JP5191194B2 - Processed pigment, pigment dispersion composition using the same, colored photosensitive composition, and color filter - Google Patents

Abstract

Provided are a processed pigment excellent in dispersibility and dispersion stability, a pigment-dispersed composition excellent in dispersibility and dispersion stability of a pigment that uses the processed pigment, a colored photosensitive composition using the pigment-dispersed composition, and a color filter having improved color properties that uses the colored photosensitive composition, in which a pigment is covered with at least one of a specific polymer compound selected from the following (SP-1) to (SP-3); (SP-1) A polymer compound having a heterocycle on a side chain, (SP-2) A graft polymer compound having a weight average molecular weight of from 1,000 to 100000, (SP-3) A polymer compound represented by the following formula (3-1), wherein, RC, RD, A1 and P1 respectively represent an organic linkage group, a single bond or a divalent organic linkage group, a monovalent organic group containing such as an organic dye structure, and a polymer skeleton.

Description

  The present invention is excellent in pigment dispersibility, excellent in fluidity and coloring power of the pigment dispersion composition and colored photosensitive composition, 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 dispersion composition, a colored photosensitive composition containing the same, and a color filter produced using the colored photosensitive composition.

  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).
Also, a pigment dispersion composition that uses a polymer compound having a heterocyclic ring in the side chain during the dispersion step as a dispersant in the pigment dispersion step, and has excellent dispersion stability and can form a high-contrast color pattern for color filters. In addition, a technique for obtaining a colored photosensitive composition and a color filter has also been proposed (see, for example, Patent Document 3).
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.
Japanese Patent No. 3130217 JP 2004-233727 A JP 2003-26950 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, Is to provide a processed pigment excellent in dispersion stability in which dispersed primary particles are stably maintained.
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 dispersant. It is to provide a composition.
Another object of the present invention is to provide a color filter having a good color characteristic with a high contrast and small color density unevenness, which has a colored pattern using the colored photosensitive composition of the present invention.

The present inventors have found that the above problems can be achieved by the following method, and have reached the present invention.
<1> including a repeating unit having an unsaturated nitrogen-containing heterocyclic ring in a side chain derived from at least one monomer selected from the group consisting of M- 1 to M-27 and M-31 described below; machining pigment formed by coating a pigment with a polymeric compound having a carboxyl group in the range of 50 mg KOH / g or more 200 mg KOH / g.
<2> Repeating units having an unsaturated nitrogen-containing heterocycle in the side chain are M-1, M-4, M-6, M-11, M-14, M-15, M-25 and M described later. The processed pigment according to <1>, which is a repeating unit derived from at least one monomer selected from the group consisting of -31.
<3> The average primary particle diameter, Ru der least 25nm or less 5 nm <1> or processing Pigments according to <2>.
< 4> The processing according to any one of <1> to <3>, wherein a liberated amount of the polymer compound when the processed pigment is washed with 1-methoxy-2-propanol is 30% by mass or less. Pigments.
<5> processed pigment according to the above-described polymer compound, was prepared by adding a pigment refining process <1> in any one of <4>.

<6><1> a processed pigment according to any one of <5> to, Ru Pigment dispersion composition Na was dispersed in an organic solvent.
<7> The pigment dispersion composition according to <6> , further comprising a pigment dispersant.
<8> Ru is used for the formation of colored regions in the color filter <6> or pigment dispersion composition according to <7>.
<9> pigment dispersion composition according to any one of <6> to <8>, a photopolymerizable compound, and wearing colored photosensitive composition you a photopolymerization initiator.
<10> The colored photosensitive composition according to <9>, wherein the photopolymerization initiator is an s-triazine photopolymerization initiator.
<11> The colored photosensitive composition according to <9> or <10>, wherein the photopolymerizable compound is a tetrafunctional or higher functional acrylate compound.
<12> onto a substrate, Luca color filter having a colored region formed by the colored photosensitive composition according to any one of <11> to <9>.
<13> Ru comprising the color filter according to <12> liquid crystal display device.
<14> solid-state imaging device that includes a color filter according to <12>.

