KR20110089059A - Pigment dispersion composition, photosensitive colored composition, color filter using the same, and liquid crystal display - Google Patents

Abstract

PURPOSE: A photosensitive colored composition is provided to respond to high request characteristics in precision image-related apparatuses such as a liquid crystal display and to ensure high contrast and high brightness. CONSTITUTION: A photosensitive colored composition for a color filter includes pigment red 146 and pigment red 254 as red pigment and further yellow pigments. The pigment red 146 has a microparticle phase and the average first particle diameter thereof is 50nm or less, and the crystal particle size is 2~20 nm. 40% or more and less than 100% of the red pigment is the pigment red 146. The yellow pigment is pigment yellow 150 or pigment yellow 138.

Description

Pigment dispersion composition, photosensitive coloring composition, color filter using this, and liquid crystal display device {PIGMENT DISPERSION COMPOSITION, PHOTOSENSITIVE COLORED COMPOSITION, COLOR FILTER USING THE SAME, AND LIQUID CRYSTAL DISPLAY}

The present invention relates to a pigment dispersion composition, a photosensitive coloring composition using the same, an inkjet ink, a photosensitive resin transfer material, a red pixel, a color filter, and a liquid crystal display device.

1. It is proposed to use pigment fine particles as a color material for color filters used in liquid crystal display devices (LCD, etc.) and solid-state imaging devices (CCD, CMOS, etc.). By using a pigment, the light resistance and heat resistance which were the problems at the time of using a dye are improved, and it can be set as the product with high durability. On the other hand, in the color filter using a pigment, contrast improvement becomes a subject and for the realization, the pigment of a smaller particle size is calculated | required. In addition, in view of production aptitude, attempts have been made to lower the viscosity of the photosensitive coloring composition and to improve the dispersion stability. With respect to this point, various photosensitive coloring compositions having favorable characteristics to which improvements have been proposed have been proposed so far (see Patent Document 1, Patent Document 2, etc.).

By the way, with respect to the recent high demand for environmental suitability, energy saving is further demanded also regarding the precision image-related apparatuses including this kind of liquid crystal display device. This is not limited to industrial demands, and the extent to which energy consumption is reduced also greatly affects the purchase trend even in commercial products sold in stores. So-called energy saving (eco) has come to occupy a large position in the performance of this kind of products, along with basic performance such as image reproducibility. For the problem, the luminance represented by the color material used for the red pixel of the color filter is listed as an important development item.

At present, the mixed color material of Pigment Red 177 (PR177) and Pigment Red 254 (PR254), which are mainly used for the red (R) pixels of the color filter, exhibits high contrast, while the Y value (luminance) is lowered. In particular, when the color filter is used in three colors (R, G, B), the luminance of the jack color pixel by the mixed color material is relatively lower than that of the green pixel and the blue pixel. As a result, in the case of a liquid crystal display device, a high output backlight must be used in accordance with the luminance of the red pixel in order to realize sufficient color reproducibility and sharpness of the color image. On the contrary, if the brightness of the red pixel can be made high without reducing the contrast, the brightness of the backlight can be lowered to reduce the power consumption. Specifically, Pigment Red 176 (PR176) having a large specific surface area has been proposed for PR254 for the purpose of improving the luminance and contrast of the red pigment (see Patent Document 3).

2. High performance and high quality are demanded about a color filter, and the improvement of the organic pigment used for the manufacture is tried. Specifically, what is excellent in storage stability in preparation of a pigment dispersion, what is excellent in the contrast of the coating film of the color filter colored pixel part using this, etc. is calculated | required. In order to meet these requirements, the research which small sized and disperse | distributes a pigment particle to the range of 10-100 nm, for example, is vigorously progressing. As a result, the nanometer size makes it possible to make use of the effect produced for the first time and to effectively draw out new characteristics that have not been previously predicted. In addition to the color filter applications described above, research and development are also being conducted in paints, printing inks, electrophotographic toners, inkjet inks, and the like. In particular, the above-mentioned color filters and inkjet inks are coped with for high performance utilizing fine chemical technology, and the results are expected.

Here, the dispersion method of the organic pigment is largely divided into the breakdown method and the liquid phase method, and the breakdown method includes a method of miniaturizing the pigment by various milling methods such as the bead mill method and the salt milling method. Patent Literature 4, Patent Literature 5, and the like have been disclosed in which the pigment fine particles prepared by the breakdown method are utilized for an ink or the like. On the other hand, as a liquid phase method, the reprecipitation method which precipitates a nanoparticle by mixing the pigment solution which melt | dissolved a pigment in the good solvent (1st solvent), and a poor solvent (2nd solvent) is mentioned. In recent years, adding a predetermined high molecular compound as a dispersing agent to the dispersion liquid obtained by this reprecipitation method is proposed (refer patent document 6-patent document 8).

Until now, the pigment fine particles suitable for a high performance display device or a ignition device have been developed in the direction of miniaturizing the pigment fine particles down to the nanometer size by using the breakdown method and the liquid phase method as described above, and providing good dispersibility. come. As a method other than that, there are few examples which consider combining several pigments, for example, and there is little knowledge about the physical property and a color characteristic. Even in view of the red color material applied to the color filter, it has been assumed that PR254 alone or a combination of this and PR177 is considered in consideration of color characteristics as a display device. Among them, it may be proposed to combine Pigment Red 242 (PR242) with PR177 to PR254 for the purpose of improving transparency while maintaining the red color characteristics (see Patent Document 9). However, even with respect to this patent document, the detailed performance of the particle size and color filter of the pigment fine particles is not disclosed, and it is not known whether the high-contrastization and high light resistance of the color filter required in recent years can be satisfied. In particular, when the average particle diameter of the particles is reduced and finely divided in consideration of improving the contrast, the light resistance is inversely lowered. Usually, either must be sacrificed, and compatibility of these characteristics was difficult.

Japanese Patent Publication No. 2007-262378 Japanese Patent Publication No. 2009-84417 Japanese Patent Publication No. 2009-237462 Japanese Patent Publication No. 2007-186681 Japanese Patent Publication No. 2000-160084 International Publication No. WO 2006/121016 Brochure Japanese Patent Publication No. 2004-43776 Japanese Patent Publication No. 2007-119586 Japanese Patent No. 3927872

In view of the above points, the first object of the present invention is to provide a photosensitive coloring composition having both high contrast and high brightness (Y value) that can meet high demand characteristics in precision image-related devices such as liquid crystal displays, which are recently required; It is to provide a red pixel, a color filter, and a liquid crystal display device using the same.

A second object of the present invention is to use a pigment dispersion composition capable of achieving high contrast and high light resistance when using a color filter capable of meeting high demand characteristics in a precision image related device such as a liquid crystal display device recently required, and using the same. An object of the present invention is to provide a colored photosensitive resin composition, an inkjet ink and a photosensitive resin transfer material, a color filter, and a liquid crystal display device.

The problem has been solved by the following means.

(1-1) The photosensitive coloring composition for color filters containing Pigment Red 146 and Pigment Red 254 as a red pigment.

(1-2) The photosensitive coloring composition for color filters of (1-1) which further contains a yellow pigment.

(1-3) In (1-1) or (1-2), the Pigment Red 146 is in a particulate form, the average primary particle size of which is 50 nm or less, and the crystal grain size of 2 to 20 nm. The photosensitive coloring composition for color filters characterized by the above-mentioned.

(1-4) The photosensitive coloring composition for color filters in any one of (1-1)-(1-3) whose 40% or more and less than 100% of a red pigment are said Pigment Red 146 by mass basis. .

(1-5) The photosensitive coloring composition for color filters in any one of (1-1)-(1-4) whose said yellow pigment is Pigment Yellow 150 or Pigment Yellow 138.

(1-6) The photosensitive coloring composition for color filters in any one of (1-1)-(1-5) which uses the organic solvent which contains a polymeric compound further as a medium.

(1-7) It formed using the photosensitive coloring composition for color filters as described in (1-6), The red pixel for color filters characterized by the above-mentioned.

(1-8) The color filter provided with the red pixel as described in (1-7).

(1-9) The color filter as described in (1-8) is provided, The liquid crystal display device characterized by the above-mentioned.

(2-1) A ratio containing two kinds of pigment fine particles of CI Pigment Red 146 and CI Pigment Red 242, wherein the mass of CI Pigment Red 146 accounts for the total mass of CI Pigmetn Red 242 and CI Pigment Red 146 ( CIPR146 / (CIPR146 + CIPR242)) is 0.1 or more and 0.95 or less, and the particle size of the said 2 types of pigment fine particles is 40 nm or less, The pigment dispersion composition characterized by the above-mentioned.

(2-2) The pigment dispersion composition as described in (2-1) whose mass ratio (CIPR146 / (CIPR146 + CIPR242)) of said C. I. Pigment Red 146 is 0.2 or more.

(2-3) The pigment dispersion composition as described in (2-1) or (2-2) containing the polymer compound of the mass mean molecular weights 1000-100000.

(2-4) The pigment dispersion composition according to any one of (2-1) to (2-3), wherein the polymer compound has an acid group in a range of 50 mgKOH / g or more and 200 mgKOH / g or less.

(2-5) Colored pigment photosensitive resin containing the pigment dispersion composition as described in any one of (2-1)-(2-4), a binder, a monomer or an oligomer, and a photoinitiator or a photoinitiator system. Composition.

(2-6) The inkjet ink for color filters containing the pigment dispersion composition as described in any one of (2-1)-(2-4), a binder, and a monomer or an oligomer.

The photosensitive resin transfer material (2-7) provided the photosensitive resin layer containing the coloring photosensitive resin composition of at least (2-5) on a support body.

(2-8) the said pigment produced using the coloring photosensitive resin composition of (2-5), the inkjet ink for color filters of (2-6), and / or the photosensitive resin transfer material of (2-7). A color filter containing pigment fine particles in a dispersion composition.

(2-9) The color filter as described in (2-8) was provided, The liquid crystal display device characterized by the above-mentioned.

Effect of the Invention

The photosensitive coloring composition by the 1st solution means of this invention is able to respond to the high demand characteristic in precision image related apparatuses, such as a liquid crystal display device which are recently requested | required, and when it uses as a color filter, it exhibits both high contrast and high brightness. Exhibits excellent effect. Moreover, the red pixel, the color filter, and the liquid crystal display device using the photosensitive coloring composition which have said characteristic can reduce the power consumption of a backlight, realizing sufficient image reproducibility, and are excellent in environmental suitability.

