particle diameter is preferably 10 nm. Moreover, content rate becomes like this. Preferably it is 20 mass% or more with respect to the total solid of a colored resin composition, More preferably, it is 25 mass% or more. It is preferable that the upper limit of the said content rate is 50 mass% of the total solid of a colored resin composition.

If the content rate of the blue organic pigment is 15 mass% or more, the color reproduction required as an LCD (liquid crystal display device) can be implement | achieved even if the coating film of a color filter is a thin film.

In the present invention, when the colorant is a dye, it can be uniformly dissolved in the colored resin composition and obtained as a colored composition.

There is no restriction | limiting in particular as said dye, A conventionally well-known dye can be used for a color filter. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Registration 2592207, U.S. Patent No. 4,808,501, U.S. Patent 5,667,920, U.S. Patent 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115 Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. Hei 8-211599, Japanese Patent Laid-Open No. Hei 4-249549, Japanese Patent Laid-Open No. Hei 10-123316, Japanese Patent Laid-Open No. 11-302283 JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416 Japanese Patent Laid-Open Publication No. 2002-14220, Japanese Patent Laid-Open Publication No. 2002-14221, Japanese Patent Laid-Open Publication 2002-14222, Japanese Patent Laid-Open Publication 2002-14223, Japanese Patent Laid-Open Publication No. 8-302224, Japanese Patent Publication The pigment | dye described in Unexamined-Japanese-Patent No. 8-73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, etc. can be used.

Examples of the chemical structure of the dye include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthripyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine, Pyrrolopyrazole azomethine series, xanthene series, phthalocyanine series, benzopyran system, indigo system, etc. are mentioned.

In addition, when it is comprised by the resist system which performs water or alkali image development, an acid dye and / or its derivative can be used preferably from a viewpoint of completely removing the binder and / or dye of an unhardened part by image development. In addition, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes, and / or derivatives thereof are also useful.

The acid dye is not particularly limited as long as it has an acid group such as sulfonic acid or carboxylic acid, but is not particularly limited, solubility in an organic solvent or developer, salt formation with a basic compound, absorbance, interaction with other components in the composition, light resistance, and heat resistance. The performance is selected in consideration of all the required performance.

Hereinafter, the specific example of acid dye is shown. However, in this invention, it is not limited to these. For example,

acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; And derivatives of these dyes.

Among them, acid dyes include acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63, 74; acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217; acid violet 7; acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; Dyes such as acid green 25 and derivatives of these dyes are preferred.

Moreover, the azo-type, xanthene type, and phthalocyanine-type acid dye of that excepting the above is also preferable, C.I. Solvent Blue 44, 38; C.I. Solvent orange 45; Acid dyes such as Rhodamine B, Rhodamine 110 and derivatives thereof are also preferably used.

The average particle diameter, the range of content rate, and the preferable range of each for red, green, and blue in the colored resin composition at the time of using dye as a coloring agent are the same as the case of the organic pigment mentioned above.

A conventionally well-known pigment dispersant and surfactant can be added to a coloring resin composition for the purpose of improving the dispersibility of the said pigment. Although many kinds of compounds can be used as the dispersant, for example, phthalocyanine derivatives [commercially available product EFKA-745 (manufactured by Efca Co., Ltd.), Solsper's 5000 [manufactured by Geneca Co., Ltd.]; organosiloxane polymer KP341 )], (Meth) acrylic-acid type (co) polymer polyflow No.75, No.90, No.95 [cationic surfactant, such as Kyesisha Yushikagaku Kogyo Co., Ltd.], W001 (made by Yusho Corporation), etc. Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan Nonionic surfactant, such as fatty acid ester, Anionic surfactant, such as W004, W005, W017 (made by Yusho Corporation), EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA Polymer 450 [or higher, Polymer dispersing agents such as Morishita Sangyo Co., Ltd., Disperse Ade 6, Disperse Ade 8, Disperse Ade 15 and Disperse Ade 9100 (manufactured by Sanofucco); Solsper's 3000, Copper 5000, Copper 9000, Copper 12000 Various solvent dispersants (manufactured by Geneca Co., Ltd.), such as 13240, 1313, 17000, 24000, 26000, 28000, etc .; Adeka Pluronic L31, East F38, East L42, East L44, East L61 , Copper L64, Copper F68, Copper L72, Copper P95, Copper F77, Copper P84, Copper F87, Copper P94, Copper L101, Copper P103, Copper F108, Copper L121, Copper P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 [made by Sanyokasei Co., Ltd.] is mentioned.

Alkali-soluble resin

The colored resin composition of this invention contains 1 or more types of alkali-soluble resin which has one or more of a carboxyl group and a phosphoric acid group, and a sulfonic acid group in one molecule (henceforth "alkali-soluble resin which concerns on this invention"). Even if the particle size of the colorant used is small (that is, the surface area is large), the reduction of the voltage retention (VHR) can be effectively suppressed when the liquid crystal display panel is configured and the image is displayed, and the image reproducibility is good and stable image display can be performed. Can be. Moreover, by containing alkali-soluble resin which concerns on this invention, even if the particle | grains of a coloring agent (for example, a pigment) are fine, the storage safety of a coloring resin composition can be improved significantly. That is, even if the colored resin composition of this invention is preserve | saved for a long time, it has the advantage that hardly a viscosity change is seen.