In yet a preferred embodiment <15> before Symbol high molecular compound, wherein the weight average molecular weight from 1,000 to 100,000 <1> processed pigment according Incidentally, "free volume" in <4> Is a surface treatment agent obtained by immersing a processed pigment in 1-methoxy-2-propanol as a solvent and dissolving in the solvent (in the present invention, the polymer compound (hereinafter referred to as “ polymer compound having a heterocyclic ring in a side chain ” ). The amount of the surface treatment agent used is divided by the amount of the surface treatment agent used.

The present invention relates to a processed pigment coated with a polymer compound having a heterocyclic ring in a side chain, and its application. By using this processed pigment, the present invention is superior in dispersibility and dispersion stability than the conventional ones. A pigment dispersion composition and color filter with high contrast and small color density unevenness can be obtained.
That is, when the polymer compound having a heterocyclic ring in the side chain of the present invention is used for pigment treatment, formation of secondary aggregates, which are aggregates of primary particles of pigment, is effectively suppressed, or secondary aggregates It is considered that the cohesive force of 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 polymer compound used for coating has a heterocyclic ring in the side chain, the structure and the pigment have a strong electrostatic interaction, and the polymer compound is strong. Due to the intermolecular force, the polymer compound is strongly adsorbed on the primary pigment particles, and the coated polymer compound is not desorbed even during slurry, filtration, and water washing. It is thought that it is suppressing.

  In the present invention, it is one of the features that the pigment is coated with a specific polymer compound to obtain a processed pigment, and it is particularly effective to apply the coating simultaneously with the step of refining the primary particles of the pigment. . That is, as in Patent Document 3, in the dispersion step after the miniaturization step, the surface activity generated by the miniaturization is compared with a method in which the graft polymer compound containing a heterocyclic ring is adsorbed to stabilize the dispersion. The polymer compound having a heterocyclic ring in the side chain of the present invention is adsorbed by a strong electrostatic action on the new interface of the high pigment, and forms a strong coating layer of the polymer compound. It is thought that the processed pigment which has is obtained. That is, in the present invention, the coated pigment is hardly liberated after processing with an organic solvent that dissolves the polymer. On the other hand, with the pigment in Patent Document 3, when the polymer compound is washed with an organic solvent, many of the polymer compounds that are dispersants are desorbed from the pigment, so that the finely divided pigment is likely to aggregate and high dispersion stability can be obtained. There is nothing.

  In addition, the color filter using the processed pigment coated with the polymer compound having a heterocyclic ring in the side chain of the present invention solves the problem that the color filter layer becomes cloudy at high temperature and high humidity, and becomes cloudy when the color filter is created. it can. 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 polymer compound having a heterocyclic ring in the side chain according to the present invention has a high molecular compound having a heterocyclic ring in the side chain strongly adsorbed to the fine pigment. This is considered to be because the aggregation between each other is effectively suppressed.

  Furthermore, the color filter using the processed pigment coated with the polymer compound having a heterocyclic ring in the side chain 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 polymer compound having a heterocyclic ring in the side chain of the present invention is strongly adsorbed to the fine pigment for the reason described above. This is thought to be because it is possible to effectively suppress the elution of.

In addition, the colored photosensitive composition using the processed pigment coated with the polymer compound having a heterocyclic ring in the side chain of the present invention has an advantage that precipitates are hardly generated in the developing solution in the development process of color filter production. have. 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 polymer compound is strongly adsorbed to the fine pigment, the polymer compound is not desorbed even by an alkaline developer, and it is considered that precipitates are hardly generated in the developer.
When the polymer compound having a heterocyclic ring in the side chain disclosed in Patent Document 3 is used as a pigment dispersant in the dispersion step, since the adsorption to the pigment is insufficient, these effects cannot be sufficiently exhibited. These performances have not been improved.

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 in which is stably maintained.
According to the present invention, by using the processed pigment of the present invention, a pigment dispersion composition having excellent pigment dispersibility and dispersion stability, and a case of containing a large amount of pigment comprising such a pigment dispersant However, a colored photosensitive composition having excellent curability 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.

