JP5611520B2 - Processed pigment, pigment dispersion composition using the same, colored photosensitive composition, color filter, liquid crystal display element, solid-state image sensor, and process pigment manufacturing method - Google Patents

Description

  The present invention is excellent in dispersibility of pigments, excellent in fluidity and coloring power of pigment dispersion compositions and colored photosensitive compositions, and can be suitably used in a wide range of paints, printing inks, color display plates and the like. The present invention relates to a pigment, a pigment dispersion composition, a colored photosensitive composition containing the same, a color filter produced using the colored photosensitive composition, a liquid crystal display device, and a solid-state imaging device.

  The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a colored photosensitive composition. It is manufactured by forming a colored pattern by a photolithography method, an ink jet method or the like.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for use in image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction in color unevenness and improvement in color resolution.

  In response to the above requirements, the pigment contained in the colored photosensitive composition is dispersed in a finer state (good dispersibility), and is dispersed in a stable state (good dispersion stability). Is required. When the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the colored pixels formed by the photolithographic method, and there are many undeveloped residues (residues) on the substrate. There are problems that the chromaticity and dimensional accuracy of the color filter are lowered and the contrast is remarkably deteriorated. In addition, when the dispersion stability of the pigment is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the colored curable composition is reduced, or the sensitivity in the exposure process. Or the alkali solubility in the development process is likely to be reduced. Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored curable composition cause aggregation to increase in viscosity with time and the pot life becomes extremely short. In order to improve color characteristics such as the contrast of color filters, it is effective to reduce the particle diameter of the pigment. However, if the particle diameter of the pigment is reduced, the surface area of the pigment particles increases, so the aggregation between the pigment particles It is often difficult to increase the strength and achieve both a high level of dispersibility and dispersion stability.

The following is known regarding the refinement of pigment particles and the improvement of dispersibility.
In general, the primary particles of the pigment are made fine by a method of kneading a pigment, a water-soluble inorganic salt, or a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader (a salt milling method). Are known. The obtained mixture of primary particles of fine pigment is put into water and stirred with a mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried to obtain a fine pigment as a secondary aggregate that is an aggregate of primary particles of the pigment. The dispersion step in a normal disperser such as a sand mill or a ball mill is a step of loosening a secondary aggregate that is an aggregate of primary particles of a pigment to obtain a dispersion close to the primary particles.

  However, when the primary particles of the pigment are made finer, aggregation tends to occur, and aggregates (secondary aggregates) are likely to be generated during slurry or drying. Further, as the primary particles of the pigment become finer, strong secondary aggregation tends to occur. For this reason, it is generally very difficult to redisperse the refined pigment to primary particles. A color filter formed using a dispersion containing a large amount of secondary aggregates has a large light scattering, and the contrast is remarkably lowered and color density unevenness occurs. Therefore, the pigment dispersion composition aggregates. It is desirable that the primary particles are stably dispersed and the properties are easy to handle.

In order to suppress the strong secondary aggregation of the refined pigment, a rosin, a rosin derivative, or a water-insoluble monomer or oligomer is added in the salt milling process to treat the pigment. There has been proposed a technique for obtaining a color filter having a high contrast by using it (see, for example, Patent Documents 1 and 2).
However, even these methods cannot meet the demand for higher contrast from the market, and further higher dispersibility and dispersion stability in fine pigments have been desired.
In addition, a technique of using a block copolymer as a pigment dispersant to suppress aggregation of pigments has been proposed (Patent Document 3). However, with this technology, it is difficult to obtain effective dispersion stability because the adsorbability of the dispersant to the pigment and its sustainability are insufficient, and strong secondary aggregation of the fine pigment is suppressed for a long period of time. It was difficult to do.
Japanese Patent No. 3130217 JP 2004-233727 A JP 2006-526670 A

That is, the subject of the present invention is a processed pigment with improved dispersibility that can be dispersed in the form of primary particles while suppressing the formation of secondary agglomerates even in a refined pigment, An object of the present invention is to provide a processed pigment excellent in dispersion stability in which dispersed primary particles are stably maintained and a method for producing the processed pigment.
A further object of the present invention is to provide a pigment dispersion composition having excellent pigment dispersibility and dispersion stability using such a processed pigment, and a colored photosensitivity having excellent curability comprising such a pigment dispersion composition. It is to provide a sex composition.
Another object of the present invention is to provide a color filter, a liquid crystal display element, and a solid having a color pattern using the colored photosensitive composition of the present invention, having high contrast and low color density unevenness, and good color characteristics. The object is to provide an imaging device.

The present inventors have found that the above problems can be achieved by the following method, and have reached the present invention.
<1> A pigment, a block copolymer having a pigment adsorbing block and a pigment non-adsorbing block, a water-soluble inorganic salt, and a water-soluble organic solvent that does not dissolve the water-soluble inorganic salt, A processed pigment obtained by coating the pigment with the block copolymer by mechanically kneading in the conversion step,
The block copolymer has neither a pigment-adsorbing block composed of one or more monomers having an organic dye structure or a heterocyclic structure, nor an organic dye structure or a heterocyclic structure. ) acrylate ester le; crotonic acid ester le; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester Le; (meth) acrylamide; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene , Isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene, hydroxy styrene protected with groups deprotectable by acidic substances, vinyl benzoic acid Methyl , And alpha-1 one styrene compound selected from styrene; Biniruete Le; Biniruketo emissions; olefin emissions; maleimide, butyl maleimide, cyclohexyl maleimide, and one maleimide de compound selected from phenylmaleimide; and (meth) acrylonitrile anda pigment non-adsorbing blocks configured with one or more monomers selected from the group consisting of anionic living process, or a block copolymer prepared by radical living method processed pigment.
<2> The processed pigment according to <1>, wherein the block copolymer has a weight average molecular weight of 1,000 or more and 100,000 or less.
<3> The processed pigment according to <1> or <2>, wherein the average primary particle size is 5 nm or more and 25 nm or less.
<4> The processed pigment according to any one of <1> to <3>, wherein the pigment refinement step further includes a pigment drying step.
<5> The addition amount of the inorganic salt in the pigment refinement step is 5 to 25 times by mass with respect to the pigment, and the addition amount of the water-soluble organic solvent is 15 to the inorganic salt. <1>-<4> The processed pigment according to any one of <1> to <4>, wherein the processed pigment is from 35% by mass to 35% by mass.

<6> A pigment dispersion composition, wherein the processed pigment according to any one of <1> to <5> is dispersed in an organic solvent.
<7> The pigment dispersion composition according to <6>, further including a pigment dispersant.
<8> The pigment dispersion composition according to <6> or <7>, which is used for forming a colored region in a color filter.
<9> A colored photosensitive composition comprising the pigment dispersion composition according to any one of the above items <6> to <8>, a photopolymerizable compound, and a photopolymerization initiator.
<10> A color filter having a colored region formed of the colored photosensitive composition according to <9> on a substrate.
<11> A liquid crystal display device comprising the color filter according to <10>.
<12> A solid-state imaging device including the color filter according to <10>.
<13> pigment and a water-soluble inorganic salt, the water-soluble does not dissolve the inorganic salts water-soluble organic solvent, pigment adsorbing block configured with one or more monomers having an organic dye structure or a heterocyclic structure If not have any of the organic dye structure or a heterocyclic structure, (meth) acrylic acid ester le; crotonic acid ester le; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester le; ( meth) acrylamide; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichloro styrene, bromostyrene, chloromethylstyrene Deprotectable with acidic substances Selected maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide; protected hydroxystyrene group, methyl vinyl benzoate, and one styrene compound selected from α- methylstyrene; Biniruete Le; Biniruketo emissions; olefin emissions one maleimide de compound; a and a pigment non-adsorbing blocks configured with one or more monomers selected from the group consisting of (meth) acrylonitrile, manufacturing, living anionic method, or by a radical living method A step of mechanically kneading the prepared block copolymer to prepare a mixture, and
A process for producing a processed pigment, comprising: adding the obtained mixture into water and stirring to prepare a slurry containing the pigment coated with the block copolymer.
<14> The method for producing a processed pigment according to <13>, further comprising a step of drying the pigment coated with the block copolymer contained in the obtained slurry.

The present invention is a block copolymer having a pigment adsorbing block and a pigment non-adsorbing block, and a processed pigment that has been subjected to coating treatment through a finer process of the pigment using salt milling, which will be described in detail below, With regard to application, by using this processed pigment, it is possible to obtain a pigment dispersion composition and a color filter that are superior in dispersibility and dispersion stability, have high contrast, and have small color density unevenness.
That is, the pigment-adsorbing block constituted by using one or more monomers having an organic dye structure or a heterocyclic structure of the present invention, and (meth) acrylic having neither an organic dye structure nor a heterocyclic structure. acid ester le; crotonic acid ester le; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester Le; (meth) acrylamide; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl Styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene, hydroxy styrene protected with an acid deprotectable group, methyl vinyl benzoate, And α One styrene compound selected from styrene; Biniruete Le; Biniruketo emissions; olefin emissions; maleimide, butyl maleimide, cyclohexyl maleimide, and one maleimide de compound selected from phenylmaleimide; than and (meth) the group consisting of acrylonitrile When a block copolymer having a pigment non-adsorptive block composed of one or more selected one or more monomers is used for pigment treatment (hereinafter, may be referred to as a specific copolymer), It is considered that the formation of secondary aggregates, which are aggregates of primary particles of pigment, can be effectively suppressed, or the cohesive force of secondary aggregates can be effectively weakened. Therefore, in the dispersion step, a dispersion in a state close to primary particles can be obtained, and a color filter with high contrast and a color filter with small color density unevenness can be obtained.
Although the action of the present invention is not clear, the block adsorbing block of the block copolymer of the present invention is adsorbed to the pigment, whereby the block copolymer covering the pigment is strongly adsorbed to the primary pigment particles. This powerful suction, slurry, filtered, since the block copolymer was also coated during washing will not be desorbed, it is considered that to effectively suppress the aggregation of the primary particles of the pigment. For this reason, since the density of the adsorption site is higher than when the pigment is coated with a random copolymer obtained by copolymerizing a monomer having a pigment adsorbing group and a monomer having a pigment non-adsorbing group, It is considered that further improvement in adsorptivity is achieved.