The pigment dispersion composition by the 2nd solution means of this invention can respond to the high request | requirement characteristic in precision image related apparatuses, such as a liquid crystal display device which are recently requested | required, and exhibits high contrast and high light resistance at the time of setting it as a color filter It shows excellent effect. Moreover, the color filter and liquid crystal display device which were produced by the coloring photosensitive resin composition, the inkjet ink, and the photosensitive resin transfer material using the pigment dispersion composition which have the said characteristic have redness and black vividness (black by blocking the irradiation light from a backlight When the display is used, the black color is deep and dark without leakage of light), and excellent red display performance is obtained even in long-term use.

Below, this invention is demonstrated separately into 1st Embodiment and 2nd Embodiment. In addition, the invention is not limited to and interpreted by the following description, and both embodiments have the same or corresponding special technical features, and the technical relationships are related to these inventions to form a single general invention concept. .

(1st embodiment)

The photosensitive coloring composition especially suitable for the color filter use of this embodiment contains Pigment Red 146 and Pigment Red 254, It is characterized by further containing a yellow pigment preferably.

First, the constraint regarding the conventional color material is demonstrated as follows. PR254 has been widely used as a colorant for color filters because it is a pigment having excellent brightness and high coloring power. On the other hand, PR254 is low in heat resistance after miniaturization, and contrast is reduced when it is used as a coloring coating film. In order to supplement this point, it is generally performed to mix PR177 with high contrast and to make a pigment composition. However, on the contrary, since PR177 has low luminance and coloring power, the content cannot be increased. As a result, there was a limit to the improvement of the performance in both the brightness and the contrast.

According to the present embodiment, the combination of the plurality of pigments described above can realize both the contrast and the luminance at a higher level that were difficult with the conventional colorant (combination of PR254 and PR177). Although there is some unexplained reason for such a remarkable effect, the PR146 microparticles are very close to the absorption peak and the wavelength at which the absorption becomes zero, and the switching between the absorbing light and the transmitted light is clear. I think.

[Pigment]

In this embodiment, Pigment Red 146 and Pigment Red 254 are used as a red pigment. Although the content rate of both is not specifically limited, In consideration of general color tone etc. of a color filter use, it is preferable that PR146 is 10-300 mass parts with respect to 100 mass parts of PR254, and it is more preferable that it is 67-300 mass parts. By using the said both pigments in combination in said range, especially high brightness is obtained in addition to a favorable contrast, and it is preferable. Speaking as the ratio of PR146 which occupies for pigment whole quantity, it is preferable that it is 40 mass% or more and less than 100 mass%, and it is more preferable that it is 50 mass% or more and 80 mass% or less.

In this embodiment, it is preferable to use a combination of a yellow pigment further, and PY150 or PY138 is mentioned as a yellow pigment. Although the content rate of a yellow pigment is not specifically limited, It is preferable that it is 1-30 mass parts with respect to 100 mass parts of PR254, and it is more preferable that it is 1-10 mass parts. By using a yellow pigment in combination in the said range, since the luminance of the photosensitive coloring composition becomes high further, as well as the coloring property as a color material, it is preferable.

10 mass%-70 mass% are preferable with respect to the total solid component, and, as for the total content rate of the pigment in the photosensitive coloring composition of this embodiment, 20 mass%-60 mass% are more preferable, 30 mass%-50 mass mass % Is most preferred. By setting it as the said lower limit or more, the pigment microparticles | fine-particles refine | miniaturized and the surface area increased can be disperse | distributed stably, and below the said upper limit can prevent the fall of the color value by the addition of a pigment derivative. In addition, in this embodiment, using in combination further with the pigment of that excepting the above in the range which does not impair the desired effect is not prevented.

○ pigment fine particles

In this embodiment, 100 nm or less is preferable, as for the average particle diameter of a pigment fine particle (primary particle), 75 nm or less is more preferable, It is especially preferable that it is 50 nm or less. Although there is no special lower limit, it is practical that it is 1 nm or more. In addition, in this embodiment, CV is used as an index which shows the uniformity (monodispersibility) of particle | grains unless there is particular notice in this embodiment. CV is represented by the ratio (σ / L) of the number average particle diameter (L) and the standard deviation (σ) of L. In this embodiment, it is preferable that monodispersity, ie CV, of a pigment fine particle (primary particle) is 30% or less, and it is especially preferable that it is 20% or less. Although the crystal grain diameter of a pigment fine particle in this embodiment is not specifically limited, It is preferable that it is 2 nm or more, and it is more preferable that it is 3 nm or more. Although an upper limit is not specifically limited, It is practical that it is 20 nm or less. As a measuring method of the said particle size and a crystal grain diameter, it measures by the method employ | adopted in the Example unless there is particular notice. Moreover, as for the preferable range of the said organic pigment microparticle, it is preferable that PR146 is the said range at least, and it is more preferable that all the pigment microparticles | fine-particles contained are the said range.

○ grinding

Although the pigment fine particle used for this embodiment does not have a restriction | limiting in particular in the atomization method, It can prepare by breakdown methods, such as a grinding | pulverization method. In that case, it can obtain by mixing various solvents, resin, varnish, etc. as needed and disperse | distributing to a horizontal sand mill, a vertical sand mill, a circular bead mill, an Ato writer, etc. Moreover, what grind | pulverized the organic pigment with inorganic salt using kneading | mixing apparatus, such as a kneader, and the salt milling process so that the primary particle diameter of an organic pigment may become more fine can also be used. The specific polymer compound or other pigment dispersant described later may be dispersed after mixing all the components, but first, only the pigment, such as the pigment and the specific polymer compound (specific polymer), or the pigment and the pigment dispersant is dispersed, and then other components are dispersed. You may add and redisperse. Moreover, you may add at the time of an atomization process.

In addition, before dispersing with a horizontal sand mill, a vertical sand mill, a circular bead mill, an atorite, etc., predispersion using a meat mixer such as a kneader and three roll mills, solid dispersion by two roll mills or the like, or basicity to a pigment The synergy and / or dispersant having a group may be treated. Moreover, dispersers and mixers, such as a high speed mixer, a homo mixer, a ball mill, a roll mill, a mill mill, an ultrasonic disperser, can be used.

○ reprecipitation

In the present embodiment, the organic pigment particles have compatibility with the solution of the organic pigment in which the organic pigment is dissolved in a good solvent (hereinafter may be referred to as a first solvent) and the good solvent. What was produced by mixing the solvent used as a poor solvent (Hereinafter, this may be called a 2nd solvent) can be used. For example, Japanese Unexamined-Japanese-Patent No. 2008-291193, Japanese Unexamined-Japanese-Patent No. 2007-262378, 2004-43776, 2008-231415, etc. can be referred.

[Polymerizable Compound]

In this embodiment, you may use a polymeric compound. As a polymeric compound, the addition polymeric compound which has at least 1 ethylenically unsaturated double bond can be mentioned, for example. Specifically, it is selected from compounds which have at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is well known in the said industrial field, and can use these without a restriction | limiting in this embodiment. These may be, for example, any of the chemical forms of monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides and their (co) Polymers are listed, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds and their (co) polymers. Moreover, addition reaction, monofunctional or polyfunctional carboxylic acid of unsaturated carboxylic acid ester or amide which has nucleophilic substituent, such as a hydroxyl group, an amino group, and a mercapto group, and monofunctional or polyfunctional isocyanate, or epoxys Dehydration condensation reactants and the like are also preferably used. Moreover, the addition reaction product of unsaturated carboxylic acid ester or amides which have electrophilic substituents, such as an isocyanate group and an epoxy group, and monofunctional or polyfunctional alcohol, amines, and thiols, and also detachable substituents, such as a halogen group and a tosyloxy group, can be used. Substituted reactants of unsaturated carboxylic acid esters or amides having monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

As a specific example of the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, it is an acrylic ester, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3- butanediol diacrylate, tetramethylene glycol diacryl Rate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1, 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol tree Acrylic ray And sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate, and the like.

Moreover, as methacrylic acid ester, for example, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, Ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate Acrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p -(Methacryloxyethoxy) phenyl] dimethylmethane etc. are mentioned.

As itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaco Nate, sorbitol tetrataconate, and the like are also crotonic acid esters, for example, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, and the like. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. are also maleic acid esters, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate Sorbitol tetramalate, etc. It is exemplified.

As examples of other esters, for example, aliphatic alcohol esters described in JP-A-51-47334, JP-A-57-196231, JP-A-59-5240, and JP-A-JP The thing which has the aromatic skeleton of Unexamined-Japanese-Patent No. 59-5241, Unexamined-Japanese-Patent No. 2-226149, containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. is also used preferably. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the monomer of the amide of an aliphatic polyhydric amine compound and an unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As an example of the other preferable amide monomer, what has the cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 can be mentioned.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable, As this specific example, polyisocyanate which has two or more isocyanate groups in 1 molecule as described in Unexamined-Japanese-Patent No. 48-41708, for example. The vinyl urethane compound etc. which contain two or more polymerizable vinyl groups in 1 molecule which added the vinyl monomer containing the hydroxyl group represented by following General formula (A) to a compound are mentioned.

CH ₂ = C (R) COOCH ₂ CH (R ′) OH... (A)

[In Formula (A), R and R 'each independently represent H or CH _3. ]

About these polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of the photosensitive coloring composition. For example, a structure with many unsaturated group content per molecule is preferable from a viewpoint of a sensitivity, and in many cases, bifunctional or more is preferable. Moreover, from a viewpoint of raising the intensity | strength of a colored cured film, a trifunctional or more thing is good, and also by using together the thing of another functional water and another polymerizable group (for example, acrylic acid ester, methacrylic acid ester, a styrene type compound, a vinyl ether type compound) The method of adjusting both sensitivity and intensity is also effective. In addition, the compatibility and dispersibility with other components (for example, a photopolymerization initiator, a colorant (pigment), a binder polymer, etc.) contained in the photosensitive coloring composition are also important factors. Compatibility may be improved by using a low-purity compound or using 2 or more types together. Moreover, a specific structure can also be selected from a viewpoint of improving adhesiveness with hard surfaces, such as a support body.

There is no restriction | limiting in particular as content (in the case of 2 or more types, total content) of the polymeric compound in the total solid of the photosensitive coloring composition, 10 mass%-80 mass% are preferable from a viewpoint which acquires the effect of this embodiment more effectively. 15 mass%-75 mass% are more preferable, and 20 mass%-60 mass% are especially preferable.