Hereinafter, the present invention will be described in detail.
<Processed pigment>
The processed pigment of the present invention is characterized by being coated with a polymer compound having a heterocyclic ring in the side chain.
The production of such finely processed pigments consists of i) pigments, ii) water-soluble inorganic salts, iii) small amounts of water-soluble organic solvents that do not substantially dissolve ii), and iv) heterocyclic rings in the side chain. A step of mechanically kneading with a kneader or the like (this step is referred to as salt milling), a step of adding this mixture into water, stirring with a high-speed mixer or the like to form a slurry, 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, at the time of salt milling, by using iv) at least a partly soluble resin in combination with the above iii) organic solvent, the surface is further refined and iv) coated with at least a partly soluble resin. A processed pigment with little aggregation of the pigment is 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, the timing which adds the high molecular compound which has a iv) heterocyclic ring in a side chain may add all at the initial stage of a salt milling process, and may divide and add.

[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 photocurable composition containing the same, 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, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. 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. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. 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. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, when the ratio exceeds 100: 200, the dominant wavelength tends to be longer and the deviation from the NTSC target hue may become large. 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. If it is 100: 61 or more, the dispersion stability may decrease.

[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 is 50% by mass or more, the kneaded composition becomes too soft and the kneaded composition is less likely to be sheared, 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) Polymer compound having a heterocyclic ring in the side chain]
The polymer compound used in the present invention is not particularly limited as long as it is a polymer compound having a heterocyclic ring in the side chain.
Such a polymer compound is preferably a monomer represented by the following general formula (1) or a polymer containing a polymer unit derived from a monomer comprising a maleimide or a maleimide derivative. A polymer containing a polymer unit derived from the monomer represented by the general formula (1) is particularly preferable.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
As the alkyl group for R ¹ , an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of the preferred alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ¹ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
The alkylene group represented by R ² may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

  In general formula (1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

  Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formulas (2), (3), and (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  In the polymer compound having a heterocyclic ring in the side chain of the present invention, preferred specific examples of the monomer represented by the following general formula (1), maleimide, and maleimide derivatives are listed below, but the present invention is not limited thereto. It is not something.

The iv) polymer compound having a heterocyclic ring in the side chain used in the present invention contains only one type of copolymer unit derived from the monomer represented by the general formula (1), maleimide, and maleimide derivative. There may be two or more kinds.
In the polymer compound having a heterocyclic ring in the side chain of the present invention, the content of the copolymer unit derived from the monomer represented by the general formula (1), maleimide, and maleimide derivative is not particularly limited. Copolymer derived from monomer represented by general formula (1), maleimide, and maleimide derivative when the total structural unit contained in the polymer compound having a heterocyclic ring in the side chain of the invention is 100% by mass It is preferable to contain 5 mass% or more of a unit, and it is more preferable to contain 10-50 mass%. Among the monomers represented by the general formula (1), maleimide, and maleimide derivatives, the monomer represented by the general formula (1) is preferable because of its high adsorptivity to the pigment.

  That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively weaken the cohesive force of the secondary aggregates, it is represented by the general formula (1). The content of the copolymer unit derived from the monomer, maleimide, and maleimide derivative is preferably 5% by mass or more. From the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the content of copolymer units derived from the monomer represented by the general formula (1) Is preferably 50% by mass or less.

The polymer compound having a heterocyclic ring in the side chain of the present invention preferably further contains a copolymer unit derived from a monomer having an acid group. When the polymer compound further contains a copolymer unit derived from a monomer having an acid group, when the pigment dispersion composition is applied to the photosensitive composition, the development removability of the unexposed area is excellent.
As monomers having an acid group, 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-polycaprolacto It can be mentioned mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate. The polymer compound 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.

  In the polymer compound having a heterocyclic ring in the side chain of the present invention, the content of the copolymer unit derived from the monomer having an acid group is preferably 50 to 200 mgKOH / g, particularly preferably 80 to 200 mgKOH / g. g. A more preferable range is 100 to 180 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of copolymer units derived from the monomer having an acid group is preferably 50 mgKOH / g or more. When the acid value is 200 mgKOH / g or more, aggregation between acid groups becomes strong, aggregation between processed pigments occurs, and dispersibility deteriorates. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively weaken the cohesive force of the secondary aggregates, it is derived from a monomer having an acid group. The content of the copolymerized unit is preferably in the above range.