One feature of the present invention is that the pigment is coated with a block copolymer having a pigment adsorbing block and a pigment non-adsorbing block to obtain a processed pigment, and the coating refines the primary particles of the pigment. process and to facilities at the same time. That is, in the dispersion step after the micronization step, a block copolymer having a pigment adsorbing block and pigment non-adsorbing block compared to a method of stabilizing a dispersion I'll be adsorbed, resulting in finer surface The block copolymer having the pigment adsorbing block and the pigment non-adsorbing block of the present invention is adsorbed to the new interface of the highly active pigment by a strong electrostatic action, and a strong coating layer of the block copolymer is formed. Therefore, it is considered that a processed pigment having higher dispersion stability can be obtained. That is, in the present invention, the processed block copolymer is hardly released even if it is washed with an organic solvent that dissolves the block copolymer. On the other hand, in the pigment disclosed in JP-A-2006-526670, when washed with an organic solvent, most of the block copolymer, which is a dispersant, is desorbed from the pigment. Stability is not obtained.

The color filter using the processed pigment which is coated with the block copolymer (JP Jotomo polymer) having a pigment adsorbing block of the present invention and a pigment non-adsorbing block, color under high temperature and high humidity Problems such as cloudiness of the filter layer and turbidity when creating a color filter can also be solved. These problems are considered to occur as fine pigment particles in the filter aggregate and grow as crystals, and are more likely to occur as the primary particles of the pigment are finer. The processed pigment coated with the specific copolymer of the present invention is because the specific copolymer is strongly adsorbed to the fine pigment, and thus effectively suppresses aggregation of pigment particles even in the filter. it is conceivable that.

  Furthermore, the color filter using the processed pigment coated with the specific copolymer of the present invention is excellent in the voltage holding ratio of the liquid crystal. The decrease in the voltage holding ratio of the liquid crystal is likely to occur when the metal ion concentration in the color filter is high. This problem is likely to occur especially when the pigment is refined using the salt milling method. This is because the inorganic salt (ions) used in the salt milling process is adsorbed to the pigment particles during the salt milling process, and the dispersion process, color This is probably because the pigment particles are eluted after the filter manufacturing process or the liquid crystal display element is formed. The finer the primary particles of the pigment, the easier it is to include an ionic compound and the removal by water washing and filtration becomes difficult. The processed pigment coated with the specific copolymer of the present invention has an effect of elution of ions in the dispersion process or in the color filter because the specific copolymer is strongly adsorbed to the fine pigment for the reasons described above. It is thought that it can be suppressed.

  In addition, the colored photosensitive composition using the processed pigment coated with the specific copolymer of the present invention has an advantage that precipitates are hardly generated in the developing solution in the development process of color filter production. Precipitates are often aggregates of pigment particles. Precipitation is considered to be a phenomenon in which the pigment dispersion dispersed with the dispersant is desorbed by the alkaline developer, and the fine pigment particles aggregate and crystallize and precipitate. In the processed pigment of the present invention, since the specific copolymer is strongly adsorbed to the fine pigment, the specific copolymer is not desorbed even by an alkaline developer, and precipitates are not easily generated in the developer. it is conceivable that.

According to the present invention, even in a refined pigment, the formation of secondary aggregates is suppressed, and the processed pigment with improved dispersibility that can be dispersed in the form of primary particles, and dispersed primary particles It is possible to provide a processed pigment excellent in dispersion stability and a method for producing the same .
Further, according to the present invention, by using the processed pigment of the present invention, a pigment dispersion composition having excellent dispersibility and dispersion stability of the pigment, and a colored photosensitivity having excellent curability including the pigment dispersion composition. Sex compositions can be provided.
Further, according to the present invention, it is possible to provide a color filter having a color pattern using the colored photosensitive composition of the present invention, having a high contrast and a small color density unevenness and good color characteristics. In addition, it is possible to provide a liquid crystal display device and a solid-state imaging device provided with this color filter.

Hereinafter, the present invention will be described in detail.
<Processed pigment>
The processed pigment of the present invention has neither a pigment-adsorbing block composed of one or more monomers having an organic dye structure or a heterocyclic structure, nor an organic dye structure or a heterocyclic structure. ) acrylate ester le; crotonic acid ester le; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester Le; (meth) acrylamide; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene , Isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene, hydroxy styrene protected with groups deprotectable by acidic substances, vinyl benzoic acid Methyl, And one styrene compound selected from α- methylstyrene; Biniruete Le; Biniruketo emissions; olefin emissions; maleimide, butyl maleimide, cyclohexyl maleimide, and one maleimide de compound selected from phenylmaleimide; and from (meth) acrylonitrile A non-adsorptive pigment block composed of at least one monomer selected from the group consisting of a block copolymer produced by an anion living method or a radical living method, It is characterized in that it has been coated in the pigment refinement step described in detail.

  The processed pigment of the present invention is excellent in dispersibility and dispersion stability because the pigment surface is firmly coated with the block copolymer of the present invention, and this block copolymer is hardly released even when immersed in an organic solvent. The processed pigment has a wide range of applications and is particularly useful for the preparation of pigment dispersion compositions.

  The production of such microfabricated pigments comprises i) a pigment, ii) a water-soluble inorganic salt, iii) a small amount of a water-soluble organic solvent that does not substantially dissolve ii), and iv) a pigment-adsorbing block. A step of adding a block copolymer having a non-pigmentable block and mechanically kneading with a kneader or the like (this step is called salt milling), putting this mixture into water, stirring it with a high speed mixer or the like, and slurrying And the slurry is filtered, washed with water, and dried if necessary. By such a production method, the processed pigment of the present invention is obtained which is fine and has little aggregation of the pigment during drying.

The salt milling described above will be described more specifically. First, add a small amount of iii) a water-soluble organic solvent as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, knead strongly with a kneader, etc., and then throw this mixture into water. Stir with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When used in an oily varnish, it is possible to disperse the treated pigment before drying (referred to as filter cake) in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.
In the present invention, by using iv), which is a resin that is at least partially soluble in an organic solvent, during salt milling, the resin iv) is coated with a finer and at least partially soluble resin. In addition, a processed pigment with little aggregation of the pigment when dried can be obtained.
As a method for preventing dry aggregation, an alkali-soluble resin dissolved in an alkaline aqueous solution is added to the above slurry, and the mixture is sufficiently stirred and then neutralized with an acidic aqueous solution such as hydrochloric acid or sulfuric acid to deposit the resin on the pigment, or calcium chloride. Alternatively, it is possible to prevent dry aggregation by adding an aqueous solution of a water-soluble polyvalent metal salt such as barium chloride to precipitate the resin and deposit it on the pigment.
In addition, iv) The timing which adds the block copolymer which has a pigment adsorbing block and a pigment non-adsorbing block may add all at the initial stage of a salt milling process, and may add separately.

[I) Pigment]
As the pigment used in the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used. As the particle size of the pigment, considering that the color filter in which the pigment dispersion composition of the present invention is suitably used preferably has a high transmittance, an organic pigment is preferable, and a pigment having a particle size as small as possible. Is preferably used. Considering the handling properties of the pigment dispersion composition and the colored photosensitive composition containing it, the average primary particle diameter of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 to 25 nm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast. The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7

  These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them and a disazo yellow pigment, an isoindoline yellow pigment or a quinophthalone yellow pigment, Alternatively, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them and a mixture of a perylene red pigment, an anthraquinone red pigment or a diketopyrrolopyrrole red pigment, etc. Can do. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. When the mass ratio of the red pigment to the other pigment is 100: 5 to 100: 80, the light transmittance from 400 nm to 500 nm can be suppressed and the color purity can be increased. Further, a decrease in coloring power is suppressed. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. The above range is preferable from the viewpoints of light transmittance, color purity, and NTSC target hue. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

  Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable. The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. The above range is preferable from the viewpoint of dispersion stability.

  Among the above-mentioned pigments, azo pigments and polycyclic pigments are preferable, and more preferably, insoluble azo pigments, dioxazine pigments, phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, And perylene pigments. These pigments are advantageous because they are considered to have a relatively strong interaction such as hydrogen bonding with the specific copolymer. In addition, a metal complex pigment such as a phthalocyanine pigment (for example, PG36, PB15: 6) or an azomethine pigment (for example, PY150) is coordinated with the nitrogen atom or oxygen atom of the side chain of the specific copolymer to the metal complex. It is preferable because the interaction by bonding also works and is strongly adsorbed on the primary pigment particles.

[Ii) Water-soluble inorganic salt]
The water-soluble inorganic salt used in the present invention is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used. Alternatively, it is preferable to use sodium sulfate.
The amount of the inorganic salt used for salt milling is preferably 1 to 30 times by weight, particularly 5 to 25 times by weight of the organic pigment, from the viewpoint of both processing efficiency and production efficiency. This is because the finer efficiency is higher as the amount ratio of the inorganic salt to the organic pigment is larger, but the amount of treatment of one pigment is reduced.

[Iii) A small amount of a water-soluble organic solvent that does not substantially dissolve ii)
The water-soluble organic solvent functions to wet the organic pigment and the inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol or the like is used.

The addition amount of the water-soluble organic solvent is preferably 5% by mass to 50% by mass with respect to the inorganic salt. More preferably, it is 10 mass%-40 mass% with respect to an inorganic salt, and optimally it is 15 mass%-35 mass% with respect to an inorganic salt. When the addition amount is less than 5% by mass, uniform kneading becomes difficult, and the particle size distribution becomes large, which is not preferable. When the addition amount exceeds 50% by mass, the kneaded composition becomes too soft, and it becomes difficult to apply shear to the kneaded composition, so that a sufficient refinement effect cannot be obtained.
iii) The water-soluble organic solvent may be added in the initial stage of salt milling, or may be added separately. A water-soluble organic solvent may be used independently and can also use 2 or more types together.

[Iv) an organic dye structure or pigment adsorbing block constituted by a monomer having a heterocyclic structure, no any of the organic dye structure or a heterocyclic structure, (meth) acrylic acid ester le; crotonic acid ester le ; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester Le; (meth) acrylamide; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, Is methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with groups deprotectable by acidic substances, methyl vinylbenzoate, and α-methylstyrene? One styrene compound selected; Biniruete Le; Biniruketo emissions; olefin emissions; maleimide, butyl maleimide, cyclohexyl maleimide, and one maleimide de compound selected from phenylmaleimide; and (meth) 1 selected from the group consisting of acrylonitrile Block copolymer produced by anion living method or radical living method having a pigment non-adsorbing block composed of more than one kind of monomer)
The block copolymer (specific copolymer) used in the present invention has a pigment adsorbing block and a pigment non-adsorbing block described in detail below.
The pigment adsorbing block is composed of a monomer having a functional group that can be adsorbed to the pigment (hereinafter sometimes referred to as an adsorbing group or a pigment adsorbing group).
Specifically, the monomer is a monomer selected from monomers having an organic dye structure or a heterocyclic structure, and may further include a monomer having an acidic group, a monomer having a basic nitrogen atom, and the like. The specific copolymer of the present invention essentially uses a monomer having an organic dye structure or a heterocyclic structure. The organic dye structure or the heterocyclic structure may be the same as or different from the structure of the pigment, but is preferably similar to the pigment structure from the viewpoint of the interaction between the pigment and the pigment adsorbing group. from the viewpoint of adsorption to the pigment derivative, a chromatic advantage in having a acid-base interactions functional group.

Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, anthanthrone series, Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolino , Mention may be made of benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, a monomer having a heterocyclic structure anthraquinone. Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

When the pigment-adsorbing block of the specific copolymer used in the present invention further includes a copolymer unit derived from a monomer having an acidic group, when the pigment dispersion composition is applied to the photosensitive composition, the unexposed area It has excellent development removability.
This acidic group has a pigment adsorptivity and an alkali-soluble function.

Examples of monomers having an acidic group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycap Mono (meth) acrylates such as both terminal carboxy polymer such as a lactone mono methacrylate. The block copolymer of the present invention may contain only one type of copolymer unit derived from a monomer having an acid group, or may contain two or more types.
Among these, it is preferable to use a vinyl monomer having a carboxyl group or a vinyl monomer having a sulfonic acid group.

  Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono ( A (meth) acrylate etc. can also be utilized. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  Examples of the monomer having a basic nitrogen atom include vinyl pyridine, vinyl imidazole, vinyl triazole, and the like as (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N , N-dimethylaminopropyl, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N (meth) acrylic acid, N-diethylaminoethyl, N, N-diisopropylaminoethyl (meth) acrylate, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylamino (meth) acrylate Ethyl, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, (meth) acrylic acid -Pyrrolidinoethyl, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate, N, N-methylphenylaminoethyl (meth) acrylate, and the like. (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ′, N′-diethylaminoethyl) acrylamide, N- (N ′, N '-Diethylaminoethyl) methacrylamide, N- (N', N'-dimethylaminopropyl) acrylamide, N- (N ', N'-dimethylaminopropyl) methacrylamide, N- (N', N'-diethylaminopropyl) ) Acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- (N, N-di) Tilamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl ( (Meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meta) ) Acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc., and styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene and the like.

  Furthermore, as the monomer constituting the pigment adsorbing block, a monomer containing an ionic functional group can be used. Examples of ionic vinyl monomers (anionic vinyl monomers, cationic vinyl monomers) include, as anionic vinyl monomers, alkali metal salts of vinyl monomers having the acidic group, organic amines (for example, triethylamine, dimethylaminoethanol, etc.) As a cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom). Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1); -18); Dia sulfate Kill (alkyl group: C1 -4) that is quaternized with such, like dialkyl diallyl ammonium salts.

  The monomer having a functional group that can be adsorbed to the pigment can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

On the other hand, the non-pigmentable block is a monomer that does not have any pigment-adsorptive group selected from an organic dye structure and a heterocyclic structure, and includes monomers exemplified below as constituent components.
Monomers constituting the pigment non-adsorbing block (meth) acrylic acid ester le; crotonic acid ester le; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester Le; (meth) acrylamide Styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene protected hydroxy styrene protecting groups, one styrene compound selected from vinyl benzoate, and α- methyl styrene; Biniruete Le; Biniruketo emissions; olefin emissions; maleimide, Buchirumare Bromide, cyclohexyl maleimide, and one maleimide de compound selected from phenylmaleimide; can be given as well (meth) monomers selected from the group consisting of acrylonitrile. These monomers may be used independently and may use 2 or more types together.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 4-hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, (meth) a 2-ethoxyethyl laurate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, vinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, (meta ) 1-propenyl acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth ) Diethylene glycol monoethyl ether acrylate, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene Glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acryl Trifluoroethyl acid, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyloxyethyl and (meth) acrylic acid γ-butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

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

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
Examples of (meth) acrylonitrile include methacrylonitrile and acrylonitrile.

The specific copolymer of the present invention has a functional group capable of adsorbing to the pigment as long as it contains a pigment adsorbing group selected from an organic dye structure and a heterocyclic structure among the functional groups capable of adsorbing to the pigment . Any one may be included, and two or more may be included. The content of the adsorptive group in the block copolymer is not particularly limited, is 100 wt% based on the total structural units contained in the block copolymer preferably contains more than 5 wt%, It is more preferable to contain 10 mass% or more and 50 mass% or less.
That is, effectively suppress the formation of secondary aggregate is an aggregate of primary particles of the pigment, or, in order to weaken the cohesive force of secondary aggregate effectively, the content of the adsorptive group 5 It is preferable that it is mass% or more. Further, from the viewpoint of developability in producing a color filter by coloring a photosensitive composition containing a pigment dispersion composition, the content of the pigment adsorbing group is preferably at most 50 mass%.

  In the specific copolymer of the present invention, the content of the copolymer unit derived from the monomer having an acid group is preferably 50 mgKOH / g or more and 200 mgKOH / g or less, particularly preferably 80 mgKOH / g or more and 200 mgKOH / g or less. is there. A more preferable range is 100 mgKOH / g or more and 180 mgKOH / g or less. That is, in terms of suppressing the formation of precipitates in the developer, the content of copolymer units derived from monomers having acid groups is preferably 50 mgKOH / g or more. When the acid value is larger than 200 mgKOH / g, aggregation between acid groups becomes strong, aggregation between processed pigments occurs, and dispersibility deteriorates, which is not preferable. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, copolymerization derived from monomers having acid groups The unit content is preferably within the above range.

The block copolymer in the present invention may further contain copolymer units derived from a copolymerizable vinyl monomer as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. As a specific example of such a vinyl monomer, the block copolymer monomer may be the same compound as the pigment non-adsorbing block monomer. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

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

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

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

The pigment adsorbing block in the specific copolymer according to the present invention is constituted by polymerizing one or more structural units having at least a pigment adsorbing group (an organic dye structure or a heterocyclic structure similar to the pigment structure). Has been. The pigment non-adsorbing block is constituted by polymerizing at least one structural unit having an acidic group. The acidic group has been introduced to impart solubility during development processing.
In addition, the “block” according to the present invention is a part of a polymer, which is composed of a plurality of the above structural units, and each block has at least one kind of characteristic that does not exist in an adjacent block.

  The preferred molecular weight of the specific copolymer according to the present invention is preferably in the range of 1,000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 400 to 50,000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. In particular, the weight average molecular weight (Mw) is most preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is in the range of 4,000 to 12,000.

That is, from the viewpoint of effectively suppressing the formation of secondary aggregates, which are aggregates of primary particles of pigment, or effectively reducing the cohesive force of secondary aggregates, The combined weight average molecular weight (Mw) is preferably 1,000 or more. From the viewpoint of developability when producing a color filter from a colored photosensitive composition containing a pigment dispersion composition, the block copolymer of the present invention has a weight average molecular weight (Mw) of 100,000 or less. It is preferable.
In the pigment dispersion composition of the present invention, the content of iv) specific copolymer according to the present invention is preferably a mass ratio, i) pigment: iv) specific copolymer = 1: 0.01 to 1: 2. More preferably, it is 1: 0.05 to 1: 1, and still more preferably 1: 0.1 to 1: 0.6.

The specific copolymer of the present invention can be synthesized according to a conventionally known polymerization method described below. For example, it can be synthesized by the method described in JP-A-2005-255832. As a polymerization method of the block copolymer, living polymerization, iniferter method, etc. are known, and as another method, thiol is used for radical polymerization of a monomer having a pigment adsorption group or a monomer having no pigment adsorption group. A polymer obtained by polymerizing a compound containing a thioester and a thiol group in a molecule such as carboxylic acid or 2-acetylthioethyl ether or 10-acetylthiodecanethiol is used as a polymer such as sodium hydroxide or ammonia. There is also known a method in which a polymer having a thiol group at one end is treated with an alkali, and the monomer of the other block is radically polymerized in the presence of the resulting polymer having a thiol group at one end. In addition, for example, W.W. J. et al. Burrant, A.M. S. Hoffman "Block and Graft polymers" (1960, Renhard); J. et al. Ceresa, “Block and Graft Polymers” (1962, Butterworths); C. Allport, W.M. H. James "Black Copolymers" (1972, Applied Sci); Noshay, J .; F. McGvath "Block Copolymers" (1977, Academic press); Huvtrez. D. J. et al. Wilson, G.G. Riess,
“NATO ASI Sev. Sev E.” 1985, 149; Percea, “Applied. Polymer Sci.” 285, 95 (1985), and the like.

For example, the ion polymerization reaction using an organometallic compound (for example, alkyllithiums, lithium diisopropylamide, alkali metal alcoholates, alkylmagnesium halides, alkylaluminum halides, etc.) as a polymerization initiator is described in T.W. E. Hogueu-Esch, J.A. Smid, “Recent Advances in Anionic Polymerization” (1987, Elsevier New York); Yoshio Okamoto, Polymer, 38, 912 (1989); Mitsuo Sawamoto, “Polymer” 38, 1018 (1989); Tadashi Narita, “High Molecules "37, 252 (1988); C. Anderson, et al, “Macromolecules” 14, 1601 (1981); Aoshima, T .; Higashimura,
“Macromolecules” 22, 1009 (1989) and the like. Regarding the ion polymerization reaction by hydrogen iodide / iodine system or the like, see T.W. Higashimura et al, “Makromol. Chem., Macromol. Symp.”, 13/14, 457 (1988); Toshinobu Higashimura, Mitsuo Sawamoto, “Polymer Papers” 46, 189 (1989), etc. . For group transfer polymerization reaction, see D.C. Y. Sogah et al, “Macromolecules” 20, 1473 (1987); W. Webster, D.D. Y. Sogah, “Polymer” 36, 808 (1987) and the like . Furthermore, regarding the photo-living polymerization reaction using a dithiocarbamate compound or a xanthate compound as an initiator, Takayuki Otsu, “Polymer” 37, 248 (1988); Shunichi Sasamori, Ryuichi Otsu, “Polym. Rep. Jap.” 37 3508 (1988); JP-A 64-111; JP-A 64-26619; Niwa, “Macromolecules
, 189, 2187 (1988), etc. On the other hand, a polymer containing an azo group or a peroxide group is used as an initiator. A method of synthesizing a block copolymer also by a radical polymerization reaction is described below. Ueda Akira et al., “Polymer Papers” 33, 931 (1976); Ueda Akira, “Osaka City Industrial Research Institute Report” 84, (1989); Nuyken et al,
“Macromol. Chem., Rapid. Commun.” 9, 671 (1988) and the like. In synthesizing an acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W.H. R. Hertler et al, Macromolecules, 20, 1473 (1987), K. et al. Matyaszewski et al, Chem. Rev. Known methods described in 2001, 101, 2921-2990, and the like can be employed.
Among the above methods, the anion living method or the radical living method is used for producing the specific copolymer of the present invention .