[Photopolymerization Initiator]

The photosensitive coloring composition of this embodiment may contain the photoinitiator. This is not necessarily necessary in the case of the color resist of the type used as inkjet ink, and it is preferable to set it as the color resist containing a polymerization initiator in the coating method mentioned later. There is no restriction | limiting in particular if a photoinitiator can superpose | polymerize the above-mentioned polymeric compound, It is preferable to select from a viewpoint of a characteristic, start efficiency, absorption wavelength, availability, cost, etc.

As the photopolymerization initiator, for example, at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a ropin dimer, a benzophenone compound, an acetophenone compound, and Derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP2004-295116A. Especially, an oxime type compound is preferable at the point of rapid polymerization reaction.

There is no restriction | limiting in particular as said oxime type compound (henceforth an "oxime type photoinitiator"), For example, Unexamined-Japanese-Patent No. 2000-80068, WO 02/100903 A1, Unexamined-Japanese-Patent No. 2001-233842, etc. Listed oxime compounds are listed.

Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4- (Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione, 2 -(O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane On, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) -9H- Le carbazole-3-yl] ethanone are listed the like. However, it is not limited to these.

Among them, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl]-in terms of obtaining a good pattern of a shape (particularly, a rectangular shape of a pattern in the case of a solid-state imaging device) with a smaller exposure dose. Oxime-O-acyl, such as 1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone System compounds are particularly preferable, and specific examples thereof include CGI-124, CGI-242 (above, manufactured by Ciba Specialty Chemicals KK), and the like.

In addition, in this embodiment, the compound represented by following General formula (1) as an oxime compound is more preferable from a viewpoint of a sensitivity, stability with time, and coloring at the time of post-heating.

In said general formula (1), R and X respectively independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

As R, an acyl group is preferable at the point of high sensitivity, and an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are specifically, preferable.

A is an alkylene group substituted with an unsubstituted alkylene group, an alkyl group (eg, methyl group, ethyl group, tert-butyl group, dodecyl group) and alkenyl group (eg For example, an alkylene group substituted with a vinyl group or an allyl group, or an aryl group (for example, a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) Substituted alkylene groups are preferred.

As Ar, a substituted or unsubstituted phenyl group is preferable at the point which raises a sensitivity and suppresses coloring by the time of heating. In the case of a substituted phenyl group, as this substituent, halogen groups, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, are preferable, for example.

X may be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent in view of solvent solubility and the absorption efficiency improvement of a long wavelength region. The alkoxy group, the aryloxy group which may have a substituent, the alkylthioxy group which may have a substituent, the arylthioxy group which may have a substituent, and the amino group which may have a substituent are preferable.

Moreover, the integer of 1-2 is preferable in n in General formula (1).

Moreover, you may use other well-known photoinitiator of Paragraph of Unexamined-Japanese-Patent No. 2004-295116 for the photosensitive coloring composition of this embodiment other than said photoinitiator. A photoinitiator can be contained individually by 1 type or in combination of 2 or more types. As for content (in the case of 2 or more types, total content) of the photoinitiator in the total solid of the photosensitive coloring composition, 3 mass%-20 mass% are preferable from a viewpoint of obtaining the effect of this embodiment more effectively, 4 mass%-19 Mass% is more preferable, and 5 mass%-18 mass% are especially preferable.

[Organic Solvent]

It is preferable that the photosensitive coloring composition of this embodiment uses an organic solvent as a medium. The organic solvent is basically not particularly limited as long as it forms a continuous phase that can satisfy the solubility of each component to coexist and the coating properties when the photosensitive coloring composition is used. In particular, the organic solvent is selected in consideration of the solubility, coating property, and safety of the binder. It is desirable to. As an organic solvent, it is preferable that it is at least 1 sort (s) chosen from the group which consists of the following ester compound (s) solvent, an ether compound (s) solvent, and a hydrocarbon aromatic hydrogen compound (s) solvent.

As the organic solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically methyl methoxyacetate, methoxyacetate, methoxyacetate butyl, ethoxyacetate, ethyl ethoxyacetate) And 3-oxypropionate alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-) Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) and 2-oxypropionic acid alkyl esters (for example, 2-oxypropionic acid). Methyl, 2-oxypropionate, propyl 2-oxypropionate and the like (specifically, 2-methoxypropionate methyl, 2-methoxypropionate, 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, etc.)), methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate (specifically methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2, etc.). -Ethyl methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc. are mentioned.

Moreover, as ether, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.

As ketones, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example.

As aromatic hydrocarbons, toluene, xylene, etc. are mentioned preferably, for example.

When these organic solvents contain the solubility and alkali-soluble binder of each component mentioned above, it is also preferable to mix 2 or more types from a viewpoint of the solubility, improvement of a coated surface shape, etc. In this case, Especially preferably, 3-ethoxy propionate methyl, 3-ethoxy propionate ethyl, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy propionate methyl, 2-heptanone , Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

As content in the photosensitive coloring composition of an organic solvent, the quantity which becomes 10 mass%-80 mass% of the total solid content concentration in a composition is preferable, and the quantity which becomes 15 mass%-60 mass% is more preferable.

[Other Ingredients]

○ alkali-soluble binder

The photosensitive coloring composition of this embodiment may further contain alkali-soluble binder in the range which does not impair the effect further to said each component. An alkali-soluble binder is not specifically limited except having alkali solubility, Preferably, it can select from a viewpoint of heat resistance, developability, water availability, etc .. The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed in a weak alkaline aqueous solution. As such a linear organic polymer, a polymer having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, as described in the respective publications of 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048; Maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and likewise, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

As alkali-soluble binder in this embodiment other than what was mentioned above, what added the acid anhydride to the polymer which has a hydroxyl group, etc., polyhydroxy styrene resin, polysiloxane resin, poly (2-hydroxyethyl ( Meta) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like. In addition, the linear organic polymer may be a copolymer of a monomer having hydrophilicity. Examples include alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycerol (meth) acrylates, (meth) acrylamides, N-methylol acrylamides, secondary or tertiary alkylacrylamides, di Alkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) An acrylate, a branched or linear propyl (meth) acrylate, a branched or linear butyl (meth) acrylate, a phenoxyhydroxypropyl (meth) acrylate, etc. are mentioned. In addition, the hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphate ester group, quaternary ammonium base group, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and group derived from salt thereof, morpholine ethyl group and the like. Monomers are also useful.

Moreover, an alkali-soluble binder may have a polymeric group in a side chain in order to improve crosslinking efficiency, For example, the polymer etc. which contain an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are also useful. Examples of the polymer containing the polymerizable group include commercially available products KS Resist-106 (trade name, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), Cyclomer P series (trade name, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), And the like. In addition, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane, epichlorohydrin, etc. are also useful in order to raise the strength of a hardened film.

Among these various alkali-soluble binders, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins and acryl / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and acrylic resins, Acrylamide type resin and acryl / acrylamide copolymer resin are preferable.

As said acrylic resin, KS Resist-106 (OSAKA ORGANIC CHEMICAL INDUSTRY) of the copolymer which consists of a monomer chosen from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., or a commercial item LTD.), Cyclomer P series (product of DAICEL CHEMICAL INDUSTRIES, LTD.) And the like.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by the GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and more preferably 2000 to 1 × 10 ⁵ . The polymer of 5000-5 * 10 <^4> is especially preferable.

○ crosslinking agent

The hardness of the colored cured film formed by hardening | curing the photosensitive coloring composition using a crosslinking agent supplementally to the photosensitive coloring composition of this embodiment can also be made higher. As a crosslinking agent, if it hardens | cures a film by crosslinking reaction, there will be no limitation in particular, For example, the melamine compound substituted by the at least 1 substituent chosen from (a) epoxy resin, (b) methylol group, an alkoxy methyl group, and an acyloxymethyl group. And phenol compounds, naphthol compounds or hydroxyanthracene compounds substituted with at least one substituent selected from, guanamine compounds, glycoluril compounds or urea compounds, (c) methylol groups, alkoxymethyl groups and acyloxymethyl groups. Especially, polyfunctional epoxy resin is preferable. For details, such as the specific example of a crosslinking agent, description of Paragraph [0134]-[0147] of Unexamined-Japanese-Patent No. 2004-295116 can be referred.

○ Other additives

To the photosensitive coloring composition, various additives, for example, fillers, polymer compounds other than those described above, surfactants such as nonionics, cationics and anionics, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like may be blended. Can be. As these additives, the thing of Paragraph [0155]-[0156] of Unexamined-Japanese-Patent No. 2004-295116 can be mentioned. In the photosensitive coloring composition of this embodiment, the sensitizer and light stabilizer of Paragraph [0078] of Unexamined-Japanese-Patent No. 2004-295116, and the thermal polymerization inhibitor of Paragraph [0081] of the same publication can be contained.

Moreover, when promoting alkali solubility of a non-exposure area | region and further improving developability of a photosensitive coloring composition, addition of organic carboxylic acid, preferably low molecular weight organic carboxylic acid of molecular weight 1000 or less to the said composition. It is preferable to carry out.

Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic 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, hydratropinic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid and umbelic acid. .

[Preparation and Characteristics of Photosensitive Coloring Composition]

The photosensitive coloring composition of this embodiment can be prepared by mixing the above-mentioned essential component and arbitrary components as needed. Moreover, in order to improve the dispersibility of a pigment, the pigment dispersion liquid which disperse | distributed the pigment previously is prepared, and you may prepare the photosensitive coloring composition using this pigment dispersion liquid.

The photosensitive coloring composition of this embodiment is preferable because it is excellent in storage stability, the light resistance as an advantage by using a pigment becomes further high, and can form the colored cured film excellent as a color material for color filters especially produced industrially. For example, it is useful for forming colored pixels, such as a color filter used for a liquid crystal display element (LCD) and a solid-state image sensor (for example, CCD, CMOS, etc.). Moreover, it can use suitably as a manufacturing use of printing ink, inkjet ink, and a coating material. Moreover, it can use suitably for coloring pixel formation for liquid crystal display elements, such as CCD and CMOS.

[Color filter and its manufacturing method]

○ Coating method

In the manufacturing method of a color filter, the photosensitive coloring composition mentioned above can be used. As a manufacturing method which concerns on the said embodiment, the said photosensitive coloring is carried out by apply | coating the above-mentioned photosensitive coloring composition on a base material (support body or temporary support body), and forming a photosensitive coloring composition layer (henceforth an application process.) And the said photosensitive coloring through a mask. After exposing a composition layer, it develops and forms a coloring pattern (henceforth an exposure and development process.). Hereinafter, the coating step and the exposure and development step will be described.