The improvement of the voltage retention (VHR) is presumed to be due to the introduction of sulfonic acid groups having a small pKa in the molecule, which strongly attracts the electric charges contributing to the polarization, thereby suppressing the movement of electric charges even when a voltage is applied. In addition, sulfonic acid groups with small pKa are strongly adsorbed to specific sites (presumed to be strong basic points) on the surface of the pigment particles, while carboxyl groups and phosphate groups are adsorbed to weak basic points, whereby a large protective colloid of the pigment It is estimated that the particles are formed around the particles to maintain a high dispersion state. Moreover, since it is strongly adsorbed, it is estimated that it does not aggregate even in long term storage.

As alkali-soluble resin which concerns on this invention, it can select suitably from the thing which has alkali solubility which contains 1 or more of a carboxyl group and a phosphoric acid group, and a sulfonic acid group in a molecule | numerator (preferably an acryl-type copolymer, the molecule which has a styrene-type copolymer as a main chain). .

Such alkali-soluble resin is obtained by copolymerizing the monomer which has a carboxylic acid component as follows, the monomer which has a phosphoric acid component, and the monomer which has a sulfonic acid component.

Examples of monomers having a carboxylic acid component include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, and the like, and JP-A-59-44615, JP-A-54-34327, Japanese Patent Laid-Open No. 58-12577, Japanese Patent Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048. Examples of the monomers having a phosphoric acid component, for example, 2- (meth) acryloyl phosphate, etc. yl-oxy, to of D-1 ~ D-9 (formula compound, Q ₂ denotes a -H or -CH ₃ , j represents an integer of 2 to 18, l represents an integer of 1 to 4, and m represents an integer of 1 to 12.

Monomers having a sulfonic acid component include, for example, the following compounds D-10 to D-16 (wherein, Q ₂ represents -H or -CH ₃ , j represents an integer of 2 to 18, and m represents 1 to 1). And an integer of 12.).

Monomers having these acid components can be copolymerized with other copolymerizable monomers to obtain alkali-soluble resins according to the present invention. When the monomer component having an acid group increases, solubility in a solvent is insufficient, so that it is preferable to copolymerize with other copolymerizable monomers having no acid component.

As said "other copolymerizable monomer", an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned, for example. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the substituent.

Examples of the alkyl (meth) acrylate and aryl (meth) acrylate, for ^{_{example, CH 2 = C (R 1}} ) (COOR 3) [here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R <^3> represents a C1-C8 alkyl group or a C6-C12 aralkyl group. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) Acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (Meth) acrylate (alkyl is a C1-C8 alkyl group), hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.] etc. are mentioned.

Moreover, the resin which has a polyalkylene oxide chain in a molecular side chain is also preferable.

As said polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or these side chains can be used together, The terminal is a hydrogen atom or a linear or branched alkyl group.

1-20 are preferable and, as for the repeating unit number of the said polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Examples of the acrylic copolymer having a polyalkylene oxide chain in these side chains include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol. Mono (meth) acrylate, poly (ethylene glycol propylene glycol) mono (meth) acrylate, etc., and compounds which alkyl-blocked these terminal OH groups, for example, methoxy polyethylene glycol mono (meth) acrylate, It is an acrylic copolymer which uses methoxy polypropylene glycol mono (meth) acrylate, methoxy poly (ethylene glycol propylene glycol) mono (meth) acrylate, etc. as a copolymerization component.

Furthermore, in CH ^₂ = CR ¹ R ₂ where [Examples of the vinyl compounds, R ¹ denotes a hydrogen atom or an alkyl group having a carbon number of 1 ~ 5, R ² represents an aromatic hydrocarbon ring having 6 to 10. Specifically, styrene, (alpha) -methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, a polystyrene macromonomer, a polymethylmethacrylate macromonomer, etc.] etc. are mentioned. Preferred copolymerizable other monomers are alkyl (meth) acrylates (alkyl is an alkyl group having 2 to 4 carbon atoms), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.

It is preferable that carboxylic acid group containing alkali-soluble resin (for example, acrylic resin) has an acid value of 20-200 mgKOH / g by adjusting the copolymerization ratio of each monomer suitably. When the acid value exceeds 200, the alkali-soluble resin (e.g., acrylic resin) may become too soluble in alkali, resulting in narrowing of the developing development range (developing latitude). Solubility may be small and developing may take too much time. The acid amount of the same grade is also suitable also about alkali-soluble resin containing phosphoric acid group (for example, acrylic resin).

In addition, as weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of alkali-soluble resin (for example, acrylic resin), in order to implement | achieve the viscosity range which is easy to use normally, such as apply | coating a color resist, and also film strength It is preferable that it is 2,000-100,000, More preferably, it is 3,000-50,000 in order to ensure the.

It is preferable that the quantity of alkali-soluble resin in the colored resin composition of this invention is 5-90 mass% of the total solid of a composition, More preferably, it is 10-60 mass%. When the amount of the alkali-soluble resin is less than 5% by mass, the film strength may be lowered. When the amount of the alkali-soluble resin is higher than 90% by mass, the acid component is increased, so that the solubility is difficult to control, or the pigment is relatively low, so that sufficient image density is not obtained. I do not do it. In particular, a high yield and a favorable coating film can be obtained with respect to slit coating which is suitable for the application | coating to the board | substrate of a wide area with wide width.

Moreover, in order to improve the crosslinking efficiency of the colored resin composition of this invention, you may use resin which has a polymeric group in alkali-soluble resin alone, or it can be used with alkali-soluble resin which does not have a polymeric group, and an aryl group and a (meth) acryl group And polymers having an aryloxyalkyl group and the like in the side chain are useful. Alkali-soluble resin which has a polymerizable double bond can be developed by alkaline developing solution, and is further equipped with photocurability.