Examples of the solvent used in the synthesis of the specific polymer such as this, for example, ethylene dichloride, 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-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, etc. Can be mentioned. These solvents may be used alone or in combination of two or more. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

The processed pigment of the present invention is characterized in that a pigment particle such as an organic pigment is coated with a specific copolymer by performing salt milling, which is a process of refining the pigment, and the polymer compound is coated on the surface of the pigment particle. The effect of the present invention is obtained by being firmly coated on a part or all of the above, and is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (free rate) of the specific copolymer by washing with an organic solvent shown below. That is, when the specific copolymer is simply adsorbed to the pigment, most of the specific copolymer, specifically, 65% or more is liberated and removed by washing with an organic solvent. In the case of a processed pigment whose surface is coated with a copolymer, the liberation rate of the specific copolymer is extremely small, for example, 30% or less.
The processed pigment of the present invention is washed with 1-methoxy-2-propanol and the free amount is calculated. In this method, 10 g of the processed pigment is put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Next, the pigment is allowed to settle for 8 hours at 80,000 rpm with a centrifuge, and the solid content of the supernatant is determined from the drying method. Then, the mass of the specific copolymer released from the pigment is obtained, and the liberation rate (%) is calculated from the ratio with the mass of the specific copolymer used in the initial treatment.

The liberation rate of commercially available processed pigments can be measured by the following method. That is, after dissolving the entire processed pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. Then, it is calculated as “mass of the polymer compound used in the initial treatment”. Separately, the processed pigment was washed with 1-methoxy-2-propanol, and the obtained release amount was divided by this “mass of the polymer compound used in the initial treatment” to obtain the release rate (%). Ask.
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

Moreover, you may use another compound simultaneously as needed other than the above-mentioned specific copolymer. Preferably, it should be solid at room temperature, insoluble in water, and at least partially soluble in a water-soluble organic solvent used as a wetting agent during salt milling. A modified synthetic resin or the like is used.
When using a dried treated pigment, the compound used is preferably solid at room temperature. The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include epoxy resin, acrylic resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, and the like. Examples of the synthetic resin modified with a natural resin include rosin-modified maleic resin and rosin-modified phenol resin.

  Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

  The processed pigment of the present invention thus obtained has a highly dispersible and stable dispersion because the pigment surface is firmly coated with the specific copolymer and does not release even when immersed in an organic solvent. It becomes a pigment and its application range is wide, and it is particularly useful for the preparation of a pigment dispersion composition. The processed pigment of the present invention is excellent in dispersibility, and the pigment dispersion composition and the colored photosensitive composition using the processed pigment of the present invention are excellent in fluidity, coloring power and the like. These can be suitably used in a wide range of paints, printing inks, color display boards and the like.

<Pigment dispersion composition>
Next, the pigment dispersion composition of the present invention using the processed pigment of the present invention will be described.
The pigment dispersion composition of the present invention is obtained by dispersing the processed pigment of the present invention in an organic solvent.
Moreover, when dispersing the processed pigment of this invention in the organic solvent, it is also a preferable aspect to use (A) a pigment derivative and (B) a dispersing agent suitably as needed.

〔Organic solvent〕
The solvent in the pigment dispersion composition of the present invention is not particularly limited as long as it is an organic solvent, and can be appropriately selected from known solvents such as 1-methoxy-2-propyl acetate and 1-methoxy-2. -(Poly) alkylene glycol monoalkyl ethers such as propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and their acetates Acetates such as ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate and i-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl Ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, alcohols such as glycerin, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alkylene glycol monoalkyl ethers and their acetates, acetates, methyl ethyl ketone, and the like are preferable.

  The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition. When the pigment dispersion composition is used for the preparation of a colored photosensitive composition to be described later, from the viewpoint of handleability, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass. Can do.

[(A) Pigment derivative]
A pigment derivative is added to the pigment dispersion composition of the present invention as necessary. The pigment is dispersed in the colored photosensitive composition as fine particles by adsorbing the pigment derivative with a part having affinity with the dispersant or a polar group introduced onto the pigment surface and using this as the adsorption point of the dispersant. Therefore, the reaggregation can be prevented, and it is effective in constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, the dispersion can be favorably performed while the viscosity is kept low, the dispersion stability after dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The dispersion method is, for example, using a bead disperser using zirconia beads or the like (for example, a disperse mat made by GETZMANN Co., Ltd.) that has been previously mixed with a pigment and a dispersant and previously dispersed with a homogenizer or the like. This can be done by fine dispersion. The dispersion time is preferably about 3 to 6 hours.

[(B) Dispersant]
For the purpose of further improving the dispersibility of the pigment, conventionally known dispersants such as pigment dispersants and surfactants, and other components may be added.
Known dispersants (pigment dispersants) include polymer dispersants such as polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth). Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
The polymer dispersant is adsorbed on the surface of the pigment in the dispersion step to prevent reaggregation in the same manner as the block copolymer having the pigment adsorbing block and the pigment non-adsorbing block of the present invention. Works. For this reason, a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

(Block type polymer) As the block type polymer, the same block copolymer as that for coating the pigment is used.

(Graft-type polymer) The graft-type polymer is not particularly limited, but is a compound obtained by reacting a polyalkyleneimine and a polyester compound described in JP-A Nos. 54-37082 and 61-174939. Preferable examples include a compound in which the amino group of the side chain of polyallylamine described in JP-A-9-169821 is modified with polyester, a polyester polyol-added polyurethane described in JP-A-60-166318, and the like. As described in JP-A-9-171253 and Macromonomer Chemistry and Industry (IPC Publishing Department, 1989), a graft-type polymer having a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component. Molecules can also be preferably mentioned.

  As the branch part of the graft polymer, polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, and the like are preferably mentioned. The structural unit represented by the following general formula (5) is a branch part. More preferred is a graft polymer having at least

In the general formula (5), R ⁷⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Q is a cyano group, an aryl group having 6 to 30 carbon atoms, or —COOR ⁷⁵ (where, R ⁷⁵ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

In general formula (5), the alkyl group represented by R ⁷⁴ may have a substituent, preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. Examples of the substituent for the alkyl group include a halogen atom, a carboxyl group, an alkoxycarbonyl group, and an alkoxy group. Specific examples of such an alkyl group include a methyl group, an ethyl group, a hexyl group, an octyl group, a trifluoromethyl group, a carboxymethyl group, and a methoxycarbonylmethyl group. Of such R ⁷⁴ , a hydrogen atom and a methyl group are preferable.

  In general formula (5), the aryl group represented by Q may have a substituent, preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms. Examples of the substituent for the aryl group include a halogen atom, an alkyl group, an alkoxy group, and an alkoxycarbonyl group. Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Examples thereof include a phenyl group, a decyloxyphenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, and a butoxycarbonylphenyl group. Among such aryl groups, an unsubstituted aryl group, or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferred, and an unsubstituted aryl group or an aryl group substituted with an alkyl group is particularly preferred. preferable.

In -COOR ⁷⁵ represented by Q in the general formula (5), the alkyl group represented by R ⁷⁵ may have a substituent, preferably an alkyl group having 1 to 12 carbon atoms, particularly carbon. An alkyl group having 1 to 8 atoms is preferred. Examples of the substituent for the alkyl group include a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a carbamoyl group. Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl. Group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 2-bromopropyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl Group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, cyclohexyl Group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, bicyclo [3.2.1] oct-2-yl group, 1-adamantyl group, dimethylaminopropyl group, acetylaminoethyl group, N, N-dibutyl An aminocarbamoylmethyl group etc. are mentioned. Of these alkyl groups, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, an aryl group, or a hydroxyl group is preferred, and an unsubstituted alkyl group is particularly preferred.

In -COOR ⁷⁵ represented by Q in the general formula (5), the aryl group represented by R ⁷⁵ may have a substituent, preferably an aryl group having 6 to 20 carbon atoms, particularly carbon. An aryl group having 6 to 12 atoms is preferred. Examples of the substituent for the aryl group include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, and an acylamino group. Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Phenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodeciloylamidophenyl group, Etc. Among such aryl groups, an unsubstituted aryl group or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferable, and an aryl group substituted with an alkyl group is particularly preferable.

Of such R ⁷⁵ , a hydrogen atom and an alkyl group having 1 to 22 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are particularly preferable.
Specific examples of the branch part of the graft polymer having at least the structural unit represented by the general formula (5) in the branch part include polymethyl (meth) acrylate and poly-n-butyl (meth) acrylate. , Poly-i-butyl (meth) acrylate, copolymer of methyl (meth) acrylate and benzyl (meth) acrylate, copolymer of methyl (meth) acrylate and styrene, methyl (meth) acrylate and (meth) Examples thereof include a copolymer with acrylic acid and a copolymer of methyl (meth) acrylate and acrylonitrile.

Any known method may be used for the synthesis of the graft polymer having at least the structural unit represented by the general formula (5) in the branch.
Specific examples include copolymerization of a macromonomer having at least a structural unit represented by the general formula (5) and an ethylenically unsaturated monomer copolymerizable with the macromonomer.

  Among the macromonomers having at least the structural unit represented by the general formula (5), preferred are those represented by the following general formula (6).

In the general formula (6), R ⁷⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W is a single bond or a single linking group selected from the following linking groups or an arbitrary combination. A represents a group having at least the structural unit represented by the general formula (5).

(Z ¹ and Z ² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, and a hydroxyl group, and Z ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and the number of carbon atoms. 6 to 20 aryl groups are represented.) Specific examples of the macromonomer represented by the general formula (6) include those shown below.

A in the structure is synonymous with A in the general formula (6).
As such macromonomer available as a commercial product, one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6,000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-end methacryloylated poly -N-butyl acrylate oligomer (Mn = 6,000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated polystyrene oligomer (Mn = 6,000, trade name: AS-6, Toa Gosei Chemical Co., Ltd.).