ㆍ coating process

In a coating process, the photosensitive coloring composition is apply | coated on a support body by coating methods, such as rotational coating, casting | flow_spread coating, and roll application | coating. Prebaking is performed to the apply | coated film | membrane, and the photosensitive coloring composition layer is formed. As thickness of the formed photosensitive coloring composition layer, the range of 1.0 micrometer-5.0 micrometers is preferable, Especially the range of 1.0 micrometer-4.0 micrometers is more preferable from the viewpoint of thinning and color reproducibility of the color filter for liquid crystal display elements, 1.0 micrometer- The range of 3.0 micrometers is more preferable.

Examples of the support include soda glass, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, and photoelectric conversion element substrates, for example, silicon substrates, and the like, used in imaging devices and the like. And complementary metal oxide semiconductor (CMOS) substrates. These board | substrates may be provided with the black stripe which isolate | separates each pixel. In addition, a lower coating layer may be formed on these supports to improve adhesion to the upper layer, to prevent diffusion of materials, or to planarize the surface.

Exposure process

Subsequently, exposure through a mask is performed on the photosensitive coloring composition layer formed on the support. As light or radiation which can be applied to this exposure, ultraviolet rays such as g-ray, h-ray and i-ray are preferable. Although exposure may be performed by any of a proximity method, a mirror projection method, and a stepper method, it is preferable to perform exposure especially by a stepper method (reduced projection exposure method using a reduction projection exposure machine). The stepper method is to form a pattern by performing exposure while varying the exposure amount stepwise, and when the stepper exposure is performed, the rectangularity of the pattern can be particularly improved. Moreover, as an exposure apparatus used for stepper exposure, i line | wire stepper (brand name: FPA-3000i5 +, cannon Corporation make) etc. can be used, for example. Moreover, there is no restriction | limiting in particular as an exposure amount at the time of exposure, 50mJ / cm <2> -1000mJ / cm <2> is preferable.

Development Process

Then, image development is performed with respect to the photosensitive coloring composition layer after exposure. Development can be performed using a developing solution. As a developing solution, as long as it melt | dissolves the uncured part (unexposed part) of the photosensitive coloring composition layer, and does not melt a hardened part (exposed part), any can be used. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used. As an organic solvent, the above-mentioned organic solvent used when preparing the photosensitive coloring composition is mentioned. As alkaline aqueous solution, the alkaline aqueous solution which melt | dissolves an alkaline compound so that concentration may be 0.001 mass%-10 mass%, preferably 0.01 mass%-1 mass% is preferable, for example. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like. In addition, when alkaline aqueous solution is used as a developing solution, generally washing with water is performed after image development.

ㆍ Others (heating, etc.)

As mentioned above, a coloring pattern can be formed by going through an application | coating process and an exposure and development process. You may further heat-process to the obtained coloring pattern. The colored pattern formed can be further cured by heating (so-called postbaking). The heat treatment can be performed by, for example, a method capable of heating a pattern such as a hot plate, various heaters, an oven, and the like.

As temperature of heat processing, 160 degreeC-260 degreeC is preferable at the point which hardens efficiently, and 180 degreeC-220 degreeC is more preferable. Although the time of heat processing changes with heating temperature, it is generally preferable to carry out for 3 to 10 minutes.

In the manufacturing method of the said color filter, a color filter which has the coloring pattern (pixel) of the desired number of colors can be obtained by repeating a coating process, an exposure and image development process, and a heating process according to a desired number of colors as needed. .

○ Inkjet method

In this embodiment, you may produce a color filter by the inkjet method. Although it does not specifically limit as this embodiment as this inkjet ink, For example, the method of Unexamined-Japanese-Patent No. 2002-201387, etc. can be used preferably. It is preferable that the said inkjet ink does not use a photoinitiator or a photoinitiator system as said photosensitive coloring composition.

For inkjet inks, the ink temperature is preferably controlled so that the variation in viscosity is within ± 5%. It is preferable that the viscosity at the time of injection is 5-25 mPa * s, It is more preferable that it is 8-22 mPa * s, It is especially preferable that it is 10-20 mPa * s (In this embodiment, a viscosity is not specifically mentioned). Value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of the component to be contained in the ink. The said viscosity can be measured by normal apparatuses, such as a conical flat rotational viscometer and an E-type viscometer, for example.

In addition, it is preferable that the surface tension of the ink at the time of injection is 15-40 mN / m from the viewpoint of improving the flatness of the pixel (in this embodiment, the surface tension is a value at 23 ° C unless otherwise specified). . More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. Surface tension can be adjusted by addition of surfactant and the kind of solvent. The surface tension is measured by, for example, a surface tension measuring device (Cyowa Interface Science Co., Ltd., CBVP-Z) or a fully automatic balance type electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the platinum plate method using.

As the jet of the color filter inkjet ink, a method of controlling the electric field by continuously spraying charged ink, a method of intermittently injecting ink using a piezoelectric element, and a method of intermittently ejecting using the foam by heating the ink Various methods, such as these, can be employ | adopted. In addition, regarding the inkjet method used for forming each pixel, conventional methods such as a method of thermosetting ink, a photocuring method, and a method of forming a transparent aqueous phase layer on a substrate in advance and then performing the method can be used.

In this embodiment, it is preferable to make a partition beforehand and to provide ink to the part enclosed by the said partition, before forming a pixel using the inkjet ink for color filters. Any one of these partitions may be used. However, in the case of producing a color filter, the partitions are preferably partitions having a light shielding function having a black matrix function (hereinafter, also referred to simply as "blocks"). The partition wall can be produced by the same material and method as those of the usual black matrix for color filters.

Then, it is preferable to perform the heat processing as described in the term of the above-mentioned "heating process" and to solidify the layer of the jetted inkjet ink.

○ color filter performance

Since the color filter (color filter of this embodiment) obtained by the manufacturing method of the color filter of this embodiment uses the photosensitive coloring composition of this embodiment, it becomes excellent in light resistance. Therefore, the color filter of this invention can be used for solid-state image sensors, such as a liquid crystal display element and a CCD.

[Liquid Crystal Display Element]

When the color filter of this invention is used for television use, the chromaticity of all the monochromatic colors of red (R), green (G), and blue (B) by an F10 light source is the value shown in the following table (hereinafter, in this invention, It is preferable that it is a range within 5 within the difference ((DELTA) E) from "the target chromaticity."

In the present invention, the chromaticity is measured by a microscopic spectrophotometer (OLYMPUS CORPORATION; OSP100 or 200 [trade name]), calculated as a result of the F10 light source field of view 2 degrees, and represented by the xyY value of the xyz colorimeter. The difference from the target chromaticity is represented by the color difference of the La ^* b ^* color system.

It is preferable that the liquid crystal display device provided with the color filter of this invention is high in contrast, excellent in descriptive power, such as black clarity, and especially VA system. It can also be used suitably also as a large liquid crystal display device, such as a display for notebook PCs, a television monitor, etc. Moreover, the color filter of this invention can be used for a CCD device, and shows the outstanding performance.

(2nd embodiment)

The pigment dispersion composition of this embodiment is characterized by containing two pigment fine particles of C. I. Pigment Red 146 and C. I. Pigment Red 242. According to this embodiment, when it is set as a color filter by the combination of 2 types of pigment fine particles mentioned above, it can implement | achieve both high contrast and high light resistance at the level high enough that it was difficult to implement with conventional combination of PR254 and PR177. . Although the reason for showing such a remarkable effect is unexplained, the micronized pigment because energy transfer between the particulated PR146 and the particulated PR242 occurs when light is irradiated, and the decomposition reaction due to light absorption is suppressed. Nevertheless, it is considered that the light resistance is remarkably improved.

[Pigment]

In this embodiment, Pigment Red 146 and Pigment Red 242 are used as a red pigment. Although the content rate of both is not specifically limited, The ratio (PR146 / PR146 + PR242) with respect to both pigments of PR146 is preferably 0.1 or more and 0.95 or less, more preferably 0.2 or more and 0.95 or less, and particularly preferably 0.4 or more and 0.95 or less. Do. By using the said both pigments in combination in the said range, general color characteristics of a color filter use are satisfy | filled, and especially high light resistance is obtained in addition to favorable contrast, and it is preferable. In addition, in this embodiment, it is not prevented to contain pigment microparticles and dyes other than the above in a composition in the range of the effect, and to use.

10 mass%-70 mass% are preferable with respect to the total solid component, and, as for the total content rate of the pigment in the pigment dispersion composition of this embodiment, 20 mass%-60 mass% are more preferable, 30 mass%-50 mass mass % Is most preferred. By setting it as the said lower limit or more, the pigment microparticles | fine-particles refine | miniaturized and the surface area increased can be disperse | distributed stably, and below the said upper limit can prevent the fall of the color value by the addition of a pigment derivative. In addition, in this embodiment, using in combination further with the pigment of that excepting the above in the range which does not impair the desired effect is not prevented.

Pigment Fine Particles

In this embodiment, the average particle diameter of pigment microparticles | fine-particles (primary particle) is 40 nm or less. Maintaining light resistance in such a refined region is particularly difficult, and the effect of the present embodiment is remarkably exhibited, which is preferable. Although there is no minimum in particular, it is practical that it is 1 nm or more. In addition, unless otherwise indicated in this embodiment, CV is used as an index which shows the uniformity (monodispersibility) of particle | grains. CV is represented by the ratio (σ / L) of the number average particle diameter (L) and the standard deviation (σ) of L. In this embodiment, it is preferable that monodispersity, ie CV, of pigment microparticles | fine-particles (primary particle) is 30% or less, and it is especially preferable that it is 20% or less. Although the crystal grain diameter of a pigment fine particle in this embodiment is not specifically limited, It is preferable that it is 2 nm or more, and it is more preferable that it is 3 nm or more. Although an upper limit is not specifically limited, It is practical that it is 20 nm or less. As a measuring method of the said particle diameter and a crystal grain diameter, it measures by the method employ | adopted in the Example unless there is particular notice. Moreover, as for the preferable range of the said organic pigment microparticle, it is preferable that PR146 is the said range at least, and it is more preferable that all the pigment microparticles | fine-particles contained are the said range.

ㆍ grinding method

Although the pigment microparticles | fine-particles used by this embodiment do not have a restriction | limiting in particular in the atomization method, It can prepare by breakdown methods, such as a grinding | pulverization method. In this case, various solvents, resins, varnishes, and the like may be mixed and dispersed in a horizontal sand mill, a vertical sand mill, a circular bead mill, an atomizer, or the like as necessary. Moreover, what grind | pulverized an organic pigment with an inorganic salt using kneading apparatuses, such as a kneader, and performed salt milling process so that the primary particle diameter of an organic pigment may become finer may be used. Although the specific polymeric compound and other pigment dispersants mentioned later may disperse | distribute after mixing all the components, only the pigments, such as a pigment and a specific polymeric compound (specific polymer), or only a pigment and a pigment dispersant are disperse | distributed first, and then another component You may add and disperse again. Moreover, you may add at the time of an atomization process.

