JP2009084452A - Processed pigment, pigment dispersion composition using the same, colored photosensitive composition, color filter, liquid crystal display element having the color filter and solid-state image pickup device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processed pigment having improved dispersibility, a pigment dispersion composition having excellent pigment dispersibility and dispersion stability, a colored photosensitive composition having excellent curability, a color filter having a high contrast, and a liquid crystal display element and a solid-state image pickup device having the color filter. <P>SOLUTION: The processed pigment is prepared by coating a pigment with a polymer compound containing a structural unit represented by the general formula (1) (R<SP>1</SP>is a hydrogen atom or a methyl group; X is an oxygen atom or -NR<SP>2</SP>-; R<SP>2</SP>is a hydrogen atom or a monofunctional organic group; L is an organic connecting group; and n is an integer of 1-4). The pigment dispersion composition uses the processed pigment. The colored photosensitive composition, the color filter, the liquid crystal display element and the solid-state image pickup device, each of which uses the processed segment, are also provided. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is produced using a processed pigment, a pigment dispersion composition, a colored photosensitive composition containing the same, and a colored photosensitive composition that can be suitably used in a wide range of paints, printing inks, color display boards and the like. Related to color filters. Moreover, this invention relates to a liquid crystal display element provided with the said color filter, and a solid-state image sensor.

  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.

  On the other hand, in recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). Color characteristics have been required. Similarly, in image sensor (solid-state imaging device) applications, advanced color characteristics such as reduction in color unevenness and improvement in color resolution are required.

  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. It is desirable that the primary particles be stably dispersed without being easily handled.

  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).

  Moreover, the technique which improves developability and adhesiveness using the polyester connection terminal carboxyl group containing resin as alkali-soluble resin of the photosensitive composition for color filters is proposed (for example, refer 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-A-11-258415

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 color pattern using the colored photosensitive composition of the present invention, having high contrast and small color density unevenness, and a liquid crystal comprising the color filter. A display element and a solid-state image sensor are provided.

The present inventors have found that the above problems can be achieved by the following method, and have reached the present invention.
<1> A processed pigment obtained by coating a pigment with a polymer compound containing at least a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom or —NR ² —, R ² represents a hydrogen atom or a monovalent organic group, and L represents an organic linking group. N represents an integer of 1 to 4.)

<2> The processed pigment according to <1>, wherein the general formula (1) is represented by the following general formula (2).

(In General Formula (2), Y represents an alkylene group having 2 to 4 carbon atoms. L ¹ is an alkylene group having 2 to 10 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, or 6 to 20 carbon atoms. Any one of aromatic groups, which may have a substituent, m represents an integer of 1 to 20, and R ¹ represents a hydrogen atom or a methyl group.)

<3> The processed pigment according to <1> or <2>, wherein the general formula (1) is represented by the following general formula (3).

(In general formula (3), k represents an integer of 2 to 10. i represents an integer of 1 to 20. R ¹ represents a hydrogen atom or a methyl group.)

<4> In any one of the above items <1> to <3>, L ¹ in the general formula (2) represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms. The processed pigment as described.
<5> The processed pigment according to any one of <1> to <4>, wherein k in the general formula (3) is 5 and i is an integer of 1 to 10. .
<6> The processed pigment according to any one of <1> to <5>, wherein the polymer compound has a weight average molecular weight of 1,000 or more and 100,000 or less.
<7> The processed pigment according to any one of <1> to <6>, wherein the average primary particle diameter is 5 to 25 nm.
<8> The liberated amount of the polymer compound when the processed pigment is washed with 1-methoxy-2-propanol is 30% by mass or less, according to any one of the above <1> to <7>. It is a processed pigment.
<9> The processed pigment according to any one of <1> to <8>, wherein the polymer compound is produced by adding the polymer compound in a pigment refining step.

<10> A pigment dispersion composition obtained by dispersing the processed pigment according to any one of the above items <1> to <9> in an organic solvent.
<11> The pigment dispersion composition according to <10>, further including a pigment dispersant.
<12> The pigment dispersion composition according to <10> or <11>, which is used for forming a colored region in a color filter.

<13> A colored photosensitive composition comprising the pigment dispersion composition according to any one of <9> to <12> above, a photopolymerizable compound, and a photopolymerization initiator. .
<14> A color filter having a colored region formed of the colored photosensitive composition according to <13> on a substrate.
<15> A liquid crystal display device comprising the color filter according to <14>.
<16> A solid-state imaging device comprising the color filter according to <14>.

  In addition, the “free amount” in the above <8> is a surface treatment agent in which the processed pigment is immersed in 1-methoxy-2-propanol as a solvent and dissolved in the solvent (in the present invention, the side chain has a heterocyclic ring) It is mass% obtained by dividing the amount of the polymer compound) by the amount of the surface treatment agent used.