Examples of the polymer having these polymerizable groups are shown below. However, if alkali-soluble groups, such as a COOH group and an OH group, contain a carbon-carbon unsaturated bond, it will not be limited to the following.

(1) A urethane-modified compound obtained by reacting an isocyanate group with an OH group in advance to leave at least one unreacted isocyanate group and also containing at least one (meth) acryloyl group and an acrylic resin containing a carboxyl group. Polymerizable double bond-containing acrylic resin,

(2) an unsaturated group-containing acrylic resin obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;

(3) acid pendant epoxy acrylate resin,

(4) Acrylic resin containing an OH group A polymerizable double bond-containing acrylic resin obtained by reacting a dibasic acid anhydride having a polymerizable double bond.

Among the above, resin of (1) and (2) is especially preferable.

As acid value of alkali-soluble resin which has a polymerizable double bond, Preferably it is 30-150 mgKOH / g, More preferably, it is 35-120 mgKOH / g, As weight average molecular weight Mw, Preferably it is 2,000-50,000, More preferably, Is 3,000 to 30,000.

As content in the colored resin composition of alkali-soluble resin which concerns on this invention, 0.5-150 mass% is preferable with respect to the mass of the said coloring agent, and 1-120 mass% is more preferable. When the content of the alkali-soluble resin according to the present invention is within the above range, in the case of constituting a system in which a colorant having a small particle size is dispersed, it is possible to effectively suppress a decrease in voltage retention at the time of displaying an image, and to have good image reproducibility. It is effective for performing stable image display.

Photopolymerizable Compound

The colored resin composition of this invention can be preferably comprised using 1 or more types of photopolymerizable compounds. As a photopolymerizable compound, if it is a polymeric compound which can be photopolymerized by the action of the photoinitiator mentioned later, it can select without particular limitation.

Especially, the compound which has one or more addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure is preferable, and especially a tetrafunctional or more acrylate compound is preferable.

As a compound which has one or more addition-polymerizable ethylenically unsaturated group and whose boiling point is 100 degreeC or more at normal pressure, for example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acryl Monofunctional acrylates and methacrylates such as a rate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane, etc. (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japan Urethane acrylates described in Patent Publications No. 50-6034 and Japanese Patent Laid-Open Nos. 51-37193, Japanese Patent Publication No. 48-64183, Japan Polyfunctional acrylates and meta, such as the polyester acrylates described in each of Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490, and epoxy acrylate which is a reaction product of an epoxy resin and (meth) acrylic acid. Acrylate is mentioned. Moreover, the thing introduce | transduced as a photocurable monomer and an oligomer can also be used by Japanese adhesive association Vol.20, No. 7, 300-308.

Moreover, the compound which (meth) acrylated after adding ethylene oxide or a propylene oxide to the said polyfunctional alcohol is the specific example of General Formula (1) and (2) as Unexamined-Japanese-Patent No. 10-62986, and its specific example. It is described together. These can also be used as a photopolymerizable compound.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types can also be used.

A photopolymerizable compound can be used individually by 1 type or in combination of 2 or more types.

Content in the colored resin composition of a photopolymerizable compound becomes like this. Preferably it is 20-80 mass parts with respect to 100 mass parts of total solids of a colored resin composition, More preferably, it is 30-70 mass parts. If content of a photopolymerizable compound exists in the said range, hardening can be performed favorably.

Photoinitiator

The colored resin composition of this invention can be preferably comprised using 1 or more types of photoinitiators. This photoinitiator is contained together with the said photopolymerizable compound, and while high hardening degree is obtained, it is also possible to control curability as desired.

As a photoinitiator, For example, Halomethyloxadiazole of Unexamined-Japanese-Patent No. 57-6096; Active halogen compounds such as halomethyl-s-triazine described in JP-A-59-1281, JP-A-53-133428, and the like; Aromatic carbonyl compounds such as ketal, acetal or benzoin alkyl ethers described in US Patent USP-4318791, European Patent Publication EP-88050A and the like; Aromatic ketone compounds such as benzophenones described in US Patent USP-4199420; (Thio) xanthones or acridines compounds described in Fr-2456741; Compounds such as coumarins or ropin dimers described in JP-A-10-62986; Sulfonium organoboron complexes such as JP-A-8-015521; Etc. can be used.

Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarins series, ropin dimer series, biimidazole series and the like. Preferred photopolymerization initiators.

As acetophenone type photoinitiator, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino, for example Acetophenone, 4'-isopropyl-2-hydroxy-2-methyl- propiophenone, etc. are mentioned preferably.

As said ketal type photoinitiator, benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl acetal, etc. are mentioned preferably, for example.

As said benzophenone type photoinitiator, a benzophenone, 4,4'- (bisdimethylamino) benzophenone, 4,4'- (bisdiethylamino) benzophenone, 4,4'- dichloro benzophenone, for example , 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-tolyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 etc. are mentioned preferably.

As said benzoin- or benzoyl-type photoinitiator, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o- benzoyl benzoate, etc. are mentioned preferably, for example.

As said xanthone type photoinitiator, diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chloro thioxanthone, etc. are mentioned preferably, for example.

As said triazine type photoinitiator, 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine and 2, 4-bis (trichloromethyl) -6-p- Methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4- Bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxysty Reyl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6 -Di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxy Carbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine etc. are mentioned preferably.

As said halomethyloxadiazole type photoinitiator, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole and 2-trichloromethyl-5- (cyanostyryl) -1, for example , 3,4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) Styryl-1,3,4-oxodiazole etc. are mentioned preferably.