In addition, before dispersing with a horizontal sand mill, a vertical sand mill, an annular bead mill, an atomizer, and the like, a solid dispersion or a basic group to a pigment by pre-dispersion using a meat mixer such as a kneader or three roll mills, two roll mills, or the like You may perform the process of the synergy and / or dispersing agent which have. Moreover, dispersers and mixers, such as a high speed mixer, a homo mixer, a ball mill, a roll mill, a mill mill, an ultrasonic disperser, can be used.

Reprecipitation

In the present embodiment, the organic pigment particles have compatibility with the solution of the organic pigment in which the organic pigment is dissolved in a good solvent (hereinafter may be referred to as a first solvent) and the good solvent. What was produced by mixing the solvent used as a poor solvent (Hereinafter, this may be called a 2nd solvent) can be used. For example, Japanese Unexamined-Japanese-Patent No. 2008-291193, Japanese Unexamined-Japanese-Patent No. 2007-262378, 2004-43776, 2008-231415, etc. can be referred.

[Polymer dispersant]

In this embodiment, it is preferable to contain the polymer compound of the mass mean molecular weights 1000-100000 in the dispersion prepared by the grinding | pulverization method or the reprecipitation method as mentioned above, and it is more preferable to contain the high molecular compound of the mass mean molecular weights 5000-70000. Do. At this time, it is preferable to remove a solvent and replace with a predetermined organic solvent etc. about the dispersion obtained by the reprecipitation method. At this time, in order to improve the dispersibility of a pigment further, dispersing agents, such as a specific pigment dispersing agent and surfactant, can also be added unless the effect of this embodiment is impaired. In addition, you may use the dispersing agent used here in the reprecipitation method mentioned above and coexist at the time of precipitation of pigment microparticles | fine-particles, for example. In addition, in this embodiment, unless it mentions especially molecular weight, it means a mass mean molecular weight, and molecular weight and dispersion degree mean the value measured by the following measuring method.

(Measurement Method of Molecular Weight and Dispersion of Polymer Compound)

Molecular weight and dispersion degree are measured using GPC (gel filtration chromatography) method unless otherwise stated. The gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit. Examples thereof include gels composed of styrene-divinylbenzene copolymers. It is preferable to use two to six columns. Examples of the solvent used include ether solvents such as tetrahydrofuran and amide solvents such as N-methylpyrrolidinone, but ether solvents such as tetrahydrofuran are preferable. It is preferable to perform a measurement in the range whose solvent flow rate is 0.1-2 mL / min, and it is most preferable to carry out in the range which is 0.5-1.5 mL / min. By performing the measurement within this range, no load is applied to the device, and the measurement can be performed more efficiently. It is preferable to perform measurement temperature at 10-50 degreeC, and it is most preferable to carry out at 20-40 degreeC.

Specific conditions of molecular weight measurement are shown below.

Device: HLC-8220 GPC (manufactured by TOSOH Corporation)

Detector: Differential Refractometer (RI Detector)

Precolumn: TSK GUARD COLUMN MP (XL)

          6 mm x 40 mm (manufactured by TOSOH Corporation)

Sample side column: Directly connect two of the following (all manufactured by TOSOH Corporation)

ㆍ TSK-GEL Multipore-HXL-M 7.8mm × 300mm

Reference side column: same for sample side column

Bath temperature: 40 ℃

Mobile layer: tetrahydrofuran

Sample-side mobile bed flow rate: 1.0 mL / min

Moving bed reference flow rate: 0.3 mL / min

Sample concentration: 0.1% by mass

Sample injection volume: 100 μl

Data collection time: 16 to 46 minutes after sample injection

Sampling Pitch: 300msec

Moreover, it is preferable that the said high molecular compound has an acidic group, and acid value is 50 mgKOH / g or more and 200 mgKOH / g or less, and it is more preferable that it is 70 mgKOH / g or more and 160 mgKOH / g or less. By setting it as such a range, the production suppression effect of the precipitate in a developing solution can be exhibited and the cohesion force of a secondary aggregate can be weakened effectively. Hereinafter, the dispersing agent A and the dispersing agent B which are preferable examples of the said high molecular compound are demonstrated.

(Dispersant A)

You may add dispersing agents, such as a pigment dispersing agent and surfactant, to the pigment dispersion of this embodiment in order to improve the dispersibility of a process pigment further. As a dispersant (pigment dispersant), a polymeric dispersant [for example, polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, ( Meta) acrylic copolymers, naphthalenesulfonic acid formalin condensates] and polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanolamines, pigment derivatives, and the like. Polymeric dispersants may be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers in the structure thereof.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. Therefore, terminal modified polymers, graft polymers, and block polymers having anchor sites on the pigment surface can be listed as preferable structures. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface. The polymer dispersant adsorbs on the surface of the pigment in the dispersing process and acts to prevent reagglomeration. Therefore, block type polymers, graft type polymers, and terminal modified polymers having anchor sites on the pigment surface can be enumerated as preferable structures. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Graft Type Polymer

Although it does not restrict | limit especially about a graft type polymer, The compound which made the polyalkylene imine and the polyester compound react as described in Unexamined-Japanese-Patent No. 54-37082, 61-174939, etc., Unexamined-Japanese-Patent No. 9 The compound which modified the amino group of the side chain of polyallylamine of Unexamined-Japanese-Patent No. 169821 with polyester, the polyester polyol addition polyurethane of Unexamined-Japanese-Patent No. 60-166318, etc. are mentioned preferably, Furthermore, Unexamined-Japanese-Patent No. Graft-type polymers containing a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component may also be preferably listed, as described in Japanese Patent Application Publication No. 9-171253 and the chemistry and industry of macromonomers (IPC Publishing, 1989). Moreover, the graft type polymer which has the organic pigment | dye part of Unexamined-Japanese-Patent No. 2003-238837 is preferable at the point which adsorb | sucks to a pigment and gives favorable dispersibility. The branched portion of the graft polymer is preferably polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, or the like, but a graft polymer having a polycaprolactone chain is more preferable. Commercially available products of the graft polymer include Solsperse 24000, Solserse 28000, Solsperse 32000, Solsperse 38500, Solsperse 39000, Solsperse 55000 (above Lubrizol), Disperbyk-161, Disperbyk-171, Disperbyk-174 (above, BYK Chemie) [All brand names] are listed.

Terminal modified polymer

As the terminal-modified polymer, for example, the polymers described in Japanese Patent Application Laid-Open No. 9-77994, Japanese Patent Application Laid-Open No. 2002-273191, Japanese Patent Application Laid-Open No. 2007-277514, Japanese Patent Application Laid-Open No. 2007-140487, and the like. The polymer which has a functional group at the terminal can be mentioned.

Block type polymer

Although it does not specifically limit as a block type polymer, The block type polymer which consists of a pigment adsorption block and the block which is not adsorb | sucked by a pigment is mentioned. Although it does not specifically limit as a monomer which comprises a pigment adsorption block, For example, the monomer which has a functional group which can be adsorb | sucked to a pigment is mentioned. Specifically, the monomer which has an organic pigment | dye structure or heterocyclic structure, the monomer which has an acidic group, the monomer which has a basic nitrogen atom, etc. can be mentioned. As a monomer which has an organic pigment | dye structure or a heterocyclic structure, the organic pigment | dye skeleton, maleimide derivative, etc. which were described, for example in Unexamined-Japanese-Patent No. 2003-238837 are mentioned. It is also possible to use a commercial item as a block polymer. As a specific example, Disperbyk-2000, Disperbyk-2001 (above, BYK Chemie), EFKA 4330, EFKA 4340 (above, EFKA), etc. (all are brand names) can be mentioned.

Although the usage-amount of the dispersing agent A in a dispersion is not specifically limited, When using as a color material with a color filter, for example, it is preferable that it is 10-400 mass parts with respect to 100 mass parts of pigments, and it is more preferable that it is 20-200 mass parts. Do.

(Dispersant B)

In this embodiment, the polymeric compound containing the at least 1 sort (s) of repeating unit chosen from the repeating unit represented by either of following General formula (I) and General formula (II) may be called "dispersant B." It is preferable to contain).

In Formulas (I) and (II), R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ²¹ and X ²² each independently represent -CO- and -C (= 0). O-, -CONH-, -OC (= O)-or a phenylene group, L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group, and A ²¹ and A ²² each independently represent a monovalent An organic group is represented, ma and na respectively independently represent the integer of 2-8, p and q each independently represent the integer of 1-100.

R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group. As monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, A C1-C8 alkyl group is more preferable, A C1-C4 alkyl group is especially preferable. When the alkyl group has a substituent, for example, as the substituent, a hydroxy group, an alkoxy group (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), methoxy group, ethoxy group, cyclohex And siloxy groups. Specifically as a preferable alkyl group, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, a cyclohexyl group, 2-hydroxyethyl group, 3-hydroxy A hydroxypropyl group, 2-hydroxypropyl group, and 2-methoxyethyl group are mentioned. As R <^21> , R <^22> , R <^24> and R <^{25>, a} hydrogen atom is preferable and R <^23> and R <^26> are the most preferable also at the point of the adsorption efficiency on a pigment surface as a hydrogen atom or a methyl group.

X ²¹ and X ²² each independently represent a —CO—, —C (═O) O—, —CONH—, —OC (═O) — or a phenylene group. Especially, -C (= O) O-, -CONH-, and a phenylene group are preferable from a viewpoint of adsorption to a pigment, and -C (= O) O- is the most preferable.

L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group. As a divalent organic coupling group, the bivalent organic coupling group which consists of a substituted or unsubstituted alkylene group and the partial structure containing the said alkylene group and a hetero atom or a hetero atom is preferable. Here, as an alkylene group, a C1-C12 alkylene group is preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Especially, an oxygen atom and a nitrogen atom are preferable. As a preferable alkylene group, a methylene group, an ethylene group, a propylene group, trimethylene group, tetramethylene group is mentioned specifically ,. When an alkylene group has a substituent, the said hydroxyl group etc. are mentioned, for example. The divalent organic linking group has a partial structure containing a hetero atom or a hetero atom selected from -C (= 0)-, -OC (= 0)-, and -NHC (= 0)-at the terminal of the alkylene group. In connection with the adjacent oxygen atom through the heterostructure or the partial structure containing a hetero atom, it is preferable at the point of adsorption to a pigment. Here, an adjacent oxygen atom means the oxygen atom couple | bonded with L <^21> in general formula (I) and L <^22> in general formula (II) by the side chain terminal side.