  The molecular weight of the macromonomer is preferably a polystyrene-equivalent number average molecular weight (Mn) of 1,000 to 20,000, and more preferably 2,000 to 15,000. When the number average molecular weight is within the above range, the steric repulsion effect as a pigment dispersant can be more effectively obtained.

  As the ethylenically unsaturated monomer copolymerizable with the macromonomer described above, it is preferable to use the “monomer constituting the pigment adsorption block” in order to improve the dispersibility and dispersion stability of the pigment. Further, as the other copolymerization component, the “monomer constituting a block that is not adsorbed to the pigment” may be copolymerized.

  The weight average molecular weight of the graft polymer is not particularly limited, but is preferably in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.

  Commercially available products of the graft-type polymer include Solsperse 24000, 28000, 32000, 38500, 39000, 35000 (above Lubrizol), Disperbyk-161, -171, -174 (above BYK). Chemie)).

(Terminal modified polymer)
Examples of the terminal-modified polymer include polymers having a functional group at the end of the polymer described in JP-A-9-77994, JP-A-2002-273191, and the like.

A method for synthesizing a polymer having a functional group at the end of the polymer is not particularly limited, and examples thereof include the following methods and a combination thereof.
1. 1. A method of synthesizing by polymerization (for example, radical polymerization, anionic polymerization, cationic polymerization, etc.) using a functional group-containing polymerization initiator Method of synthesizing by radical polymerization using a functional group-containing chain transfer agent The functional group introduced here is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, Examples thereof include a group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. Moreover, you may be a functional group which can be induced | guided | derived to these adsorption sites.

  Examples of the chain transfer agent capable of introducing a functional group at the polymer terminal include mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- ( 2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3- Mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol 3-mercapto-2-butano , Mercaptophenol, 2-mercaptoethylamine, 2-mecarpurimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or oxidized products of these mercapto compounds Examples thereof include disulfide compounds and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

  Moreover, as a polymerization initiator which can introduce | transduce a functional group into a polymer terminal, for example, 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 4,4'- Azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2, 2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide ] Or this Like derivatives of.

  As the monomer used for the polymerization, for example, the above-mentioned “monomer constituting a block that is not adsorbed to the pigment” can be used as the radical polymerizable monomer.

  The molecular weight of the terminal-modified polymer is preferably a weight average molecular weight of 1,000 to 50,000. When the weight average molecular weight is 1,000 or more, the steric repulsion effect as a pigment dispersant can be more effectively obtained, and when it is 50,000 or less, the steric effect is more effectively suppressed, and the pigment The adsorption time can be shortened.

Examples of commercially available terminal-modified polymers include Solsperse 3000, 17000, 27000 (manufactured by Lubrizol).
As the dispersant, the block copolymer, graft polymer, and terminal-modified polymer of the present invention are preferable, and among them, the graft polymer containing a copolymer unit derived from a monomer having an organic dye structure or a heterocyclic structure. A terminal-modified polymer having an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, or a urethane group as a terminal group is particularly preferable.

In the case of a polymer dispersant, the amount of the dispersant added is preferably 0.5 to 100% by weight, more preferably 3 to 100% by weight, and more preferably 5 to 80% by weight with respect to the pigment. % Is particularly preferred. When the amount of the pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimum addition amount of the dispersant is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and the like.
The ratio of the block copolymer of the present invention coated with the pigment and the dispersant is not particularly limited. However, when the dispersant is a polymer dispersant, a ratio of 10/90 to 90/10 is preferable, and in particular, 20 / An 80-80 / 20 mass ratio is preferred.

-Preparation of pigment dispersion composition-
A preferred embodiment of the present invention is a pigment dispersion composition obtained by dispersing the processed pigment coated with the block copolymer of the present invention and a solvent, and if necessary, a dispersant or an alkali-soluble resin.

  The processed pigment of the present invention, a solvent and, if necessary, a dispersant or an alkali-soluble resin are added and kneaded and dispersed. Dispersion is mainly carried out using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., and finely dispersed with beads made of glass having a particle diameter of 0.01 to 1 mm, zirconia, etc., and pigment dispersion A composition is obtained. Kneading with a strong shearing force using a two-roll mill, three-roll mill, ball mill, tron mill, disperser, kneader, kneader, homogenizer, blender, single-screw or twin-screw extruder, etc. before bead dispersion It is also possible to perform distributed processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  The photosensitive composition of the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the processed pigment coated with the block copolymer of the present invention described above, If necessary, an additive such as a surfactant is mixed, and it can be prepared by a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.

  The pigment dispersion of the present invention is suitably used for a colored photosensitive composition used for producing a color filter.

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises the above-described pigment dispersion composition of the present invention, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and other components as necessary. May be included. The details of the pigment dispersion composition of the present invention are as described above. Hereinafter, each component will be described in detail.

<Alkali-soluble resin>
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, polymers having a hydroxyl group, an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are at least one selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. Seeds, particularly preferably CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  As content in the coloring photosensitive composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-12 mass%, Especially preferably, 3 to 10% by mass.

<Photopolymerizable compound>
As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable, and a tetrafunctional or higher functional acrylate compound is more preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

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

The photopolymerizable compound can be used in combination of two or more, in addition to being used alone.
As content in the coloring photosensitive composition of a photopolymerizable compound, 3-55 mass parts is preferable with respect to 100 mass parts of total solid content of this composition, More preferably, it is 10-50 mass parts. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. 4,318,791 and European Patent Publication EP-88050A, benzophenones described in US Pat. Aromatic thiol compounds, etc., (thio) xanthone or acridine compounds described in French Patent Invention 2456741, coumarin or biimidazole compounds described in JP-A-10-62986, JP-A-8 -Sulfonium organoboron complexes, etc., such as 015521 It can be mentioned.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (triazine, halomethyloxadiazole, coumarin), acridine, biimidazole Initiators such as oxime esters are preferred.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Suitable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. Can do.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen compound (for example, triazine-based, oxadiazole-based, or coumarin-based compound) include, for example, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2, 6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl) -s-triazine, , 4-Dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6- Di (chloromethyl) -s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazo 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3 Preferable examples include -phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the coloring photosensitive composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0. % By mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

<Sensitizing dye>
The sensitizing dye is, for example, one that promotes a radical generation reaction of a photopolymerization initiator and a polymerization reaction of a polymerizable compound thereby by exposure at a wavelength that can be absorbed. Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Preferred spectral sensitizing dyes or dyes as sensitizing dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines ( For example, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), Phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll, chlorophyllin, Heart metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

(In General Formula (XIV), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus of the dye in combination with adjacent A ¹ and an adjacent carbon atom. R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.)
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

(In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (XIV).)
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

(In General Formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

(In General Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁶³ , R ⁶³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently represent a monovalent group. Can be bonded to each other to form an aliphatic or aromatic ring.)
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

  In addition, examples of suitable sensitizing dyes used in the present invention include those represented by the following formula (XVIII).

(In General Formula (XVIII), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom or a sulfur atom or —N (R ¹ ) —, and Y represents an oxygen atom or -N (R ¹ )-, wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, and R ¹ , R ² and R ³ each represent A To form an aliphatic or aromatic ring.)

Here, when R ¹ , R ² , and R ³ represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ¹ , R ² and R ³ will be specifically described. Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group, N, N-dialkylureido group, N-arylureido Group, N, N-diarylureido group, N-alkyl-N-arylureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido Group, N, N-dialkyl-N-alkylureido group, N, N-dialkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N- Diaryl-N-alkylureido group, N, N-diaryl-N-arylureido group, N- Alkyl-N-aryl-N-alkylureido group, N-alkyl-N-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N- Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group , Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group Nyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphonate Group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group). ), A phosphonooxy group (—OPO ₃ H ₂₎ and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (—OPO ₃ ( _{aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and as a particularly preferred example of the heteroaryl ring in the heteroaryl group, Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza , Include phenoxazine and the like, it may be further benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonato group, monoaryl phosphono group, aryl phospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , or R ³ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Rubonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N- Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, Methyl Phosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Specific examples of preferred aryl groups as R ¹ , R ² , or R ³ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of the preferred substituted aryl group as R ¹ , R ² , or R ³ include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ² and R ³ include a substituted or unsubstituted alkyl group. Further, more preferred examples of R ¹ include a substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, A in the general formula (XVIII) will be described. A represents an aromatic ring or a heterocyclic ring which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ¹ and R ² in the general formula (XVIII). , Or the same as those exemplified in the above description of R ³ .
Among them, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A includes an aryl group having an amino group.

  Next, Y in the general formula (XVIII) will be described. Y represents a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with the above-described A and adjacent carbon atoms. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

Examples of nitrogen-containing heterocycles include L. G. Brooker et al., Journal of American Chemical Society, J. Am. Chem. Soc., Vol. 73 (1951), p. Any of those known to constitute a basic nucleus in merocyanine dyes described in 5326-5358 and references can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7,6,4,5-thiazoles (eg 4-methoxythianaphtheno-7,6,4,5-thiazole etc.), oxazoles (eg 4-methyl Oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole) 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxyben Zooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),

  Naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, Naphtho [2,1] selenazole, etc.], thiazolines (for example, thiazoline, 4-methylthiazoline, 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5 -Diphenylthiazoline, 4,5-di (p-methoxyphenyl) thi Zoline, etc.), 2-quinolines (for example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6- Ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, Isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), benzimidazoles (eg, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3) -Phenylbenzimidazole, etc.), 3,3-dialkylin Renins (eg, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (eg, pyridine, 5-methylpyridine, Etc.), 4-pyridine (for example, pyridine etc.) and the like. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

  Of the examples of the nitrogen-containing or sulfur-containing heterocycle formed by Y in cooperation with the above-mentioned A and the adjacent carbon atom in the general formula (XVIII) described above, the partial structure of the following general formula (XVIII-2) The dye having the structure represented by the formula is particularly preferable because it provides a photosensitive composition having high sensitizing ability and extremely excellent storage stability. The dye having the structure represented by the general formula (XVIII-2) is a compound described in detail in Japanese Patent Application No. 2003-31253 as a novel compound.

(In General Formula (XVIII-2), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or -N (R ¹ )-. R ¹ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ , R ⁵ and R ⁶ are bonded to each other to form an aliphatic group. Or aromatic ring can be formed.)
In formula (XVIII-2), A and ^{R 1} are the same as in the general formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) And R ⁶ has the same meaning as R ¹ in formula (XVIII).

  Next, the compound represented by formula (XVIII-3), which is a preferred embodiment of the compound represented by formula (XVIII) used in the present invention, will be described.