In the present invention, the polymer compound having a heterocyclic ring in the side chain may further contain a copolymer unit 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. Specific examples of such vinyl monomers include the following compounds. 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 preferred molecular weight of the polymer compound having a heterocyclic ring in the side chain 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). It is preferable that it is the range of these. 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 weight average molecular weight (Mw) of the polymer compound having a heterocyclic ring is preferably 1,000 or more. From the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the weight average molecular weight (Mw) of the polymer compound having a heterocyclic ring in the side chain of the present invention is It is preferable that it is 100,000 or less.
In the pigment dispersion composition of the present invention, the content of the polymer compound having iv) a heterocyclic ring in the side chain according to the present invention is by mass, i) pigment: iv) the polymer compound having a heterocyclic ring in the side chain = 1: 0.01 to 1: 2 is preferable, more preferably 1: 0.05 to 1: 1, and still more preferably 1: 0.1 to 1: 0.6.

The iv) polymer compound having a heterocyclic ring in the side chain includes, for example, a monomer represented by the general formula (1), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component. And can be produced by an ordinary radical polymerization method. In general, a suspension polymerization method or a solution polymerization method is used. Solvents used in the synthesis of such polymers include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl. Examples include acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. . 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 i) pigment particles such as organic pigments are coated with a polymer compound having iv) a heterocyclic ring in the side chain, and the polymer compound is a part of the pigment particle surface or The effect of the present invention is achieved by being firmly coated all over, 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 (release rate) of the polymer compound by washing with an organic solvent described below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed, but in the case of a processed pigment whose surface is coated as in the present invention, it is liberated. The rate is very small, 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 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 allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound 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%.

If necessary, other compounds may be used at the same time in addition to the specific polymer compound described above. 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. Natural resins, modified natural resins, synthetic resins, natural resins 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 is a processed pigment excellent in dispersibility and dispersion stability because the pigment surface is firmly coated with the polymer compound and does not release even when immersed in an organic solvent. The application range is wide, and it is particularly useful for the preparation of a pigment dispersion composition.

<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 photocurable composition to be described later, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass from the viewpoint of handleability. Can do.

[(A) Pigment derivative]
A pigment derivative is added to the pigment dispersion composition of the present invention as necessary. The pigment is introduced into the photocurable composition as fine particles by adsorbing the pigment derivative with a part having affinity with the dispersant or a polar group to the pigment surface and using it 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 polymer compound having a weight average molecular weight of 1,000 or more having a heterocyclic ring in the side chain of the present invention. Act on. 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) The block-type polymer is not particularly limited, and examples thereof include a block-type polymer composed of a pigment adsorption block and a block that does not adsorb to the pigment.
Although it does not restrict | limit especially as a monomer which comprises a pigment adsorption block, For example, the monomer which has a functional group which can adsorb | suck to a pigment is mentioned. Specific examples include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic nitrogen atom.

  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, ansanthrone 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. More specifically, although not particularly limited, monomers having the following structures can be exemplified.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and 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, 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 (meth) acrylates can also be used. 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 monomers having a heterocyclic ring, and (meth) acrylic acid ester as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, ( (Meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N-diisopropylaminoethyl, (meth) acrylic acid N, N-di-n-butylaminoethyl, (meth) acrylic acid N, N- Di-i-butylaminoethyl, morpholinoethyl (meth) acrylate, piperidy (meth) acrylate Ethyl, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate, and N, N-methylphenylaminoethyl (meth) acrylate, and the like ( As meta) acrylamides, N- (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) methacrylate Luamide, 2- (N, N-dimethylamino) 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 (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc., and styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, etc. .

  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.

  Furthermore, 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 capable of adsorbing 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.

  The monomer constituting the block that is not adsorbed by the pigment is not particularly limited. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid Examples include diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, and (meth) acrylonitrile. These monomers may be used independently and may use 2 or more types together. When applied to a photocurable composition that requires an alkali development treatment, a monomer that constitutes a block that is not adsorbed by the pigment and a vinyl monomer having an acidic group may be used in combination.