As said acridine-type photoinitiator, 9-phenyl acridine, 1, 7-bis (9-acridinyl) heptane, etc. are mentioned preferably, for example.

As a photoinitiator of the said coumarins system, for example, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-(( s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, etc. are preferable. have.

As a photoinitiator of the said lophine dimer type, 2- (o-chlorophenyl) -4,5-diphenyl imidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenyl are mentioned, for example. Midazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, etc. are mentioned preferably.

As said biimidazole type photoinitiator, 2-mercaptobenzimidazole, 2,2'- benzothiazolyl disulfide, etc. are mentioned preferably, for example.

In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6- Trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, and the like.

In this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, bisinalpolyketolaldonyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, US Pat. No. 2,448,828 Acyloinethers, aromatic acyloin compounds substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512, multinuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. Combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in the specification of 3,549,367, benzothiazole compound / trihalomethyl-s-triazine compound disclosed in Japanese Patent Publication No. 51-48516 Etc. can be mentioned.

Moreover, these photoinitiators can also be used together.

As content in the colored resin composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 0.5-5.0 mass%. When content of a photoinitiator is the said range, superposition | polymerization hardening can be performed favorably and high film strength can be obtained.

-solvent-

The colored resin composition of this invention can be prepared generally using a solvent.

Examples of the solvent include esters, for example ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl acid butyrate, ethyl butyrate, butyrate butyl, alkyl esters and lactic acid Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxy acetate, ethyl methoxyacetate, butyl butyl acetate, ethoxy acetate, ethyl ethoxy acetate, and methyl 3-oxypropionate, 3 3-oxypropionic acid alkyl esters such as ethyl oxypropionate (for example, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate, etc.), 2- 2-oxypropionic acid alkyl esters such as methyl oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionic acid (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methok) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionate, etc.), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. ;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Aromatic hydrocarbons such as toluene, xylene,

Etc. can be mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.

You may use a solvent in combination of 2 or more type other than using independently.

-Other ingredients

The colored resin composition of this invention can contain various additives, such as a thermal polymerization inhibitor, another filler, a high molecular compound other than the said alkali-soluble resin, surfactant, adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor as needed.

<Heat polymerization inhibitor>

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful.

<Various additives>

Specific examples of the various additives include fillers such as glass and alumina; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, addition of acid anhydride to a polymer having a hydroxyl group, formed of alcohol soluble nylon, bisphenol A and epichlorohydrin Alkali-soluble resins such as phenoxy resins; Mega pack F171, copper F172, copper F173, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437 [above, Dainippon Ink & Chemical Co., Ltd.], Florid FC430, copper FC431, copper FC171 (above, made by Sumitomo Industries Co., Ltd.), saffron S-382, copper SC-101, copper SC-103, copper SC-104, copper SC-105, copper SC1068, copper SC-381, Fluorine-based organic compounds such as SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.); Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And aggregation inhibitors such as sodium polyacrylate.

In addition, when promoting the alkali solubility of an unhardened part, and for the further improvement of developability of the colored resin composition of this invention, the colored resin composition of this invention has organic carboxylic acid, Preferably the low molecular weight organic carboxyl of 1000 or less molecular weight is carried out. More acid can be added. Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, a butyric acid, a gil acetic acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid, and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamylidene acetate, fumaric acid, and unbelic acid. Can be.

The coloring resin composition of this invention is a coloring agent with an average particle diameter of 200 nm or less, and alkali-soluble resin which has at least 1 of a carboxyl group and a phosphoric acid group and a sulfonic acid group in 1 molecule, and a photopolymerizable compound, a photoinitiator, and another component as needed (preferably It can be preferably prepared by mixing with a solvent) and going through a mixed dispersion step of mixing and dispersing using various mixers and dispersers.

In addition, the form of the mixed dispersion step is preferably configured by providing a mixed dispersion and a microdispersion treatment performed subsequently. However, it is also possible to omit mixed dispersion.

In the colored resin composition of this invention, Preferably, the colorant is mixed-dispersed-processed using a dispersing agent so that the viscosity after a dispersing process may become comparatively high viscosity (10,000 mPa * s or more, Preferably 100,000 mPa * s or more), and then this invention The alkali-soluble resin according to the present invention is added and subjected to microdispersion treatment so that the viscosity after the treatment becomes a relatively low viscosity (1,000 mPa · s or less, preferably 100 mPa · s or less).

In mixed dispersion processing, it is preferable to use two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single-axis and twin-screw extruders, etc. Let's do it. Subsequently, the solvent and the alkali-soluble resin according to the present invention are added, and are mainly used as beads (glass having a particle diameter of 0.1 to 1 mm, zirconia, etc.) using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. Distributed processing It is also possible to omit the mixed dispersion process here. In that case, bead dispersion is performed with a pigment, a dispersing agent, or a surface treating agent, an acrylic copolymer, and a solvent. In addition, for details of mixing and dispersion | distribution, T.C. "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964).

The color filter for liquid crystal display elements of this invention is used for a liquid crystal display element (LCD). Preparation of this color filter can apply it, image forming by the photolithographic method, after apply | coating the coloring resin composition of this invention mentioned above on a board | substrate. In the case of the photolithography method, the colored resin composition of the present invention is applied to a coating method (preferably slit coating using a slit coater) such as rotation coating, slit coating, cast coating, roll coating, or the like directly on a substrate or through another layer. By coating, drying (prebaking) to form a coating film of the colored resin composition, exposing through a predetermined mask pattern, forming a latent image in the cured portion and the non-cured portion by light irradiation, and the uncured portion by the development treatment. By removing the development and leaving only the hardened portion (for example, a single color, or two or more colors of three or four colors), a pattern consisting of a colored pattern image (that is, colored pixels) can be formed to obtain a color filter.