The present invention relates to a processed pigment obtained by coating a pigment with a polymer compound containing at least the structural unit represented by the general formula (1) (hereinafter referred to as a specific polymer compound), and its application. Is excellent in dispersibility, and by using this processed pigment, a pigment dispersion composition in which the pigment is dispersed better than the conventional one and a colored photosensitive composition having a pigment in a good dispersion state can be obtained. And it is providing the color filter with high contrast, and a liquid crystal display element provided with the same, and a solid-state image sensor by using the said coloring photosensitive composition.
That is, when a specific polymer compound is used for pigment treatment, it effectively suppresses the formation of secondary aggregates that are aggregates of primary particles of the pigment, or effectively reduces the cohesive force of the secondary aggregates. It is thought that you can. Therefore, a dispersion in a state close to primary particles can be obtained in the dispersion step.

Although this action is not clear, when the specific polymer compound is used for pigment treatment, the formation of secondary aggregates, which are aggregates of primary particles of pigment, is effectively suppressed, or the aggregation of secondary aggregates Can effectively weaken the power. Therefore, it is considered that a dispersion in a state close to primary particles can be obtained in the dispersion step.
The specific polymer compound has a carboxyl group linked to the side chain via a spacer group, so that the structure and the pigment have an appropriate electrostatic interaction, and a strong molecule due to the specific polymer compound. This is considered to be because the primary particles are strongly adsorbed by the interstitial force and are not desorbed even during slurry, filtration, and washing with water, effectively suppressing aggregation of the primary pigment particles.

  Further, by using the processed pigment of the present invention, it is possible to solve the problem that the color filter becomes cloudy under high temperature and high humidity, and becomes cloudy when producing the color filter. These problems are considered to be a phenomenon caused by aggregation of fine pigment particles in the color filter and crystal growth. The finer the primary pigment particles, the more likely it is. Therefore, the above problem can be solved because the processed pigment of the present invention is strongly adsorbed to the fine pigment because of the same reason as above, and the aggregation of the pigment particles is also effective in the color filter. It is thought that it is because it is restrained.

  Moreover, a color filter is excellent in a voltage holding rate by using the processed pigment of this invention. The decrease in voltage holding ratio is likely to occur when the metal ion concentration in the color filter is high. In particular, when a fine pigment is prepared using the salt milling method, it is a problem that easily occurs. This is because inorganic salts (ions) used for salt milling adsorbed on the pigment particles are eluted from the pigment particles. The finer the primary pigment particles, the easier it is to contain ionic compounds and the more difficult the removal by water washing and filtration. Therefore, an excellent voltage holding ratio can be obtained because the processed pigment of the present invention is strongly adsorbed to the fine pigment for the same reason as described above, so that the ion in the dispersion process or the color filter can be obtained. This is thought to be because it is possible to effectively suppress the elution of.

Further, the use of the processed pigment of the present invention has an advantage that precipitates are hardly generated in the developer during the color filter manufacturing process. The precipitate is often an aggregate of pigment particles. Precipitation is considered to be a phenomenon in which the pigment dispersion dispersed by the dispersant is desorbed by the alkaline developer, and the fine pigment particles are aggregated and crystallized to precipitate. Therefore, because the processed pigment of the present invention is strongly adsorbed to the fine pigment for the same reason as described above, the polymer compound is not desorbed even by an alkaline developer, and is stable even in an alkaline developer. Therefore, it is considered that precipitates are hardly generated in the developer.
Further, by using the liquid crystal display device and the solid-state imaging device provided with the color filter of the present invention, there is an advantage that precipitates are hardly generated in the developer during the color filter manufacturing process.

According to the present invention, even in a refined pigment, the formation of secondary aggregates is suppressed, and the processed pigment having 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.
Further, according to the present invention, by using the processed pigment of the present invention, a pigment dispersion composition excellent in dispersibility and dispersion stability of the pigment and a large amount of pigment containing such a pigment dispersant are contained. Even if it does, the colored photosensitive composition excellent in sclerosis | hardenability can be provided.
Furthermore, according to the present invention, a color filter having a color pattern using the colored photosensitive composition of the present invention and having good color characteristics with high contrast and small color density unevenness can be provided.
In addition, a liquid crystal display device and a solid-state imaging device including the color filter can be provided.

Hereinafter, the present invention will be described in detail.
<Processed pigment>
The processed pigment of the present invention is characterized in that the pigment is coated with a polymer compound containing at least a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom or —NR ² —, R ² represents a hydrogen atom or a monovalent organic group, and L represents an organic linking group. N represents an integer of 1 to 4.)