  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.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group and 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, 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 (meth) acrylates can also be used. 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. 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.
Furthermore, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group can be used as the vinyl monomer having an acidic group.

  As a method for obtaining the block polymer in the present invention, a conventionally known method can be used. For example, living polymerization, iniferter method and the like are known, and as another method, in radical polymerization of a monomer having a pigment adsorption group or a monomer having no pigment adsorption group, thiolcarboxylic acid or 2 A polymer obtained by polymerizing a compound containing a thioester and a thiol group in a molecule such as -acetylthioethyl ether or 10-acetylthiodecanethiol is treated with an alkali such as sodium hydroxide or ammonia. A method is also known in which a polymer having a thiol group at one end and radical polymerization of the monomer component of the other block in the presence of the resulting polymer having a thiol group at one end is known. Among these, living polymerization is preferable.

  The weight average molecular weight of the block 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 can be used as the block polymer. Specific examples include Disperbyk-2000, -2001 (above BYK Chemie), EFKA 4330, 4340 (above EFKA) and the like.

(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.

The aryl group represented by R ⁷⁵ in —COOR ⁷⁵ represented by Q in the general formula (5) may have a substituent, and is 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).

一般式（６）中、Ｒ^７６は、水素原子または炭素原子数１〜８のアルキル基を表し、Ｗは単結合または、

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

(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. Represents an aryl group of 6 to 20.) represents a single linking group selected from an atomic group such as) or a linking group composed of any combination, and A represents a structure represented by the general formula (5). A group having at least a unit is represented.
Specific examples of the macromonomer represented by the general formula (6) include the following.

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-mercaptoimidazole, 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 number 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).
The dispersant is preferably a polymer compound having a heterocyclic ring in the side chain of the present invention, a graft polymer, or a terminal-modified polymer, and among them, a copolymer derived from a monomer having an organic dye structure or a heterocyclic structure Particularly preferred are graft-type polymers containing units, and terminal-modified polymers 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 terminal groups.

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 polymer compound having a heterocyclic ring in the side chain of the present invention coated with the pigment and the dispersant is not particularly limited, but when the dispersant is a polymer dispersant, the ratio is 10/90 to 90/10 mass ratio. Is preferable, and 20/80 to 80/20 mass ratio is particularly preferable.

-Preparation of pigment dispersion composition-
A preferred embodiment of the present invention is a pigment dispersion composition obtained by dispersing a processed pigment coated with a polymer compound having a heterocyclic ring in a side chain 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. Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform 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 comprises an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably a coated pigment coated with a polymer compound having a heterocyclic ring in the side chain of the present invention described above. It can be prepared by mixing (dispersing with a solvent), mixing an additive such as a surfactant as necessary, and mixing and dispersing using various mixers and dispersers.

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

<Photocurable composition>
The photocurable 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 selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ = CR ¹ R ² and / or CH ₂ = C (R ¹ ) (COOR ³ ).

  As content in the photocurable 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%, Most 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, pages 300 to 308, those introduced as photocurable monomers and oligomers 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 photocurable composition of a photopolymerizable compound, 20-200 mass parts is preferable with respect to 100 mass parts of total solid content of this composition, More preferably, it is 50-120 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. US Pat. No. 4,318791 and European Patent Publication EP-88050A, described in US Pat. No. 4,1994,420 Aromatic ketone compounds such as benzophenones, (thio) xanthones or acridine compounds described in Fr-2456541, compounds such as coumarins or lophine dimers described in JP-A-10-62986, JP-A Sulfonium organoboron such as in Japanese Patent No. 8-015521 Body, etc., etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biphenyl Imidazole type, oxime ester type and the like are preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

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

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  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 triazine photopolymerization initiator include 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, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 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 and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 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 A preferred example is 4-oxodiazole.

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

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole, 2,2′-benzothiazolyl disulfide and the like.

  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 photocurable 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.