As the radiation to be irradiated at this time, particularly ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used.

Drying (prebaking) of the coating film comprised from the colored resin composition of this invention apply | coated on the board | substrate can be performed in 10 to 300 second at the temperature of 50-140 degreeC using a hotplate, oven, etc.

As for the color filter for liquid crystal display elements of this invention, it is preferable that y value of green (G) in a CIE chromaticity diagram is 0.59 or more, 0.59-0.7 are more preferable, 0.60-0.68 are especially preferable. When y value is too low, the color purity of light will fall and color reproducibility tends to become low. On the other hand, x value on a CIE chromaticity diagram is a value which determines a color, Preferably it is 0.25-0.35.

Moreover, it is preferable that the x value of red (R) in a CIE chromaticity diagram is 0.60 or more, as for the color filter for liquid crystal display elements of this invention, 0.6-0.7 are more preferable, 0.62-0.68 are especially preferable. If the x value is too low, the color purity of the light is lowered and the color reproducibility tends to be lowered. On the other hand, y value on a CIE chromaticity diagram is a value which determines a color, Preferably it is 0.25-0.35.

Moreover, it is preferable that the y value of blue (B) in a CIE chromaticity diagram is 0.10 or less, as for the color filter for liquid crystal display elements of this invention, 0.04-0.1 are more preferable, 0.05-0.09 are especially preferable. If the y value is too large, the color purity of the light is lowered and the color reproducibility tends to be lowered. On the other hand, the x value on the CIE chromaticity diagram is preferably 0.1 to 0.2.

In the above, CIE chromaticity is obtained by measuring using a colorimeter (manufactured by Otsuka Denshi Co., Ltd.) on an unexposed film (for example, a coating film) formed on a substrate using a colored resin composition.

The color filter for liquid crystal display elements of the present invention has a good image reproducibility when a voltage is applied to display an image, and performs stable image display. The voltage retention is preferably 85% or more, more preferably 90% or more, and 95 % Or more is more preferable. The details of the voltage retention are as described above.

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass, and transparent conductive films attached thereto, and solid-state imaging devices (CCD, etc.) used in liquid crystal display devices (LCDs) and the like. Photoelectric conversion element substrates used for image sensors) etc., for example, a silicon substrate, etc. are mentioned. Plastic substrates are also possible. On these substrates, black stripes which isolate each pixel are usually formed. In addition, the plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

As thickness (dry film thickness) of the coating film in the case of apply | coating the colored resin composition of this invention on a board | substrate, 0.3-5.0 micrometers is preferable normally, More preferably, it is 0.5-3.5 micrometers, Most preferably, 1.0-2.5 [Mu] m.

The developing treatment can be performed by using an alkaline developer to dissolve the uncured portion in the developer without dissolving the photocured portion. An alkaline developing solution can melt | dissolve the film | membrane of the colored resin composition of an uncured part, and can use any, as long as it does not melt a hardened part. Developing temperature is 20-30 degreeC normally, and 20-90 second is preferable as developing time.

In addition, after the image development treatment, the excess developer is generally washed and removed and dried, followed by heat treatment (post bake) at a temperature of 50 to 240 ° C.

By repeating the above steps sequentially for each color by the desired color, it is possible to obtain a cured film (including a color filter) which is difficult in process and colored at high quality and low cost.

As said alkaline developing solution, as long as it is a composition which melt | dissolves the uncured part of the colored resin composition of this invention, and does not melt a hardened part, it can select without limitation, Specifically, the combination of various organic solvents or alkaline aqueous solution Can be used.

The organic solvent mentioned above which can be used for preparation of the colored resin composition of this invention is mentioned.

As an alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide The concentration of the alkaline compounds such as roxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001-10% by mass, preferably 0.01-1 The alkaline aqueous solution melt | dissolved and prepared so that it may become mass% can be used. In addition, when alkaline developing solution is used, washing | cleaning (rinse) with water is generally performed after image development processing.

The said postbaking is heating after the development process for making hardening complete, and heating (hard baking) of about 200-220 degreeC is normally performed. Post-baking can be performed continuously or collectively using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that it may become said condition with respect to the coating film after image development processing.

Although the coloring resin composition of this invention was demonstrated mainly centering on the manufacture use of a color filter, it is applicable also to preparation of the black matrix formed between the colored pixels which comprise a color filter. A black matrix can be produced by exposing and developing the colored resin composition of this invention prepared using black coloring agents, such as carbon black and titanium black, as a coloring agent, post-baking as needed, and promoting film hardening.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

In addition, the weight average molecular weight was measured by gel permeation chromatography (GPC). GPC uses HLC-8120GPC and SC-8020 (manufactured by Tosoh Corporation), uses two TSKgel and Super HM-H [manufactured by Tosoh Corporation, 6.0 mmID × 15 cm] as a column, and THF as an eluent. (Tetrahydrofuran) was used. As conditions, the sample concentration was 0.5 mass%, the flow rate was 0.6 ml / min, the sample injection amount was 10 μl, the measurement temperature was 40 ° C., and an IR detector was used. In addition, the analytical curve is made by the Tosoh Corporation "polystyrene standard sample TSK standard": "A-500", "F-1", "F-10", "F-80", "F-380", "A-2500" , "F-4", "F-40", "F-128", and "F-700" were produced with ten samples.