In the general formula (XVIII-3), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or -N (R ¹ )-. R ¹ , R ⁴ , and R ⁵ are each independently a hydrogen atom or a monovalent non-metallic atomic group, and R ¹ , R ⁴ , and R ⁵ are each bonded to A to be aliphatic or aromatic A family ring can be formed. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In formula (XVIII-3), A and ^{R 1} have the same meanings as in formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) It is synonymous with. Ar represents an aromatic ring or heterocyclic ring having a substituent, and specific examples thereof include an aromatic ring or heterocyclic ring having a substituent among those previously described in the description of A in the general formula (XVIII). The specific example which concerns is mentioned similarly. However, as a substituent that can be introduced into Ar in the general formula (XVIII-3), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (For example, —SOCH ₃ , m: 0.52, p: 0.45), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxyl group (—COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Preferred specific examples of the sensitizing dye represented by the general formula (XVIII) according to the present invention [Exemplary Compound (F1) to Illustrative Compound (F56)] are shown below, but the present invention is not limited to these. Absent.

  Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep part curability.

  The above sensitizing dye can be subjected to various chemical modifications as described below for the purpose of improving the characteristics of the colored photosensitive composition. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, An improvement in the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film can be obtained.

The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1% with respect to the total solid content of the colored photosensitive composition. ˜5 mass%.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

(solvent)
In general, the colored photosensitive composition of the present invention can be suitably prepared using a solvent together with the above components.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently.

-Other components-
In the colored photosensitive composition of the present invention, a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, and other than the above alkali-soluble resin, if necessary. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

(Chain transfer agent)
Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. Examples include a mercapto compound having a heterocyclic ring and an aliphatic polyfunctional mercapto compound.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

<Fluorine organic compounds>
By containing a fluorinated organic compound, liquid properties (particularly fluidity) when the colored photosensitive composition of the present invention is used as a coating liquid can be improved, and uniformity of coating thickness and liquid-saving property can be improved. it can. That is, by reducing the interfacial tension between the substrate and the coating solution, the wettability to the substrate is improved and the coating property to the substrate is improved, so when a thin film of about several μm is formed with a small amount of liquid. Even in such a case, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).
As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (Manufactured by JEMCO).

  The fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Further, it is also effective in slit coating that is liable to cause liquid breakage.

  0.001-2.0 mass% is preferable with respect to the total mass of a coloring photosensitive composition, and, as for the addition amount of a fluorine-type organic compound, More preferably, it is 0.005-1.0 mass%.

<Thermal polymerization initiator>
It is also effective to contain a thermal polymerization initiator in the colored photosensitive composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

<Thermal polymerization component>
It is also effective to contain a thermal polymerization component in the colored photosensitive composition of the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. Examples of the epoxy compound include compounds having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. Examples of bisphenol A type compounds include Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF- 170 and the like (manufactured by Tohto Kasei), Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical) These similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above made by Tohto Kasei), Denacol EM-125, etc. (above made by Nagase Kasei), biphenyl type Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine type epoxy resins, and glycidyl esters in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin can be used.

<Surfactant>
The colored photosensitive composition of the present invention preferably contains various surfactants from the viewpoint of improving coatability. In addition to the above-mentioned fluorosurfactants, various nonionic, cationic and anionic types are available. Surfactants can be used. Of these, fluorine-based surfactants having a perfluoroalkyl group and nonionic surfactants are preferred as the nonionic surfactant.

  Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Kasei Co., Ltd., etc. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

  In addition to the above, various additives can be added to the colored photosensitive composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers And alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.

  Further, when the alkali solubility of the uncured part is promoted and the developability of the colored photosensitive composition is further improved, the colored photosensitive composition contains an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<Thermal polymerization inhibitor>
In addition to the above, a thermal polymerization inhibitor is preferably added to the colored photosensitive composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

The colored photosensitive composition of the present invention is applied to a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc., and a photocurable coating film The film is exposed through a predetermined mask pattern, and after the exposure, the uncured portion is developed and removed with a developer to form a pattern film composed of pixels of each color (three colors or four colors), and a color filter It can be.
In this case, ultraviolet rays such as g-line, h-line, i-line and j-line are particularly preferable as the radiation to be used. For color filters for liquid crystal display devices, exposure using mainly h-line and i-line is preferable in proximity exposure machines and mirror projection exposure machines. In color filters for solid-state image sensors, i-line is mainly used in stepper exposure machines. It is preferable to do.

  The color filter of the present invention is formed on a substrate such as glass using the above-described colored photosensitive composition of the present invention, and the colored photosensitive composition of the present invention is directly or via other layers. Then, after forming a coating film on the substrate by, for example, slit coating, the coating film is dried, subjected to pattern exposure, and development processing using a developer can be sequentially performed. Thereby, the color filter used for a liquid crystal display element and a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.

  Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, and solid-state imaging devices. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, and a plastic substrate. On these substrates, a black matrix for isolating each pixel is usually formed, or a transparent resin layer is provided for promoting adhesion.

  The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface. In addition, the colored photosensitive property of the present invention is also applied to a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is arranged. A color filter can be prepared by forming a patterned film made of the composition. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel. Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of a TFT liquid crystal driving substrate or a surface of the driving substrate can be used.

  A method for applying the colored photosensitive composition of the present invention to a substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as a slit nozzle coating method). Is preferred. In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, when a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. The discharge amount of the colored photosensitive composition from the slit nozzle is usually 500 to 2000 microliter / second, preferably 800 to 1500 microliter / second, and the coating speed is usually 50 to 300 mm / second. , Preferably it is 100-200 mm / sec. The solid content of the photosensitive composition is usually 10 to 20%, preferably 13 to 18%. When forming the coating film by the photosensitive composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is generally 0.3-5.0 micrometers, Preferably it is 0.5-4. It is 0 μm, most preferably 0.5 to 3.0 μm.

Usually, a pre-baking process is performed after application. If necessary, vacuum treatment can be performed before pre-baking. The vacuum drying condition is that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed at a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven or the like, and can be performed under conditions of 10 to 300 seconds. A high frequency treatment or the like may be used in combination. The high frequency treatment can be used alone.

In the development process, the uncured portion after exposure is eluted in the developer, and only the cured portion remains. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer may be used as long as it dissolves the coating film of the photocurable photosensitive composition in the uncured portion, while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

As said organic solvent, the above-mentioned solvent which can be used when preparing the pigment dispersion composition or colored photosensitive composition of this invention is mentioned.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. In addition, development can be performed with the substrate inclined.
In the case of a solid-state image sensor, paddle development is also used.

After the development processing, after a rinsing step for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
The rinsing process is usually performed with pure water. However, to save liquid, pure water is used in the final cleaning. At the beginning of cleaning, used pure water is used, the substrate is tilted and cleaned, and ultrasonic irradiation is performed. Can be used together.

After rinsing, draining and drying are performed, and then a heat treatment of about 200 ° C. to 250 ° C. is usually performed. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.
By sequentially repeating the above operation for each color according to the desired number of hues, a color filter formed with a plurality of colored cured films can be produced.

The use of the colored photosensitive composition of the present invention has been described mainly focusing on the use for a color filter, but it can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter.
The black matrix is formed by exposing and developing the pigment dispersion composition of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-baking as necessary to promote film curing. Can be formed.
<Liquid crystal display element and solid-state image sensor>
The liquid crystal display element and the solid-state image sensor of the present invention comprise the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling and sealing the liquid crystal in the gap portion, the panel which is the liquid crystal display element of the present invention is obtained. It is done. For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

<Synthesis Example of Specific Copolymer of the Present Invention>
(Synthesis of specific copolymer P-1)
MMA 12.6 g, MAA 2.7 g, 2,6-diethyl-2,6-dimethyl-4-oxo-1- (1-phenoxy) piperidine 70.6 g and 1-methoxy-2-propanol 150 g were reacted at a reaction temperature of 145. Stir at 60 ° C. for 60 minutes. MMA 113.4 g and MAA 24.3 g were slowly added to the reaction mixture over 2.5 hours. The temperature of the reaction mixture was then maintained for 5 hours. The residual monomer was distilled off to obtain 135.6 g of MMA-MAA copolymer.
MMA-MAA copolymer (pigment non-adsorbing block described above) and M-11 (pigment adsorbing block described above) 27.0 g together with 460 g of diethylene glycol ethyl ether acetate were heated and stirred at a reaction temperature of 145 ° C. for 2 hours. Thereafter, a 30% solution of the specific copolymer P-1 was obtained.
It was 22000 as a result of measuring the weight average molecular weight of the obtained specific copolymer by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.

(Synthesis of specific copolymer P-2)
In a nitrogen atmosphere, 800 g of THF containing 24 mmol of lithium chloride is maintained at −40 ° C., 52 mmol of sec-butyllithium (SBL) is added with stirring, and 75 g of THF solution containing 25.6 g of M-14 is added dropwise. The reaction was continued for 30 minutes.
Thereafter, a small amount of the reaction solution was taken out from the reaction system, and it was confirmed by gas chromatography (hereinafter abbreviated as GC) that the M-14 monomer was completely consumed.

Next, 50 g of a THF solution containing 126.0 g of MMA and 27.0 g of MAA was added dropwise, and the reaction was continued for 30 minutes. Thereafter, a small amount of the reaction solution was taken out from the reaction system, and after confirming that the monomer was completely consumed by GC, the reaction was stopped with a THF solution containing hydrochloric acid. Thereafter, the reaction stop solution was poured into a large amount of methanol to precipitate a polymer, filtered, washed and dried under reduced pressure to obtain 152 g of a specific copolymer P-2. The obtained specific copolymer P-2 was dissolved in 506 g of 1-methoxy-2-propanol to obtain a 30% solution of the specific copolymer P-2.
It was 25000 as a result of measuring the weight average molecular weight of the obtained specific copolymer P-2 by the gel permeation chromatography method (GPC) which used the polystyrene as the standard substance.
From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.
Similarly, as shown in Table 1, specific copolymers P-3 to P-10 were synthesized by changing the pigment adsorbing parts and polymer compositions of P-1 to P-2.

  In Table 1, MAA is methacrylic acid, MMA is methyl methacrylate, and BzMA is benzyl methacrylate.

<Examples of pigment processing>
50 g of the pigment described in Tables 2 to 7, 500 g of sodium chloride, 25 g of the specific copolymer or comparative polymer compound solution, and 100 g of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture is poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to give a specific copolymer or comparative polymer compound. A processed pigment coated with was obtained.

(Measurement of average primary particle diameter of processed pigment)
The average primary particle diameter of the obtained processed pigment was obtained by observing with a transmission electron microscope (TEM), measuring 100 particle sizes at a portion where the particles were not aggregated, and calculating the average value. .