-Solvent-
In general, the pigment dispersion composition and the photocurable 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 photocurable composition of the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, the above alkali Various additives such as a polymer compound other than the soluble resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

<Fluorine organic compounds>
By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also 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, 80 2 (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 photocurable 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 pigment dispersion 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 include a thermal polymerization component in the pigment dispersion composition of the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. As an epoxy compound, it is a compound which has two or more epoxy rings in a molecule | numerator, such as a bisphenol A type, a cresol novolak type, a biphenyl type, and an alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103, etc. (more from Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (more from Daicel Chemical) and their similarities The 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 manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above manufactured by Nagase Kasei), 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 obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

<Surfactant>
The pigment dispersion composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability. In addition to the above-mentioned fluorosurfactants, nonionic, cationic, and anionic Various 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. 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 photocurable 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 pigment dispersion composition is further improved, the pigment dispersion composition may be an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. 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, it is preferable to add a thermal polymerization inhibitor to the pigment dispersion composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t -Butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful It is.

The 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., to form a photocurable coating film. Forming and exposing through a predetermined mask pattern, and developing and removing the uncured portion with a developer after exposure to form a pattern film made up of pixels of each color (three colors or four colors), can do.
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 photocurable composition of the present invention described above, and the photosensitive composition of the present invention is directly or via other layers. For example, after forming a coating film on the substrate by slit coating, the coating film is dried, subjected to pattern exposure, and development processing using a developer is 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 photo-curing 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.

  The method for applying the photosensitive composition of the present invention to the 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). preferable. 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 photocurable 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 a coating film with the photosensitive composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 μm, preferably 0.5 to 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.

Examples of the organic solvent include the above-described solvents that can be used when preparing the pigment dispersion composition or the photosensitive composition of the present invention.
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. 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 pigment dispersion composition and the photosensitive composition of the present invention has been mainly described for use in color filters. However, the present invention can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter. Can do.
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.

  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. Further, “specific polymer compound” in the table means “polymer compound having a heterocyclic ring in the side chain of the present invention” or “comparative polymer compound”.

<Synthesis example of polymer compound having heterocycle in side chain>
(Synthesis of Specific Polymer Compound 1)
M-11 27.0 g, MMA 126.0 g, MAA 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: The mixture is stirred with a three-one motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred with heating at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of the specific polymer compound 1 was obtained.
As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000.
From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.

(Synthesis of specific polymer compound 2)
M-6 27.0 g, MMA 126.0 g, MAA 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: Three One Motor) ) And heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30 mass% solution of the specific polymer compound 2 was obtained.
It was 21,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. Moreover, the acid value per solid content was 99 mgKOH / g from the titration using sodium hydroxide.
In the same manner, the specific polymer compound no. 3-No. 17 was synthesized.

表１で、ＭＡＡはメタクリル酸、ＭＭＡはメチルメタクリレート、ＢｚＭＡはベンジルメタクリレート、ＨＥＭＡは２−ヒドロキシエチルメタクリレートである。

In Table 1, MAA is methacrylic acid, MMA is methyl methacrylate, BzMA is benzyl methacrylate, and HEMA is 2-hydroxyethyl 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 polymer compound solution, and 100 g of diethylene glycol were charged into a 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, dried and processed pigment coated with a polymer compound. Got.

(Measurement of primary particle diameter of pigment)
The primary particle diameter of the pigment was determined by observing the obtained processed pigment with a transmission electron microscope (TEM).

(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 polymer compound released from the pigment was determined, and the release rate (%) was calculated from the ratio with the polymer compound used in the treatment. The smaller the liberation rate, the higher the degree of coverage on the pigment.

In addition, the detail of the compound used in the said Tables 2-7 is as follows.
<Pigment>
PR254; C.I. I. Pigment Red 254
PR177; C.I. I. Pigment Red 177
PG36; C.I. I. Pigment Green 36
PY150; C.I. I. Pigment Yellow 150
PB15: 6; C.I. I. Pigment Blue 15: 6
PV23; C.I. I. Pigment Violet 23
<Specific polymer compounds and other polymer compounds>
As for the specific polymer compound, the numbers of the exemplified compounds are listed in Table 1. The comparative polymer compound is as follows.
P-1; copolymer of methyl methacrylate / methacrylic acid = 85/15% by mass, weight average molecular weight 20,000, acid value 98 mgKOH / g
P-2: Hydrogenated rosin ester (“Ester gum HP” manufactured by Arakawa Chemical Co., Ltd.)
P-3: trimethylolpropane triacrylate P-4: copolymer of cyclohexyl methacrylate / methacrylic acid = 85/15% by mass, weight average molecular weight 20,000, acid value 98 mgKOH / g