(Examples 1-4, Comparative Examples 1-3)

(1) Synthesis of Resin

<Synthesis of alkali-soluble resin R-1>

The component in the following composition was put into the reaction container, 564 parts of propylene glycol monomethyl ether acetates, and 18 parts of azobisisobutyronitrile were added, and it melt | dissolved uniformly. And this solution was polymerized over 5 hours at 100 degreeC, and the polymer solution of alkali-soluble resin R-1 which has a carboxyl group and a sulfonic acid group in the molecule | numerator was obtained. Solid content of this polymer solution was 40.2%, and the weight average molecular weight was 12000.

-Furtherance-

Benzyl methacrylate. 300 copies

· Methacrylic acid… Part 29

2-acrylamide-2-methylpropanesulfonic acid [the compound D-16 (Q ₂ = H)]. Part 47

<Synthesis of alkali-soluble resin R-2>

The component in the following composition was put into the reaction container, 942 parts of propylene glycol monomethyl ether acetates, and 24 parts of azobisisobutyronitrile were further added and it melt | dissolved uniformly. And this solution was polymerized over 90 hours at 90 degreeC, and the polymer solution of alkali-soluble resin R-2 which has a carboxyl group, a phosphoric acid group, and a sulfonic acid group in the molecule | numerator was obtained. Solid content of this polymer solution was 40.3%, and the weight average molecular weight was 14000.

-Furtherance-

Methyl methacrylate. Part 396

2-methacryloyloxyethyl phosphate... 104 copies

2-acrylamide-2-methylpropanesulfonic acid. Part 102

<Synthesis of alkali-soluble resin R-3 (comparative)>

The component in the following composition was put into the reaction container, 1212 parts of propylene glycol monomethyl ether acetates, and 38 parts of azobisisobutyronitrile were further added and it melt | dissolved uniformly. And this solution was polymerized over 100 hours at 100 degreeC, and the polymer solution of alkali-soluble resin R-3 for comparison was obtained. Solid content of this polymer solution was 39.9%, and the weight average molecular weight was 10300.

-Furtherance-

Benzyl methacrylate. 750 copies

· Methacrylic acid… Part 92

<Synthesis of alkali-soluble resin R-4 (comparative)>

The component in the following composition was put into the reaction container, 688 parts of propylene glycol monomethyl ether acetate and 20 parts of azobisisobutyronitrile were added, and it melt | dissolved uniformly. And this solution was polymerized over 95 hours at 95 degreeC, and the polymer solution of alkali-soluble resin R-4 for comparison was obtained. Solid content of this polymer solution was 40.3%, and the weight average molecular weight was 9700.

-Furtherance-

Methyl methacrylate. 280 copies

2-methacryloyloxyethyl phosphate... Part 126

Acrylic acid… Part 43

<Synthesis of alkali-soluble resin R-5>

In the synthesis of the alkali-soluble resin R-1, 30 parts of the following compound D-10 (Q ₂ = CH ₃ , m = 4) was used instead of 47 parts of 2-acrylamide-2-methylpropanesulfonic acid. The polymer solution of alkali-soluble resin R-5 which has a carboxyl group and sulfonic acid group in the molecule | numerator was obtained like synthesis of alkali-soluble resin R-1. Solid content of this polymer solution was 38.9%, and the weight average molecular weight was 8000.

<Synthesis of Resin S for Pigment Dispersion>

The component in the following composition was put into the reaction container, 753 parts of propylene glycol monomethyl ether acetates, and 11 parts of azobisisobutyronitrile were added, and it melt | dissolved uniformly. And this solution was polymerized over 7 hours at 90 degreeC, and the polymer solution of resin S for pigment dispersion was obtained. Solid content of this polymer solution was 50.2%, and the weight average molecular weight was 29700.

-Furtherance-

Methyl methacrylate. 500 copies

2-diethylaminoethyl methacrylate... Part 123

2-hydroxyethyl methacrylate... 130 copies

(2) Preparation of Pigment Dispersion

<Preparation of Pigment Dispersion P-1>

The pigment dispersion liquid P-1 was prepared by mixing the component in the following composition, and disperse | distributing the liquid mixture to the bead disperser using the zirconia beads of an average particle diameter of 0.3 mm. Immediately after dispersion, the average primary particle diameter of the pigment was measured using a transmission electron microscope (TEM). As a result, it was 50 nm.

-Furtherance-

Polymer solution of the resin S. Part 46

C.I. Pigment Red 254... Part 40

C.I. Pigment Red 177... Part 12

Propylene glycol monomethyl ether acetate... Part 127

<Preparation of Pigment Dispersion P-2>

The pigment dispersion liquid P-2 was prepared by mixing the component in the following composition, and disperse | distributing in the same manner as the said pigment dispersion liquid P-1. The average primary particle diameter of the pigment measured similarly to the case in the said pigment dispersion liquid P-1 was 60 nm.

-Furtherance-

Polymer solution of the resin S. Part 17

Disperbyk 161 (manufactured by BYK; dispersant). Part 10

C.I. Pigment Green 36... Part 40

C.I. Pigment Yellow 150... Part 25

Propylene glycol monomethyl ether acetate... Part 162

<Preparation of Pigment Dispersion P-3>

The pigment dispersion liquid P-3 was prepared by mixing the component in the following composition, and disperse | distributing in the same manner as the said pigment dispersion liquid P-1. The average primary particle diameter of the pigment measured similarly to the case in the said pigment dispersion liquid P-1 was 40 nm.