As A ²¹ and A ²² , in terms of dispersion stability and developability, a linear chain having 1 to 20 carbon atoms, a branched phase having 3 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms Groups selected from are preferred, more preferably a straight chain of up to 4 to 15 carbon atoms, a branched up to 4 to 15 carbon atoms, and a cyclic alkyl group of up to 6 to 10 carbon atoms, More preferable is a group selected from linear alkyl groups having up to 6 to 10 carbon atoms and branched alkyl groups having up to 6 to 12 carbon atoms.

ma and na each independently represent the integer of 2-8. 4-6 are preferable and 5 is especially preferable at the point of dispersion stability and developability.

p and q respectively independently represent the integer of 1-100. Different p and different q may be mixed. 5-60 are preferable from a point of dispersion stability and developability, 5-40 are more preferable, and 5-20 are more preferable.

It is preferable that the dispersing agent B in this embodiment contains the repeating unit represented by the said General formula (I) from a point of dispersion stability.

Moreover, as a repeating unit represented by general formula (I), it is more preferable that it is a repeating unit represented with the following general formula (I) -2.

In General Formula (I) -2, R ²¹ to R ²³ each independently represent a hydrogen atom or a monovalent organic group, La represents a C2-C10 alkylene group, and Lb is -C (= 0)-or- NHC (= O)-is represented, A <^21> represents monovalent organic group, ma represents the integer of 2-8, p represents the integer of 1-100.

The repeating unit represented by general formula (I), general formula (II), or general formula (I) -2 is a monomer represented by the following general formula (i), general formula (ii) or general formula (i) -2, respectively. It is introduced as a repeating unit of a high molecular compound by superposing | polymerizing or copolymerizing.

In the general formulas (i), (ii) and (i) -2, R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ²¹ and X ²² each independently represent -CO. -, -C (= O) O-, -CONH-, -OC (= O)-or a phenylene group, L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group, and La is a carbon number 2-10 alkylene groups, Lb represents -C (= 0)-or -NHC (= 0)-, A ²¹ and A ²² each independently represent a monovalent organic group, and ma and na each independently The integer of 2-8 is represented, and p and q respectively independently represent the integer of 1-100.

Dispersant B in this embodiment may further contain the repeating unit derived from the vinyl monomer which can be copolymerized in the range which does not impair the effect.

A preferred embodiment of the dispersant B in the present embodiment is a copolymer of at least a monomer represented by the general formula (i), the general formula (ii) or the general formula (i) -2 with a monomer having an organic dye structure or a heterocyclic structure. More preferably, at least the monomer represented by general formula (i) -2 mentioned above, the monomer represented by general formula (11) above, and the monomer which has an acidic radical are copolymerized. Thereby, the pigment dispersion which is excellent in pigment adsorption and excellent in developability can be provided.

It is preferable that the preferable molecular weight of the dispersing agent B in this embodiment is the range of 400-100,000 in the range of 1,000-100,000 and the number average molecular weight (Mn) by mass average molecular weight (Mw). As for mass mean molecular weight (Mw), it is more preferable that it is the range of 2,000-30,000 in the range of 5,000-50,000, and number average molecular weight (Mn). In particular, it is most preferable that it is the range of 8,000-30,000 in mass average molecular weight (Mw), and the range of 4,000-12,000 in number average molecular weight (Mn). It is preferable that the mass mean molecular weight (Mw) of the dispersing agent B is 1000 or more from a viewpoint of effectively loosening the secondary aggregate which is an aggregate of the primary particle of a pigment, or effectively weakening reaggregation. Moreover, it is preferable that the mass mean molecular weight (Mw) of the dispersing agent B is 30000 or less from a developable viewpoint at the time of manufacturing a color filter with the coloring photosensitive composition containing a pigment dispersion.

The dispersant B in this embodiment is a radically polymerizable compound different from the monomer and copolymerization component represented by following General formula (i), General formula (ii), or General formula (i) -2 (as mentioned above), for example. Various monomers), and can be produced by a general radical polymerization method. Generally, suspension polymerization or solution polymerization is used. Examples of the solvent used when synthesizing such a dispersant B include ethylene chloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, etc. are mentioned. These solvents may be used alone or in combination of two or more thereof. In addition, a radical polymerization initiator may be used in the radical polymerization, and a chain transfer agent (for example, 2-mercaptoethanol and dodecyl mercaptan) may be further used.

As content of the dispersing agent B in the pigment dispersion of this embodiment, pigment: dispersant B = 1: 0.1-1: 2 are preferable by mass ratio, More preferably, it is 1: 0.2-1: 1, More preferably, 1: 0.4-1: 0.7.

In addition, in the range which does not impair the effect of this embodiment, you may use simultaneously other high molecular compounds other than said specific copolymer as needed. As another high molecular compound, a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, etc. are used. Rosin is typical as a natural resin, and rosin derivative, a cellulose derivative, a rubber derivative, a protein derivative, and those oligomers are mentioned as a modified natural resin. Examples of the synthetic resins include epoxy resins, acrylic resins, maleic acid resins, butyral resins, polyester resins, melamine resins, phenol resins and polyurethane resins. Examples of the synthetic resin modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins. Examples of the synthetic resin include polyamideamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, polyurethanes, polyesters, poly (meth) acrylates, (meth) acrylic copolymers, and naphthalenesulfonic acid formalin condensates. do.

The color filter, the colored photosensitive resin composition as the raw material composition and the material, the photosensitive transfer material, the inkjet ink and the like are the same as in the first embodiment with respect to the specific embodiments and the preferred ranges.

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" and "%" are mass references | standards unless there is particular notice.

[Production Example 1-1]

1 mass part of pigment C. I. Pigment Red 146 (Clariant, Permanent Carmine FBB02 [brand name]), 7 mass parts of crushed sodium chloride, and 1.6 mass parts of diethylene glycol were thrown into a twin kneader, and it knead | mixed at 100 degreeC for 4 hours. After kneading, the mixture was taken out to 100 parts by mass of 80 ° C water, stirred for 1 hour, filtered, washed with warm water at 80 ° C, dried at 90 ° C, and pulverized with a hammer mill to obtain pigment powder 1-A.

The organic pigment dispersion composition 1-A of the following composition was adjusted using pigment powder 1-A.

-------------------------------------------------- -

Pigment Powder A 12.0g

6.0 g of Disperbyk 2155 (brand name, BYK Chemie product)

Propylene Glycol Monomethyl Ether Acetate 32.0g

-------------------------------------------------- -

The organic pigment dispersion composition of the above composition was used as motor mill M-50 (trade name, manufactured by EIGER Co., Ltd.) using zirconium oxide beads having a diameter of 0.5 mm for 1 hour at 2000 rpm, followed by zirconium oxide beads having a diameter of 0.1 mm. It disperse | distributed at 2000 rpm for 4 hours, and organic pigment dispersion composition 1-A was obtained. The measurement of the average particle diameter and monodispersity of the pigment fine particles of the dispersion composition 1-A was carried out as follows.

Using a photographic image observed with an electron microscope (JEOL Ltd., JEM-1200EX (trade name)), a circle equivalent diameter was calculated for 200 particles, and the number average of the average particle diameter of the primary particles and 200 particle diameters was calculated. The standard deviation / average particle diameter was called CV. In addition, the crystal particle size performed the powder X-ray diffraction measurement using CuK (alpha) ray about the dichloro diketopyrrole pigment. The measurement was performed in the range whose Bragg angle (2theta) is 23 degrees-30 degrees according to Japanese Industrial Standard JIS K03131 (the X-ray diffraction analysis general rule). The diffraction pattern which removed the background from the obtained X-ray diffraction pattern was calculated | required. Here, the background removal method draws a straight line contacting the lower part of the Bragg angle (2θ) = 23.3 ° of the low angle side of the measurement pattern and the lower part of the Bragg angle (2θ) = 29.7 ° of the high angle side and represented by this straight line. The value of the losing X-ray diffraction intensity is set as the background, and the subtracted from the original pattern is used as the X-ray diffraction pattern from which the background is removed.

From the X-ray diffraction pattern from which the obtained background is removed, the half-angle width and the Bragg angle (2θ) of the diffraction peak are obtained for the peak giving the maximum diffraction intensity at 23.0 ° to 30.0 °. The half value width can be calculated by performing peak separation on each of the diffraction peaks existing in the measurement range using commercial data analysis software. In the example, the value of the half value width calculated by fitting the peak shape as a Voigt function using Wave Metorics product data analysis software Igor Pro is used.

The crystal grain size is calculated by the calculated diffraction peak half-width and the formula below.

D = Kλ / (10 × B × cos A)

B = Bobs-b

From here,

D: crystal grain size (nm)

Bobs: half width (rad) from (2)

b: X-ray diffraction apparatus angular resolution correction coefficient, and half value width (rad) at the time of a standard silicon crystal measurement. In the present invention, standard silicon crystals were measured under the following device configuration and measurement conditions, and b = 0.2.

A: diffraction peak Bragg angle 2θ (rad)

K: Shera integer (defined as K = 0.94)

λ: X-ray wavelength (λ = 1.54 since it is a CuKα ray)

The detail of the measurement conditions is as follows.

X-ray diffractometer: RINT 2500 from Rigaku Corporation

Goniometers: Rigaku Corporation RINT 2000 vertical goniometers

Sampling Width: 0.01 °

Step time: 1 second

Divergence Slit: 2 °

Scattering Slit: 2 °

Receiving Slit: 0.6mm

Tube Sphere: Cu

Tube voltage: 55KV

Tube current: 280mA

As a result of measurement, it was as follows.

[Manufacture example 1-2-manufacture example 1-10]

Organic pigment dispersion compositions 1-B to 1-J were obtained in the same manner as in Production Example 1-1, except that the following pigments were used instead of Pigment Red 146 in Production Example 1-1.

[Production Example 1-11]

1 part by mass of pigment CI Pigment Red 146 (Clariant, Permanent Carmine FBB02 [trade name]) was dispersed in 20 parts by mass of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), and 0.5 part by mass of 28% methanol solution of sodium methoxide was added thereto. It dripped and prepared the pigment solution. When the viscosity was measured for this pigment solution using Viscomate VM-10A-L (brand name, the product made by CBC Materials), the viscosity when the liquid temperature of a pigment solution was 24.5 degreeC was 12.3 mPa * s. Separately from this, 1000 ml of water containing 160 g of 1 mol / L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.