<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 (however, Comparative Example 4 and Comparative Example 5 were 82.7 parts)
Derivative A (the following structure [Chemical Formula 13]) 5 parts Dispersant (30% 1-methoxy-2-propylacetate solution of dispersant described in Table 8) (Amount described in 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, the viscosity η1 of the pigment dispersion composition immediately after dispersion, and after 1 week after dispersion (at room temperature) The viscosity η2 of the pigment dispersion composition 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 precipitation on the pattern was confirmed with an optical microscope. The post-baking process was repeated and observed each time. The higher the score, the better it is.
4: Deposition at the fourth post-baking 3: Deposition at the third post-baking 2: Deposition at the second post-baking 1: Deposition at the first post-baking

From the results in Table 8, the photosensitive compositions of Examples 1 to 5 and 7 to 11 using processed pigments coated with a polymer compound having a heterocyclic ring in the side chain of the present invention have high contrast and are precipitated by post-baking. It is difficult to see and the viscosity increase 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 (however, Comparative Example 11 and Comparative Example 12 were 82.7 parts)
Dispersant (30% 1-methoxy-2-propyl acetate solution of the dispersant described in Table 9) (Amount described 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. 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 differs depending on the hue, Table 9 compares green and blue. From the results of Table 9, the photosensitive compositions of Examples 13 to 15 and Examples 17 to 19 using processed pigments coated with a polymer compound having a heterocyclic ring in the side chain of the present invention have increased viscosity over time. It can be suppressed, the contrast is high, and it is difficult to deposit by post-baking.

<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 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. 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 penta-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). The value was applied to 0.650, and Examples 29 to 32 and Comparative Examples 15 and 16 were applied so that the y value as an index of color density was 0.600, and Example 33 and Comparative Example 17 and 18 were applied so that the y value as an index of color density was 0.100, and dried in an oven at 90 ° 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) Alkali developer solubility 100 g of a 10% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) is weighed into a 150 ml beaker. The photocurable composition was 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 (prebaked). 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. The solubility of the film repeatedly and the presence or absence of a suspension in the developer were visually judged. The higher the score, the better the alkali solubility.

* Judgment method Complete dissolution in 1-10 vertical motions and no suspension: 5
Completely dissolved in up and down movements 11 to 20 times and no suspension: 4
Completely dissolves in up and down movements 1 to 10, but with suspension: 3
Completely dissolves in up and down motions 11-20 times, but with suspension
Insoluble after 20 vertical movements: 1

(3) Precipitation evaluation A photocurable 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 was 20 mW / cm ² ), and 1 of alkaline developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) Development was performed at 25 ° C. using a% aqueous solution.
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.

<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 ([Chemical Formula 14] of the following structure) 20 parts 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. 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 pentahexaacrylate 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 (= 75/35 [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>
The obtained colored photosensitive composition (color resist solution) was placed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning). Examples 34 to 36 and Comparative Examples 19 and 20 were used as indicators of color density x Application was made so that the value was 0.650, and Examples 37 to 39 and Comparative Examples 21 and 22 were applied so that the y value as an index of color density was 0.600, and Examples 40 to 42 and Comparative Examples 23 and 24 were applied so that the y value serving as an index of color density was 0.100, applied so that the x value serving as an index of color density was 0.650, and 60% in an oven at 90 ° C. Dry for 2 seconds (pre-bake). 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 photocurable composition was applied on 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). Then, 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 alkaline 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 a liquid crystal MJ971189 manufactured by Merck Co., Ltd. (trade name) 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, the comparison is made between the same colors, that is, between the DLs, the DYs, and the 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.