-Furtherance-

Polymer solution of the resin S. 50 copies

C.I. Pigment Blue 15: 6. Part 87

C.I. Pigment Violet 23... Part 25

Solsperse 12000 (manufactured by ZENEKA; dispersant). Part 5

Propylene glycol monomethyl ether acetate... 200 copies

(3) Preparation of Photosensitive Colored Resin Composition

<Preparation of the photosensitive colored resin composition CR-1>

The following components were mixed and stirred to prepare a uniform red photosensitive colored resin composition CR-1.

The pigment dispersion P-1... 131 pages

· Dipentaerythritol hexaacrylate... Part 28.5

Irgacure 369. Part 1.4

  [Chiba Specialty Chemical Co., Ltd.]

Polymer solution of alkali-soluble resin R-1; Part 48.15

Propylene glycol monomethyl ether acetate... Part 291

<Preparation of the photosensitive colored resin composition CR-2>

The following components were mixed and stirred to prepare a uniform green photosensitive colored resin composition CR-2.

The pigment dispersion P-2... Part 249

· Dipentaerythritol hexaacrylate... Part 27

Irgacure 369. Part 1.4

  [Chiba Specialty Chemical Co., Ltd.]

Polymer solution of alkali-soluble resin R-2; 50 copies

Propylene glycol monomethyl ether acetate... 370 copies

<Preparation of the photosensitive colored resin composition CR-3>

The following components were mixed and stirred to prepare a uniform blue photosensitive colored resin composition CR-3.

The pigment dispersion P-3. Part 138

· Dipentaerythritol hexaacrylate... Part 41

Irgacure 369. Part 2.1

  [Chiba Specialty Chemical Co., Ltd.]

Polymer solution of alkali-soluble resin R-1; Part 91

Propylene glycol monomethyl ether acetate... 454 copies

<Preparation of the photosensitive colored resin composition CR-4 (for comparison)>

The following component was mixed and stirred to prepare a uniform red photosensitive colored resin composition CR-4.

The pigment dispersion P-1... 131 pages

· Dipentaerythritol hexaacrylate... Part 28.5

Irgacure 369. Part 1.4

  [Chiba Specialty Chemical Co., Ltd.]

Polymer solution of alkali-soluble resin R-3; Part 48.15

Propylene glycol monomethyl ether acetate... Part 291

<Preparation of the photosensitive colored resin composition CR-5 (for comparison)>

The following components were mixed and stirred to prepare a uniform green comparative photosensitive colored resin composition CR-5.

The pigment dispersion P-2... Part 249

· Dipentaerythritol hexaacrylate... Part 27

Irgacure 369. Part 1.4

  [Chiba Specialty Chemical Co., Ltd.]

Polymer solution of alkali-soluble resin R-4; 50 copies

Propylene glycol monomethyl ether acetate... 370 copies

<Preparation of the photosensitive colored resin composition CR-6 (for comparison)>

The following components were mixed and stirred to prepare a uniform blue photosensitive colored resin composition CR-6 for comparison.

The pigment dispersion P-3. Part 138

· Dipentaerythritol hexaacrylate... Part 41

Irgacure 369. Part 2.1

  [Chiba Specialty Chemical Co., Ltd.]

Polymer solution of alkali-soluble resin R-4; Part 91

Propylene glycol monomethyl ether acetate... 454 copies

<Preparation of the photosensitive colored resin composition CR-7>

In the preparation of the photosensitive colored resin composition CR-1, 49.8 parts of the polymer solution of the alkali-soluble resin R-5 was used instead of 48.15 parts of the polymer solution of the alkali-soluble resin R-1. In the same manner as in the preparation of, a uniform red photosensitive colored resin composition CR-7 was prepared.

(4) image formation

A glass substrate (10 cm × 10 cm) for a color filter with an ITO transparent electrode was prepared, and each of the photosensitive colored resin compositions CR-1 to CR-7 obtained from the above was placed on each ITO transparent electrode on a separate glass substrate. It applied to the spin coater, and mounted the glass substrate after application so that it might contact on a glass substrate surface (non-coating surface) on a 100 degreeC hotplate, it dried for 2 minutes, and formed the photosensitive colored layer whose dry layer thickness is 2.0 micrometers.

Subsequently, the formed photosensitive colored layer was pattern-exposed at the exposure amount of 100 mPa / cm <2> through the mask which has a predetermined | prescribed pattern using the ultrahigh pressure mercury lamp of 2.5 kW. After exposure, the development process was performed at 26 degreeC for 60 second using the 10% dilution liquid of developing solution CD (manufactured by Fujifilm Electronics Materials Co., Ltd.), and further rinsed with pure water to form a pixel pattern. This pixel pattern was put into a 220 degreeC convection oven for 30 minutes, and it heated and hardened | cured and fixed the pixel pattern, and obtained the color filter substrate.

(5) evaluation

It evaluated by the method shown below using each photosensitive colored resin composition and each color filter board | substrate obtained from the above. The evaluation results are shown in Tables 1 to 2 below.

-One. Voltage Retention Rate (VHR)

As shown in FIG. 1, the glass substrate (10 cm x 10 cm) which has each color filter substrate obtained above and the ITO transparent electrode prepared separately from this is made into the pixel formation surface of a color filter substrate, and the ITO transparent electrode surface of a glass substrate. The cells were arranged so as to face each other, and a small cell was produced using a sealing agent so that the cell gap became 5 µm. Liquid crystal (MLC-6846-000 by Merck Co., Ltd.) was injected into this small cell, and it heated at 100 degreeC by the oven for 1 hour. After heating, after cooling to room temperature, the voltage was applied for 60 microseconds by the voltage of 5V, and the cell voltage after 16.7 m second after voltage release was measured. The measurement was performed by wiring between the ITO transparent electrode on the color filter substrate side, and the ITO transparent electrode on the glass substrate side. At this time, voltage application was 5 volts, and the polarity was inverted and repeated several times to average the measured cell voltages. And the voltage retention (%) was calculated | required from the following formula using the obtained cell voltage.