(Evaluation of pigment coverage)
10 g of the obtained processed pigment was put into 100 mL of 1-methoxy-2-propanol, and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was precipitated with a centrifugal separator at 80,000 rpm for 8 hours. The solid content of the supernatant was determined from the drying method. The amount of the specific copolymer or comparative polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio with the specific copolymer or comparative polymer compound used in the treatment. The smaller the liberation rate, the higher the degree of coverage on the pigment.

Details of the compounds in Table 2 are as follows.
PR254: C.I. I. Pigment Red 254
Q-1: Methyl methacrylate / methacrylic acid = 85/15% by mass copolymer, weight average molecular weight 20,000, acid value 98 mgKOH / g
Q-2: Trimethylolpropane triacrylate

Details of the compounds in Table 3 are as follows.
PR177: C.I. I. Pigment Red 177
Q-2: trimethylolpropane triacrylate Q-3: cyclohexyl methacrylate / methacrylic acid = 85/15 wt% copolymer, weight average molecular weight 20,000, acid value 98 mgKOH / g

Details of the compounds in Table 4 are as follows.
PG36: C.I. I. Pigment Green 36
Q-1: Methyl methacrylate / methacrylic acid = 85/15% by weight copolymer, weight average molecular weight 20,000, acid value 98 mgKOH / g
Q-2: Trimethylolpropane triacrylate

Details of the compounds in Table 5 are as follows.
PY150: C.I. I. Pigment Yellow 150
Q-2: trimethylolpropane triacrylate Q-3: cyclohexyl methacrylate / methacrylic acid = 85/15 wt% copolymer, weight average molecular weight 20,000, acid value 98 mgKOH / g

Details of the compounds in Table 6 are as follows.
PB15: 6: C.I. I. Pigment Blue 15: 6
Q-2: trimethylolpropane triacrylate Q-3: cyclohexyl methacrylate / methacrylic acid = 85/15 wt% copolymer, weight average molecular weight 20,000, acid value 98 mgKOH / g

Details of the compounds in Table 7 are as follows.
PV23: C.I. I. Pigment Violet 23
Q-1: Methyl methacrylate / methacrylic acid = 85/15% by weight copolymer, weight average molecular weight 20,000, acid value 98 mgKOH / g
Q-2: Trimethylolpropane triacrylate

[Example 2, Comparative Example 2]
<Preparation of pigment dispersion composition>
The components of the following composition (1) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (1)]
・ Processed pigment (pigment described in Table 2) 95 parts ・ Derivative A (the following structure [Chemical Formula 28]) 5 parts ・ Dispersant (30% 1-methoxy-2-propyl acetate solution of dispersant described in Table 8) (Table 8)
750 parts of 1-methoxy-2-propyl acetate Subsequently, the mixed solution obtained above was further subjected to dispersion treatment for 6 hours with a bead disperser Dispermat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2,000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition shown in Table 8.

<Evaluation of pigment dispersion composition>
The following evaluation was performed about the obtained pigment dispersion composition. The results are shown in Table 8.
(1) Measurement and Evaluation of Viscosity For the obtained pigment dispersion composition, using an E-type viscometer (20 rpm, 30 ° C., manufactured by Tokyo Keiki Co., Ltd.), the viscosity η1 of the pigment dispersion composition immediately after dispersion, and The viscosity η2 of the pigment dispersion composition after 1 week after dispersion (at room temperature) was measured to evaluate the degree of thickening. Here, the low viscosity indicates that the increase in viscosity due to the dispersant is suppressed, and the dispersibility and dispersion stability of the pigment are good.

(2) Measurement and Evaluation of Contrast The obtained pigment dispersion composition was applied on a glass substrate, and a sample was prepared so that the thickness of the coating film after drying was 1 μm. The coated substrate is placed between two polarizing plates, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured by BM-5 Topcon Co., Ltd., contrast = luminance when parallel / right luminance when orthogonal. I asked for it. A high contrast indicates that the pigment is uniformly dispersed in a highly miniaturized state, so that the transmittance, that is, the coloring power is high.

(3) Evaluation of Precipitation The pigment dispersion composition obtained on a 100 mm × 100 mm glass substrate (trade name: 1737 manufactured by Corning) was applied so as to have a film thickness of 2.0 μm, and was subjected to 60 in an oven at 90 ° C. Dried for 2 seconds. Thereafter, the coating film was heat-treated (post-baked) for 30 minutes in an oven at 230 ° C., and the presence or absence of deposits on the cured film was confirmed with an optical microscope (manufactured by Olympus Corporation) at a magnification of 100. The post-baking process was repeated and observed each time. The higher the score, the more difficult it is to precipitate and the better the transparency of the colored pattern.
4: Generation of precipitate at the fourth post-baking 3: Generation of precipitate at the third post-baking 2: Generation of precipitate at the second post-baking 1: Generation of precipitate at the first post-baking

  From the results of Table 8, the photosensitive compositions of Example 2-1 to Example 2-8 using the processed pigment coated with the block copolymer having the pigment adsorbing block and the pigment non-adsorbing block of the present invention are as follows. It can be seen that the contrast is high compared to Comparative Examples 2-1 to 2-2, it is difficult to deposit by post-baking, and the thickening with time is small.

<Preparation of pigment dispersion composition>
The components of the following composition (2) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (2)]
Processed pigment (pigments listed in Tables 4 and 6) 100 parts Dispersant (30% 1-methoxy-2-propyl acetate solution of dispersant listed in Table 9)
(Amounts listed in Table 9)
・ 750 parts of 1-methoxy-2-propyl acetate

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3 using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition shown in Table 9.

<Evaluation of pigment dispersion composition>
The following evaluation was performed about the obtained pigment dispersion composition. The experimental method and the evaluation method are the same as the composition (1). The results are shown in Table 9.
(1) Viscosity measurement and evaluation (2) Contrast measurement and evaluation (3) Precipitation evaluation

  Since the absolute value of contrast varies depending on the hue, Table 9 compares between green and blue. From the results of Table 9, the photosensitive composition of the present example using the processed pigment coated with the specific copolymer of the present invention is suppressed in thickening with time, has high contrast, and does not easily precipitate by post-baking. I understand that.

[Example 3, Comparative Example 3]
<Preparation of pigment dispersion composition>
The components of the following composition (3) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (3)]
-Processed pigment (processed pigment described in Table 10) 120 parts-Dispersant (30% 1-methoxy-2-propyl acetate solution of the dispersant described in Table 10) 250 parts-1-methoxy-2-propyl acetate 750 Part

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2,000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain pigment dispersion compositions shown in Table 10.

<Preparation of colored photosensitive composition>
Using the obtained pigment dispersion composition, the following colored photosensitive composition was prepared.
Pigment dispersion (pigment dispersion described in Table 11) 2000 parts Dipentaerythritol hexaacrylate 80 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 30 parts (photopolymerization initiator)
-Benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) propylene glycol monomethyl ether acetate solution (solid content 30%) 300 parts (alkali-soluble resin)
・ 390 parts of 1-methoxy-2-propyl acetate (solvent)

<Preparation of color filter using colored photosensitive composition>
The obtained colored photosensitive composition (color resist solution) was placed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning), Examples 3-1 to 3-6 and Comparative Examples 3-1 and 3-2. Is applied so that the x value as an index of color density is 0.650, and Examples 3-7 and 3-8 and Comparative Examples 3-3 and 3-4 have a y value of 0 as an index of color density. In the examples 3-9 and 3-10 and in the comparative examples 3-5 and 3-6, the y value serving as an index of color density is 0.100, and 90 It was dried in an oven at 60 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 11.

(1) Contrast A polarizing plate is placed on the colored resin film of the colored filter substrate obtained above, and the colored resin film is sandwiched between them. The luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal are BM- manufactured by Topcon Corporation. A value obtained by dividing the luminance at the time of parallel by the luminance at the time of orthogonality (= the luminance at the time of paralleling / the luminance at the time of orthogonality) was used as an index for evaluating the contrast. Larger values indicate higher contrast.

(2) Alkaline developer solubility 100 g of a 10% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by FUJIFILM Electronics Materials) is weighed into a 150 ml beaker. The colored photosensitive composition is applied to a 100 mm × 100 mm glass substrate (trade name: manufactured by 1737 Corning) to a thickness of 2.5 μm and dried in an oven at 90 ° C. for 60 seconds (prebaking). The glass substrate is cut to 25 mm × 100 mm, and two of them are overlapped so that the coated surface is on the outside, soaked in a pre-prepared developer, and pulled up and down 20 times. Repeatedly, the solubility of the uncured film and the presence or absence of the suspension in the alkaline developer were visually judged. The higher the score, the better the alkali solubility.

* Judgment method 5: Uncured film is completely dissolved in up and down movements 1 to 10 times and no suspension in alkaline developer 4: Uncured film is completely dissolved in up and down movements 11 to 20 times and alkali development No suspension in liquid 3: Uncured film is completely dissolved in up and down movements 1 to 10 times, but there is suspension in alkaline developer 2: Uncured film is completely dissolved in up and down movements 11 to 20 times However, there is a suspension in the alkali developer 1: Uncured film is insoluble even after 20 vertical movements

(3) Precipitation evaluation A colored photosensitive composition was applied on a 100 mm × 100 mm glass substrate (trade name: 1737 manufactured by Corning) so as to have a film thickness of 2.0 μm, and dried in an oven at 90 ° C. for 60 seconds ( Pre-baked). Thereafter, exposure was performed at 100 mJ / cm 2 with a mask having a line width of 20 μm (illuminance is 20 mW / cm 2), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) And developed at 25 ° C.
As described above, the coating film subjected to the photocuring treatment and the development treatment was subjected to a heat treatment (post-bake) for 30 minutes in an oven at 230 ° C., and the presence or absence of precipitation on the pattern was confirmed with an optical microscope. This was repeated three more times for the same evaluation. It shows that it is hard to precipitate, so that a score is high.
Precipitation after 4th post-bake: 4
Precipitation after the third post-bake: 3
Precipitation after second bake: 2
Precipitation after first bake: 1

  In Table 11, the hue of the color filter varies depending on the test level. In particular, contrast cannot be compared between different hues. For this reason, comparison is made between the same hues, that is, between DRs, DGs, and DBs. It can be seen that the example which is a color filter using the processed pigment of the present invention has higher contrast, better alkali developer solubility than the comparative example, and is less likely to precipitate by post-baking.