Here, NP-KX-500 the pigment solution to 1000 ml of the poor solvent which temperature-controlled at 10 degreeC and stirred at 500 rpm by GK-0222-10 type | mold Ramondsterer (brand name, the product made by Fujisawa Pharmaceutical Co., Ltd.). An organic pigment particle was formed by injecting 100 ml at a flow rate of 400 ml / min from a liquid feed pipe having a flow path diameter of 1.1 mm by using a large-capacity no-flow pump (trade name, manufactured by Nippon Fine Chemical) to prepare an organic pigment nanoparticle dispersion 1-K.

The organic pigment nanoparticle dispersion liquid 1-K prepared in the above-mentioned procedure was carried out by KOKUSAN Co., Ltd. Products H-112 Centrifugal Filters and Shikishima Canvas Co., Ltd. It concentrated at 5000 rpm for 90 minutes using the product P89C type filter cloth. The obtained paste was washed with water until the salt could be removed with water, and then the organic pigment nanoparticle-concentrated paste 1-K was recovered.

This organic pigment nanoparticle concentration paste K was diluted three times with propylene glycol monomethyl ether acetate, and KOKUSAN Co., Ltd. Products H-112 Centrifugal Filters and Shikishima Canvas Co., Ltd. The product was concentrated for 90 minutes at 14000 rpm using the product P89C type filter cloth. This operation was repeated until water content became 1% or less, and organic pigment nanoparticle concentration paste 1-K (nanoparticle concentration 32.2%) was obtained.

Organic pigment dispersion composition 1-K of the following composition was prepared using organic pigment nanoparticle concentration paste 1-K.

Organic Pigment Nanoparticles Concentrate Paste 1-K 37.3g

6.0 g of Disperbyk 2155 (brand name, BYK Chemie product)

Propylene glycol monomethyl ether acetate 6.7 g

The organic pigment dispersion composition of the above composition was used as motor mill M-50 (manufactured by EIGER Co., Ltd.) at 2000 rpm using 0.5 mm zirconium oxide beads, followed by 2000 rpm using zirconium oxide beads 0.1 mm in diameter. It disperse | distributed for 4 hours and the organic pigment dispersion composition K was obtained.

#
#
Pigment (brand name) Average particle diameter
(nm) Monodispersity Crystal grain diameter
(nm)
1-1

1-A
CI Pigment Red 146
(Clariant products,
Permanent Carmine FBB02)
37.2
22.2
18.3
1-2

1-B CI Pigment Red 177
(Ciba Specialty Chemicals, KK products,
Cromophtal Red A2B)
34.1

18.5
17.6
1-3

1-C CI Pigment Red 254
(Ciba Specialty Chemicals, KK products,
Irgazine DPP Red 2030)
27.3
22.1
13.9
1-4

1-D CI Pigment Red 255
(Ciba Specialty Chemicals, KK products,
Irgazine DPP Scarlet EK)
42.1
29.6
20.6
1-5

1-E CI Pigment Red 122
(Ciba Specialty Chemicals, KK products,
Cromophtal Red PT)
35.2
24.7
18.1
1-6

1-F CI Pigment Red 208
(Clariant products,
Novoperm Red HF2B)
40.2
20.3
19.3
1-7

1-G CI Pigment Red 209
(Ciba Specialty Chemicals, KK products,
Hostaperm Red EG transp)
32.3
29.8
16.2
1-8

1-H CI Pigment Yellow 150
(LANXESS products,
Byplast Yellow E4GN)
23.5
21.6
17.9
1-9

1-I CI Pigment Yellow 138
(BASF products,
Paliotol Yellow D 0960)
38.8
30.3
23.1
1-10

1-J CI Pigment Yellow 176
(Clariant products,
Graphtol Carmine HF3C)
34.6
24.1
20.8
1-11

1-K CI Pigment Red 146
(Clariant products,
Permanent Carmine FBB02)-Build Up
28.0
15.1
15.9

(Example 1-1)

7.5 parts by mass of the organic pigment dispersion composition 1-A obtained in Production Example 1-1, 7.5 parts by mass of the organic pigment dispersion composition 1-C obtained in Production Example 1-3, alkali-soluble resin A (benzyl methacrylate / methacrylic acid ( = 75/25 [mass ratio]) 17 mass parts of propylene glycol monomethyl ether acetate solutions (solid content 30%) of a copolymer (weight average molecular weight: 12,000), 15 mass parts of propylene glycol monomethyl ether acetates were mixed, and the coloring for color filters was carried out. Composition 101a was obtained. The prepared colored photosensitive composition (color resist liquid) was applied onto a 100 mm × 100 mm glass substrate (1737, Corning) so that the x value, which is an index of color density, was 0.650, and dried in an oven at 90 ° C. for 60 seconds. The red pixel part 101 for color filters was obtained.

(Example 1-2)

11.1 parts by mass of the organic pigment dispersion composition 1-A obtained in Production Example 1-1, 1.6 parts by mass of the organic pigment dispersion composition 1-C obtained in Production Example 1-3, and 1-H of the organic pigment dispersion composition obtained in Production Example 1-8. 2.2 mass parts, 17 mass parts of alkali-soluble resin A, and 15 mass parts of propylene glycol monomethyl ether acetate were mixed, and the coloring composition 102a for color filters was obtained. The prepared colored photosensitive composition (color resist liquid) was applied onto a glass substrate (1737, manufactured by Corning) of 100 mm x 100 mm so that the x value serving as an index of color density was 0.660 and the y value was 0.320. It dried for 60 second at and obtained the red pixel part 102 for color filters.

(Example 1-3)

Red pixel part 103 for color filters similarly to Example 1-2 except having used 11.1 mass part of organic pigment dispersion compositions 1-K of Manufacturing Example 1-11 instead of the organic pigment dispersion composition 1-A of Example 1-2. Got.

(Examples 1-4)

The mixing amount of the organic pigment dispersion composition 1-A of Example 1-2 was 10.6 parts by mass, and 2.8 parts by mass of the organic pigment dispersion composition 1-I of Production Example 1-9 was used instead of the organic pigment dispersion composition 1-H. In the same manner as in Example 1-2, the red pixel portion 104 for a color filter was obtained.

(Comparative Example 1-1)

Of 15 parts by mass of the organic pigment dispersion composition 1-A obtained in Production Example 1-1 and an alkali-soluble resin A (benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) 17 mass parts of propylene glycol monomethyl ether acetate solutions (30% of solid content), and 15 mass parts of propylene glycol monomethyl ether acetates were mixed, and the coloring composition c01a for color filters was obtained. The prepared colored photosensitive composition (color resist liquid) was applied onto a glass substrate (1737, manufactured by Corning) of 100 mm x 100 mm so that the x value serving as an index of color density was 0.660 and the y value was 0.320. It dried for 60 second at and obtained the red pixel part c01 for color filters.

(Comparative Example 1-2)

It replaces with the organic pigment dispersion composition 1-A of Example 1-1, and it is set to 6.9 mass parts of organic pigment dispersion composition 1-B of manufacture example 2, except having changed the mixing amount of the organic pigment dispersion composition 1-C into 8.1 mass parts. In the same manner as in 1, the red pixel portion c02 for a color filter was obtained.

(Comparative Example 1-3)

It is 7.2 mass parts of organic pigment dispersion compositions 1-B of manufacture example 2 instead of the organic pigment dispersion composition 1-A of Example 1-2, the mixing amount of organic pigment dispersion compositions 1-C is 7.6 mass parts, and the organic pigment dispersion composition is The red pixel part c03 for color filters was obtained like Example 1-2 except having changed the mixed amount of 1-H into 0.2 mass part.

(Comparative Example 1-4)

The mixing amount of the organic pigment dispersion composition 1-A of Example 1-1 was 8.8 parts by mass, and 6.2 parts by mass of the organic pigment dispersion composition 1-D of Production Example 1-4 was used instead of the organic pigment dispersion composition 1-C. In the same manner as in Example 1-1, the red pixel portion c04 for color filters was obtained.

(Comparative Example 1-5)

A red pixel part c05 for a color filter was obtained in the same manner as in Example 1-1 except that 5 parts by mass of the organic pigment dispersion composition 1-E of Production Example 5 was used instead of the organic pigment dispersion composition 1-C of Example 1-1. .

(Comparative Example 1-6)

Except having made the mixing amount of the organic pigment dispersion composition 1-A of Example 1-1 into 7.0 mass part, and also replaced with the organic pigment dispersion composition 1-C of 8.0 mass part of organic pigment dispersion compositions 1-F of manufacture example 1-6. In the same manner as in Example 1-1, the red pixel portion c06 for a color filter was obtained.

(Comparative Example 1-7)

The mixing amount of the organic pigment dispersion composition 1-A of Example 1-1 was set to 1.5 parts by mass, and 13.5 parts by mass of the organic pigment dispersion composition 1-G of Production Example 1-7 was used instead of the organic pigment dispersion composition 1-C. In the same manner as in Example 1-1, the red pixel portion c07 for color filters was obtained.

(Comparative Example 1-8)

The red pixel part c08 for color filters was obtained like Example 1-1 except having used organic pigment dispersion composition 1-J instead of the organic pigment dispersion composition 1-A of Example 1-1. At this time, the BET specific surface area of pigment dispersion composition 1-J (PR176) was 80 m <2> / g or more.

[Evaluation Method of Color Filter Red Pixel Part]

○ contrast

A polarizing plate was placed on the color pattern of the color filter, and the coloring pattern was inserted, and the brightness at the time of parallel polarization and the brightness at orthogonality were measured using BM-5 (brand name) made by TOPCON CORPORATION, and the brightness at the time of parallel The value obtained by dividing by the luminance of time (= luminance at parallel / luminance at orthogonal angle) was used as an index for evaluating contrast. Larger values indicate higher contrast.

○ Measurement of Y value

Various color filter characteristics were evaluated using the obtained red pixel part for color filters. Color (x, y) and luminance (Y value) were determined using a brown rice spectrophotometer MCPD-3000 (trade name) manufactured by Ohtsuka. About the red pixel part for color filters, the chromaticity coordinate x value and y value in F10 light source side color, and the Y value in CIE colorimeter chromaticity were measured. If luminance Y value is 17 or more, it can be said that it is a color filter red pixel part excellent in practical use.