Voltage retention (%) = (cell voltage / 5) x 100

-2. Pattern shape

(1) Whether pixels are peeled or broken

The state of the pixel pattern after rinsing was observed using the optical microscope, and the presence or absence of peeling and a crack was evaluated.

(2) Straight or Cross-sectional Shape of Pixel Pattern and Non-Image Residue

The shape of the straight part of the pixel pattern after rinsing, and the presence or absence of the residue in a pixel non-formation area | region (non-image part) were observed using the scanning electron microscope (Side length SEM S-7800H, the Hitachi Seisakusho Co., Ltd. product). In addition, the shape of the cut surface which cut | disconnected the color filter board | substrate for every glass substrate was evaluated so that the cross section of the pixel pattern after rinsing could be observed, respectively. In addition, evaluation of the cross-sectional shape was performed by classifying into forward taper (upper), slightly vertical, inverse taper (upper), and impossible to measure.

-3. Storage stability-over time of the photosensitive coloring resin composition

The obtained photosensitive colored resin composition was filled in a brown bottle and stored in a 5-10 degreeC refrigerator. And whenever the storage period passed 2 months, the viscosity was measured at 25 degreeC using the E-type viscosity meter (model: RE550H, Toki Sangyo Co., Ltd. product).

As shown in the said Table 1-Table 2, in the Example, the color filter with a favorable pattern shape was obtained and the fall of the voltage retention was also suppressed significantly. Therefore, when a liquid crystal panel is comprised, image reproducibility is favorable and stable image display is attained. In addition, despite the small average primary particle diameter of the pigment, the storage stability was excellent.

On the other hand, in the comparative example, the color filter with a good pattern shape was obtained similarly to an Example, but the voltage retention which could maintain the stable image reproduction was not able to be maintained high because the fall of voltage retention was remarkable. Moreover, the viscosity increase was seen with time after preparation of the photosensitive colored resin composition, and favorable storage stability was not obtained.

ADVANTAGE OF THE INVENTION According to this invention, the fall of the voltage retention at the time of image display is suppressed, and the coloring resin composition and color filter for liquid crystal display elements which can perform stable image display with favorable image reproducibility of a display image can be provided. The colored resin composition of the present invention has good storage stability over time, and even when the colorant particles are fine, the viscosity change when stored over time is small, and the change over time can be suppressed small.

Claims (16)

A coloring resin composition having an average particle diameter of 200 nm or less and a alkali-soluble resin having at least one of a carboxyl group and a phosphoric acid group and a sulfonic acid group in one molecule. The colored resin composition according to claim 1, wherein the alkali-soluble resin is a resin obtained by copolymerization using at least one compound selected from the following compounds D-1 to D-9.

[Wherein, Q ₂ represents -H or -CH ₃ , j represents an integer of 2 to 18, l represents an integer of 1 to 4, and m represents an integer of 1 to 12.] The colored resin composition according to claim 1, wherein the alkali-soluble resin is a resin obtained by copolymerization using at least one compound selected from the following compounds D-10 to D-16.

[Wherein, Q ₂ denotes a -H or -CH _3, j is an integer of 2 ~ 18, m represents an integer of 1-12.] The colored resin composition of Claim 1 whose weight average molecular weight (polystyrene conversion value measured by GPC method) of the said alkali-soluble resin is 2,000-100,000. The red colorant is an average particle diameter of 150 nm or less, and the content rate with respect to the total solid of the said red colorant is 20 mass% or more, The said red colorant is characterized by the above-mentioned. Colored resin composition to be. The green coloring agent is an average particle diameter of 200 nm or less, and the content rate with respect to the total solid of the said green coloring agent is 35 mass% or more, It is characterized by the above-mentioned. Colored resin composition to be. The blue coloring agent is an average particle diameter of 150 nm or less, and the content rate with respect to the total solid of the said blue coloring agent is 15 mass% or more, The said coloring agent for blue is characterized by the above-mentioned. Colored resin composition to be. The colored resin composition according to claim 1, further comprising a photopolymerizable compound and a photopolymerization initiator. It formed using the colored resin composition of Claim 1, The color filter for liquid crystal display elements characterized by the above-mentioned. The color filter for liquid crystal display elements according to claim 9, wherein the voltage retention is 85% or more. The colored resin composition according to claim 1, wherein the colorant is an organic pigment having an average particle diameter of 10 to 100 nm. 6. The colored resin composition according to claim 5, wherein the red colorant has an average particle diameter of 10 to 100 nm and a content ratio of 25 to 50 mass% of the total solid of the red colorant. The colored resin composition according to claim 6, wherein the green colorant has an average particle diameter of 10 to 100 nm, and the content of the green colorant is 45 to 60 mass% with respect to the total solids. The said blue coloring agent is an average particle diameter of 10-100 nm, and the content rate with respect to the total solid of the said blue coloring agent is 25-50 mass%, The colored resin composition of Claim 7 characterized by the above-mentioned. Content of the said alkali-soluble resin is 0.5-150 mass% with respect to the mass of the said coloring agent, The colored resin composition of Claim 1 characterized by the above-mentioned. The colored resin composition according to claim 8, wherein the photopolymerizable compound is a tetrafunctional or higher acrylate compound.

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