[Example 4, Comparative Example 4]
<Preparation of pigment dispersion composition>
Components of the following composition (4) are mixed, and the number of revolutions is 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (4)]
-Processed pigment (processed pigment described in Table 12) 110 parts-Dispersant D-3 (30% 1-methoxy-2-propyl acetate solution)
250 parts ・ Pigment derivative B (the following structure [Chemical Formula 29]) 20 parts ・ 1-methoxy-2-propyl acetate 750 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain pigment dispersion compositions shown in Table 12.

<Preparation of colored photosensitive composition>
Using the obtained pigment dispersion composition, the following colored photosensitive composition was prepared.
Pigment dispersion (pigment dispersion described in Table 13) 2100 parts Dipentaerythritol hexaacrylate 90 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 30 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 30%) 300 parts (alkali-soluble resin)
・ 390 parts of 1-methoxy-2-propyl acetate (solvent)

<Preparation of color filter using colored photosensitive composition>
The obtained colored photosensitive composition (color resist solution) was placed on Examples 100-1 to 4-3 and Comparative Examples 4-1 and 4-2 on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning). Is applied so that the x value as an index of color density is 0.650, and Examples 4-4 to 4-6 and Comparative Examples 4-3 and 4-4 have a y value of 0 as an index of color density. In addition, Examples 4-7 to 4-9 and Comparative Examples 4-5 and 4-6 were applied so that the y value as an index of color density was 0.100. It was dried in an oven at 60 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated for contrast and alkali developer solubility in the same manner as in Table 11 above. The results are shown in Table 13.
(1) Contrast (2) Alkaline developer solubility

(3) Voltage holding ratio A colored photosensitive composition is applied to a glass substrate with an ITO electrode (trade name: 1737 manufactured by Corning) so as to have a film thickness of 2.0 μm, and dried in an oven at 90 ° C. for 60 seconds ( Pre-baked). Thereafter, exposure is performed at 100 mJ / cm ² without using a mask (illuminance is 20 mW / cm ² ), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) is used. The coating film was developed at 25 ° C. and subjected to heat treatment (post-baking) for 30 minutes in an oven at 230 ° C. Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 μm glass beads, and then liquid crystal MJ971189 (trade name) manufactured by Merck Co., Ltd. Was injected to prepare a liquid crystal cell.

  Next, after putting the liquid crystal cell in a constant temperature layer at 70 ° C. for 48 hours, the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica Co., Ltd. The higher the score, the higher the voltage holding ratio and the better electrical characteristics.

Measurement conditions / Distance between electrodes: Approximately 5 μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec
* Voltage holding ratio: liquid crystal cell potential difference after 16.7 milliseconds / value of voltage applied in 0 milliseconds * judgment method 90% or more: 5
85 to less than 90%: 4
80 to less than 85%: 3
75 to less than 80%: 2
Less than 75%: 1

  In Table 13, the hue of the color filter varies depending on the test level. In particular, contrast cannot be compared between different hues. Therefore, comparison is made between the same colors, that is, between DLs, DYs, and DVs. It can be seen that the example which is a color filter using the processed pigment of the present invention has higher contrast, better alkali developer solubility and higher voltage holding ratio than the comparative example.

[Example 5, Comparative Example 5]
<Preparation of colored photosensitive composition>
The following colored photosensitive composition was produced using the pigment dispersion composition obtained previously.
-Pigment dispersion A (pigment dispersion described in Table 14A column) 2000 parts-Pigment dispersion B (pigment dispersion described in Table 14B column) 1000 parts-Dipentaerythritol hexaacrylate 120 parts (photopolymerizable compound)
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 50 parts (photopolymerization initiator)
Benzyl methacrylate / methacrylic acid (= 75/35 [mass ratio]) copolymer (weight average molecular weight: 10,000) propylene glycol monomethyl ether acetate solution (solid content 30%) 300 parts (alkali-soluble resin)
・ 390 parts of 1-methoxy-2-propyl acetate (solvent)

<Preparation of color filter using colored photosensitive composition>
Examples 5-1 and 5-2 and Comparative Example 5-1 have the color density of the obtained colored photosensitive composition (color resist solution) on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning). Application was performed so that the x value as an index was 0.650, and Examples 5-3 and 5-4 and Comparative Example 5-2 were applied so that the y value as an index of color density was 0.600. In Examples 5-5 and 5-6 and Comparative Example 5-3, the y value serving as an index of color density was applied to be 0.100 and dried in an oven at 90 ° C. for 60 seconds (prebaking). . Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 14.
(1) Contrast (2) Alkali developer soluble (3) A colored photosensitive composition is applied on a glass substrate with a crystal-precipitating ITO electrode (trade name: 1737 manufactured by Corning) to a thickness of 2.0 μm. And drying (pre-baking) for 60 seconds in an oven at 90 ° C. Thereafter, exposure is performed at 100 mJ / cm ² without using a mask (illuminance is 20 mW / cm ² ), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) is used. The coating film was developed at 25 ° C. and subjected to heat treatment (post-baking) for 30 minutes in an oven at 230 ° C. Next, the substrate on which this pixel was formed and the substrate on which the ITO electrode was deposited in a predetermined shape were placed in a high-temperature layer at 70 ° C. and 80% humidity for 72 hours, and then the crystal precipitation on the substrate was visually evaluated. It was summarized in. The higher the score, the harder the crystals are precipitated and the more transparent the colored pattern.
3: No crystal precipitation is observed 2: Slight crystal precipitation is observed 1: Crystal precipitation is observed on the entire substrate surface

  In Table 14, the hue of the color filter varies depending on the test level. In particular, contrast cannot be compared between different hues. Therefore, comparison is made between the same colors, that is, between DRs, DGs, and DBs. It can be seen that the example which is a color filter using the processed pigment of the present invention has higher contrast, better alkali developer solubility than the comparative example, and hardly causes crystal precipitation in post-baking.

<Compounds in Examples>

D-1: MM-1 / A-1 / MAA = 20/65/15% by mass, polymer having a weight average molecular weight of 23,000 and an acid value of 100 mgKOH / g D-2: MM-2 / A-1 / BzMA / MAA = 10/58/20/12 mass%, weight average molecular weight 23,000, polymer D-3 having an acid value of 100 mgKOH / g: “Solsperse 24000” manufactured by Lubrizol
D-4: St / MAA = 75/15 mass%, polymer having a weight average molecular weight of 20,000 and an acid value of 100 mgKOH / g

D-5: MM-1 / BzMA / MAA = 20/65/15% by mass, polymer having a weight average molecular weight of 20,000 and an acid value of 100 mgKOH / g D-6: St / A-1 / MAA = 30 / Polymer of 55/15% by mass, weight average molecular weight 25,000, acid value 100 mgKOH / g

A-1: Terminal methacryloylated polymethyl methacrylate (number average molecular weight 6,000)
MAA: methacrylic acid BzMA: benzyl methacrylate St: styrene

Claims (14)

A pigment, a block copolymer having a pigment adsorbing block and a pigment non-adsorbing block, a water-soluble inorganic salt, and a water-soluble organic solvent that does not dissolve the water-soluble inorganic salt, in the refinement step of the pigment A processed pigment formed by mechanically kneading to coat the pigment with the block copolymer,
The block copolymer has neither a pigment-adsorbing block composed of one or more monomers having an organic dye structure or a heterocyclic structure, nor an organic dye structure or a heterocyclic structure. ) acrylate ester le; crotonic acid ester le; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester Le; (meth) acrylamide; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene , Isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene, hydroxy styrene protected with groups deprotectable by acidic substances, vinyl benzoic acid Methyl , And alpha-1 one styrene compound selected from styrene; Biniruete Le; Biniruketo emissions; olefin emissions; maleimide, butyl maleimide, cyclohexyl maleimide, and one maleimide de compound selected from phenylmaleimide; and (meth) acrylonitrile anda pigment non-adsorbing blocks configured with one or more monomers selected from the group consisting of anionic living process, or a block copolymer prepared by radical living method processed pigment.   The processed pigment according to claim 1, wherein the block copolymer has a weight average molecular weight of 1,000 or more and 100,000 or less.   The processed pigment according to claim 1 or 2, wherein the average primary particle diameter is 5 nm or more and 25 nm or less.   The processed pigment according to any one of claims 1 to 3, wherein the pigment refining step further includes a pigment drying step.   The addition amount of the inorganic salt in the pigment refinement step is 5 to 25 times by mass with respect to the pigment, and the addition amount of the water-soluble organic solvent is 15 to 15% by mass with respect to the inorganic salt. It is 35 mass%, The processed pigment of any one of Claims 1-4 characterized by the above-mentioned.   A pigment dispersion composition comprising the processed pigment according to any one of claims 1 to 5 dispersed in an organic solvent.   The pigment dispersion composition according to claim 6, further comprising a pigment dispersant.   The pigment dispersion composition according to claim 6 or 7, which is used for forming a colored region in a color filter.   A colored photosensitive composition comprising the pigment dispersion composition according to any one of claims 6 to 8, a photopolymerizable compound, and a photopolymerization initiator.   A color filter comprising a colored region formed of the colored photosensitive composition according to claim 9 on a substrate.   A liquid crystal display element comprising the color filter according to claim 10.   A solid-state imaging device comprising the color filter according to claim 10. A pigment, a water-soluble inorganic salt, a water-soluble organic solvent which does not dissolve the water-soluble inorganic salt, a pigment adsorbing block configured with one or more monomers having an organic dye structure or a heterocyclic structure, an organic no any of dye structure or a heterocyclic structure, (meth) acrylic acid ester le; crotonic acid ester le; vinyl ester le; maleic acid diester Le; fumarate diester Le: itaconic acid diester Le; (meth) acrylic Ami de; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichloro styrene, bromostyrene, chloromethylstyrene, acidic substance Protected with a deprotectable group Hydroxy styrene, methyl vinyl benzoate, and α- methylstyrene one styrene compound selected from; Biniruete le; Biniruketo emissions; olefin emissions; maleimide, butyl maleimide, cyclohexyl maleimide, and one selected from phenylmaleimide maleimide de compounds; and (meth) anda pigment non-adsorbing blocks configured with one or more monomers selected from the group consisting of acrylonitrile, anionic living process, or block produced by radical living method A step of mechanically kneading the copolymer to prepare a mixture, and
A process for producing a processed pigment, comprising: adding the obtained mixture into water and stirring to prepare a slurry containing the pigment coated with the block copolymer.   The method for producing a processed pigment according to claim 13, further comprising a step of drying the pigment coated with the block copolymer contained in the obtained slurry.