Yes # Pigment 1 Pigment 2 Pigment 3 Luminance Contrast Example 1-1 101 A (PR146) C (PR254) - 17.33 3844 Example 1-2 102 A (PR146) C (PR254) H (PY150) 17.58 4398 Example 1-3 103 K (PR146) * C (PR254) H (PY150) 17.43 6413 Example 1-4 104 A (PR146) C (PR254) I (PY138) 17.51 2381 Comparative Example 1-1 c01 A (PR146) - - Toning impossibility Comparative Example 1-2 c02 B (PR177) C (PR254) - 16.72 3340 Comparative Example 1-3 c03 B (PR177) C (PR254) H (PY150) 16.72 3682 Comparative Example 1-4 c04 A (PR146) D (PR255) - 16.54 1523 Comparative Example 1-5 c05 A (PR146) E (PR122) - Toning impossibility Comparative Example 1-6 c06 A (PR146) F (PR208) - 16.93 1687 Comparative Example 1-7 c07 A (PR146) G (PR209) - 15.89 102 Comparative Example 1-8 c08 J (PR176) C (PR254) - 16.87 1833

* Build up

Comparative Example 1-1 and Comparative Example 1-5 could not themselves produce a desired color (x = 0.660, y = 0.320). As can be seen from the table, the combination of R146 and R254 has a high luminance of at least 0.4 or more (compared to Comparative Example 1-6 and Example 1-1), compared to the other combinations of the other combinations. There was a difference of about 1.7 (see Comparative Example 1-7, Example 1-2), which was extremely superior as a color material for color filters.

[Production Example 2]

1 mass part of pigment C. I. Pigment Red 146 (Clariant, Permanent Carmine FBB02 [brand name]), 7 mass parts of crushed sodium chloride, and 1.6 mass parts of diethylene glycol were thrown into a twin kneader, and it knead | mixed at 100 degreeC for 4 hours. After kneading, the mixture was taken out in 100 parts by mass of 80 ° C water, stirred for 1 hour, filtered, washed with warm water at 80 ° C, dried at 90 ° C, and pulverized with a hammer mill to obtain pigment powder A.

The organic pigment dispersion composition A of the following composition was adjusted using pigment powder A.

-------------------------------------------------- -

Pigment Powder A 7.5g

4.5 g of Disperbyk 2155 (brand name, BYK Chemie product)

Propylene glycol monomethyl ether acetate 38.0 g

-------------------------------------------------- -

The organic pigment dispersion composition of the above composition was used as motor mill M-50 (trade name, manufactured by EIGER Co., Ltd.) using zirconium oxide beads having a diameter of 0.5 mm for 1 hour at 2000 rpm, followed by zirconium oxide beads having a diameter of 0.1 mm. It disperse | distributed at 2000 rpm for 4 hours and the organic pigment dispersion composition A was obtained. The measurement of the average particle diameter and monodispersity of the pigment fine particles of the dispersion composition A was carried out as follows.

Using a photographic image observed with an electron microscope (JEOL Ltd., JEM-1200EX (trade name)), a circle equivalent diameter was calculated for 200 particles, and the number average of the average particle diameter of the primary particles and 200 particle diameters was calculated. The standard deviation / average particle diameter was called CV. As a result of measurement, it was as follows.

Below, the kneading time in Pigment Red 146 and the twin kneader of the above production example was changed as shown in Table 1 to obtain pigment dispersion compositions 2-B to 2-L.

#
#
Pigment (brand name) Kneading time
(time) Average particle diameter
(nm)
Monodispersity
2-1

2-A
CI Pigment Red 146
(Clariant products,
Permanent Carmine FBB02)
4
37.2
22.2
2-2

2-B CI Pigment Red 146
(Clariant products,
Permanent Carmine FBB02)
7

18.3
25.6
2-3

2-C CI Pigment Red 146
(Clariant products,
Permanent Carmine FBB02)
2
52.1
21.8
2-4

2-D CI Pigment Red 242
(Clariant products,
Novoperm Scarlet 4RF)
4
27.3
22.1
2-5

2-E CI Pigment Red 242
(Clariant products,
Novoperm Scarlet 4RF)
7
19.6
26.0
2-6

2-F CI Pigment Red 242
(Clariant products,
Novoperm Scarlet 4RF)
2
55.0
21.1
2-7

2-G CI Pigment Red 177
(Ciba Specialty Chemicals, KK products,
Cromophtal Red A2B)
4
34.1
18.5
2-8

2-H CI Pigment Red 254
(Ciba Specialty Chemicals, KK products,
Irgazine DPP Red 2030)
4
28.1
19.6
2-9

2-I CI Pigment Red 122
(Ciba Specialty Chemicals, KK products,
Cromophtal Red PT)
4
35.2
24.7
2-10

2-J CI Pigment Red 208
(Clariant products,
Novoperm Red HF2B)
4
36.2
20.3
2-11

2-K CI Pigment Red 209
(Ciba Specialty Chemicals, KK products,
Hostaperm Red EG transp)
4
32.3
29.8
2-12

2-L CI Pigment Yellow 150
(LANXESS products,
Byplast Yellow E4GN)
4
23.5
21.6

Example 2-1

7.5 mass parts of organic pigment dispersion compositions 2-A, 7.5 mass parts of organic pigment dispersion compositions 2-C, alkali-soluble resin A (benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (mass average molecular weight : 12,000, acid value: 120 mgKOH) 17 mass parts of propylene glycol monomethyl ether acetate solutions (solid content 30%), and 15 mass parts of propylene glycol monomethyl ether acetates were mixed, and the coloring composition 201 for color filters was obtained. The prepared colored photosensitive composition (color resist liquid) was applied onto a glass substrate (1737, Coring Products) having a thickness of 100 mm x 100 mm so as to have an x value of 0.650, and dried in an oven at 90 ° C. for 60 seconds. The red pixel part 201 for color filters was obtained.

[Example 2-2-Example 2-7, Comparative Example 2-1-Comparative Example 2-13]

Except having made the pigment dispersion composition and its mass into the following Table 4, it carried out similarly to Example 2-1, and obtained the red pixel part (202-207, c11-c23) for color filters.

[Evaluation Method of Color Filter Red Pixel Part]

(Measurement and evaluation of contrast)

The obtained pigment dispersion composition was apply | coated on a glass substrate, and the sample was produced so that the thickness of the coating film after drying might be set to 1 micrometer. This sample was placed between two polarizing plates, and the amount of transmitted light when the polarization axis was parallel and perpendicular was measured, and the ratio was made to be contrast. Color filter for size TFT-LCD, Ueki, Kozeki, Fukunaga, Yamanaka). It is high.

(Measurement of light resistance)

The sample used for the measurement of the contrast was irradiated with a high-pressure mercury lamp of 90 mW / cm 2 for 24 hours, and the color difference before and after irradiation was measured to be an index of light resistance. In addition, chromaticity is measured with a microscopic spectrophotometer (OLYMPUS CORPORATION; OSP 100 or 200), it calculates as a result of 2 degree C light source visual field, and shows it as the xyY value of a xyz colorimeter. The difference in chromaticity is represented by the color difference ΔEab of the La ^* b ^* color system. The smaller the color difference, the higher the light resistance.

Table 4 shows the contrast and light resistance test results of the red pixel portion for each color filter.

As shown in the above table, in the color material in which the fine particles of the PR146 and the fine particles of the PR242 were mixed, it was found that when using this as a color filter, high contrast and light resistance could be achieved. Moreover, using the pigment composition of the said Example exists in the range of the red characteristic calculated | required by the display apparatus, and confirmed that it was useful as a color material for color filters.

Claims (18)

Pigment Red 146 and Pigment Red 254 as a red pigment, The photosensitive coloring composition for color filters characterized by the above-mentioned. The method of claim 1,
It further contains a yellow pigment, The photosensitive coloring composition for color filters characterized by the above-mentioned. The method according to claim 1 or 2,
Pigment Red 146 is in a particulate form, the average primary particle diameter is 50nm or less, and the crystal grain size is 2 ~ 20nm, the photosensitive coloring composition for color filters. The method according to any one of claims 1 to 3,
40% or more and less than 100% of the red pigment on a mass basis is Pigment Red 146. The photosensitive coloring composition for color filters, characterized in that the above. The method according to any one of claims 1 to 4,
The yellow pigment is Pigment Yellow 150 or Pigment Yellow 138, the photosensitive coloring composition for color filters, characterized in that. 6. The method according to any one of claims 1 to 5,
A photosensitive coloring composition for color filters, further comprising an organic solvent containing a polymerizable compound as a medium. It formed using the photosensitive coloring composition for color filters of Claim 6, The red pixel for color filters characterized by the above-mentioned. The red filter for color filters of Claim 7 is provided, The color filter characterized by the above-mentioned. The color filter of Claim 8 was provided. The liquid crystal display device characterized by the above-mentioned. The ratio of the mass of the CI Pigment Red 146 containing two pigment fine particles of CI Pigment Red 146 and CI Pigment Red 242 to the total mass of the CI Pigment Red 242 and the CI Pigment Red 146 (CIPR146 / (CIPR146 + CIPR242)) is 0.1 or more and 0.95 or less, The pigment dispersion composition characterized by the particle size of the said 2 types of pigment fine particles being 40 nm or less. The method of claim 10,
The ratio of the mass of CI Pigment Red 146 (CIPR146 / (CIPR146 + CIPR242)) is a pigment dispersion composition, characterized in that 0.2 or more. The method of claim 10 or 11,
The pigment dispersion composition containing the high molecular weight compound of the mass mean molecular weights 1000-100000. The method according to any one of claims 10 to 12,
The polymer compound has a pigment dispersion composition characterized in that it has an acid group in the range of 50mgKOH / g or more and 200mgKOH / g or less. The pigment dispersion composition as described in any one of Claims 10-13, a binder, a monomer or an oligomer, and a photoinitiator or a photoinitiator system are included, The coloring photosensitive resin composition characterized by the above-mentioned. The ink dispersion ink for color filters containing the pigment dispersion composition as described in any one of Claims 10-13, a binder, and a monomer or an oligomer. The photosensitive resin transfer material formed on the support body at least the photosensitive resin layer containing the coloring photosensitive resin composition of Claim 14. The pigment fine particle in the pigment dispersion composition produced using the coloring photosensitive resin composition of Claim 14, the inkjet ink for color filters of Claim 15, and / or the photosensitive resin transfer material of Claim 16 is contained, It is characterized by the above-mentioned. Color filter. The color filter of Claim 17 was provided. The liquid crystal display device characterized by the above-mentioned.