<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 pentahexaacrylate 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>
The obtained colored photosensitive composition (color resist solution) was placed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning). Examples 43 and 44 and Comparative Example 25 had an x value serving as an index of color density. It was applied so that the value was 0.650, and Examples 45 and 46 and Comparative Example 26 were applied so that the y value as an index of color density was 0.600, and Examples 47 and 48 and Comparative Example 27 were The coating was applied so that the y value as an index of color density was 0.100, and dried in an oven at 90 ° 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 14.
(1) Contrast (2) Alkali developer soluble (3) A photocurable composition was 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. Then, 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 alkaline 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. Summarized in The higher the score, the more difficult it is to precipitate crystals.
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 the DR comrades, the DG comrades, and the DB comrades. 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.

<Preparation of pigment dispersion composition>
The components of the following composition (5) 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 (5)]
Processed pigment (pigment type listed in Table 15) (Amount listed in Table 15)
Derivative A (the following structure [Chemical Formula 13]) 20 parts Dispersant (specific polymer compound described in Table 1, solid content 100%) (Amount described in Table 15)
750 parts of 1-methoxy-2-propyl acetate Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 3 hours using a bead disperser Dispermat (manufactured by GETZMANN) using 0.8 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 5 times to obtain the pigment dispersion compositions shown in Table 15.

The obtained pigment dispersion composition was evaluated as follows, and the results are shown in Table 15.
Viscosity and precipitation were evaluated in the same manner as in Table 8.
Contrast was applied to a glass substrate of 100 mm × 100 mm so that Example 49 and Comparative Example 28 had an x value as an index of color density of 0.650, and Example 50 and Comparative Example 29 were indicators of color density. Is applied so that the y value becomes 0.600, and Example 51 and Comparative Example 30 are applied so that the y value serving as an index of color density becomes 0.100, and is heated in an oven at 90 ° C. for 60 seconds. After drying, the contrast was measured as in Table 8.

  From Table 15, the pigment dispersion composition using the pigment coated with the specific polymer compound of the present invention has a dispersion stability of the pigment dispersion composition as compared with the comparative example in which the specific polymer compound is added in the dispersion step. It can be seen that the contrast is improved, the contrast is high, and crystal precipitation is difficult to occur.

<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)

The side chain derived from at least one monomer selected from the group consisting of M-1 to M-27 and M-31 below contains a repeating unit having an unsaturated nitrogen-containing heterocyclic ring, and the carboxyl group is 50 mgKOH. / g or more 200 mg KOH / g Ru machining pigment greens to coat the pigment with a polymer compound having the following range.

The repeating unit having an unsaturated nitrogen-containing heterocyclic ring in the side chain is composed of the M-1, M-4, M-6, M-11, M-14, M-15, M-25 and M-31. The processed pigment according to claim 1, which is a repeating unit derived from at least one monomer selected from the group. The average primary particle size, processed pigments according to 請 Motomeko 1 or claim 2 Ru der 5 nm or more 25nm or less. The processed pigment according to any one of claims 1 to 3, wherein a liberated amount of the polymer compound is 30% by mass or less when the processed pigment is washed with 1-methoxy-2-propanol. Processed pigment according the the polymer compound, in any one of claims 4 請 Motomeko 1 produced by adding a pigment refining process. The processed pigment according to any one of claims 1 to 5, Ru Pigment dispersion composition Na was dispersed in an organic solvent. The pigment dispersion composition according to claim 6 , further comprising a pigment dispersant. Pigment dispersion composition according to 請 Motomeko 6 or claim 7 that used to form the colored region in a color filter. Pigment dispersion composition according to any one of claims 8 claims 6, a photopolymerizable compound, and wearing colored photosensitive composition you a photopolymerization initiator. The colored photosensitive composition according to claim 9, wherein the photopolymerization initiator is an s-triazine photopolymerization initiator. The colored photosensitive composition according to claim 9 or 10, wherein the photopolymerizable compound is a tetrafunctional or higher functional acrylate compound. On a substrate, Luca color filter having a colored region formed by the colored photosensitive composition according to any one of claims 11 claim 9. Liquid crystal display element Ru with a color filter according to claim 12. Solid-state imaging device that includes a color filter according to claim 12.