  Suitable examples of the production of such finely processed pigments are i) which is a pigment, ii) which is a water-soluble inorganic salt, and a small amount of water-soluble organic solvent which does not substantially dissolve ii). iii) and iv) which is a polymer compound (hereinafter sometimes referred to as a specific polymer compound) containing at least the structural unit represented by the general formula (1), and mechanically kneaded with a kneader or the like Through a step (referred to as salt milling), a step of adding this mixture into water, stirring it with a high speed mixer or the like to form a slurry, and a step of filtering, washing the slurry and drying it if necessary An example of implementation is given. 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, i) a small amount of a water-soluble organic solvent iii) as a wetting agent is added to i) which is a mixture of an organic pigment i) and a water-soluble inorganic salt, and kneaded strongly with a kneader or the like. The mixture is poured into water and stirred 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. In addition, when used by dispersing in an oily varnish, it is also possible to disperse the treated pigment before drying (referred to as a 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 the surface is coated with a resin that is iv) at least partly soluble. 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 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.
Note that iv) At least the specific polymer compound may be added at the initial stage of the salt milling process, or may be added separately.

[I) Pigment]
As the pigment used in the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used. As the particle size of the pigment, considering that the color filter in which the pigment dispersion composition of the present invention is suitably used preferably has a high transmittance, an organic pigment is preferable, and a pigment having a particle size as small as possible. Is preferably used. Considering the handling properties of the pigment dispersion composition and the 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, etc.

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. The above range is preferable from the viewpoints of light transmittance, color purity, and coloring power. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

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

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

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

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

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

[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 is easily evaporated. 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) Specific polymer compound]
The specific polymer compound of the present invention is not particularly limited as long as it is a polymer compound containing at least a structural unit represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. X represents an oxygen atom or —NR ² —. R ² represents a hydrogen atom or a monovalent organic group. L represents an organic linking group. n represents an integer of 1 to 4.

Examples of the monovalent organic group represented by R ² include linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms. The organic linking group represented by L is a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. And an organic linking group consisting of 0 to 20 sulfur atoms is preferred, and the organic linking group may be unsubstituted or may further have a substituent.

  Specific examples of the organic linking group include the following structural units or groups formed by combining the structural units.

When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.
Since the organic linking group L has good adsorbability to the pigment due to its flexible structure and good stability due to good affinity with the solvent in the pigment dispersion composition, the ester group —C ( Those having ═O) O— are preferred.

Furthermore, as the specific polymer compound containing the structural unit represented by the general formula (1), a specific polymer compound containing the structural unit represented by the following general formula (2) or the following general formula (3) may be used. From the viewpoints of adsorbability and dispersion stability.

In the general formula (2), Y represents an alkylene group. The alkylene group represented by Y is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. In the general formula (2), R ¹ represents a hydrogen atom or a methyl group.

  Moreover, in the said General formula (2), m represents the integer of 1-20, the integer of 1-10 is preferable and the integer of 1-4 is more preferable. When the value of m exceeds 20, the adsorptivity to the pigment decreases.

L ¹ represents any one of an alkylene group having 2 to 10 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and these may have a substituent. .

The L ¹ is an alkylene having 2 to 10 carbon atoms because it has good adsorbability to the pigment due to its flexible structure and good stability due to good affinity with the solvent in the pigment dispersion composition. Group is preferable, and a linear alkylene group having 2 to 6 carbon atoms is particularly preferable.

When L ¹ represents a cycloaliphatic group, the cycloaliphatic group has 3 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms.
Examples of the cycloaliphatic group having 3 to 20 carbon atoms include cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, norbornane, decahydronaphthalene, perhydrofluorene, tricyclo [5. 2.1.0 ^2.6 ] Decane, adamantane, quadricyclane, congressan, cubane, spiro [4.4] octane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclo Heptatriene, cyclodecatriene, cyclooctatetraene, norbornylene, octahydronaphthalene, bicyclo [2.2.1] heptadiene, bicyclo [4.3.0] nona Ene, dicyclopentadiene, hexa hydro anthracene, spiro [4.5] decadiene, and the like.
Of these, cyclohexane, tricyclo [5.2.1.0 ^2.6 ] decane, and cyclohexene are preferable from the viewpoints of dispersibility and developability.

In the case where L ¹ represents an aromatic group, the aromatic group has 6 to 20 carbon atoms, and preferably 6 to 10 carbon atoms.
Examples of the aromatic group include benzene, indane, 1,2,3,4-tetrahydronaphthalene, biphenyl, naphthalene, fluorene, anthracene, phenanthrene and the like. Among these, it is preferable from the viewpoint of dispersibility and developability.

In the said General formula (3), k represents the integer of 2-10, 4-8 are more preferable from the point of the adsorptivity to a pigment, and 4-6 are especially preferable. Moreover, in this General formula (3), i represents the integer of 1-20, 2-15 are more preferable from the point of the adsorptivity to a pigment, and 4-10 are especially preferable. In general formula (3), R ¹ represents a hydrogen atom or a methyl group.

The specific polymer compound may contain only one type of structural unit represented by the general formula (1), or may contain two or more types.
As the specific polymer compound containing the structural unit represented by the general formula (1) in the present invention, the general formula (2) and the general formula (3) are preferable. From the viewpoint of the stability of the liquid, it is more preferable to include at least a structural unit represented by the general formula (3).

  In the specific polymer compound, the content of the structural unit represented by the general formula (1) is not particularly limited, but when the total structural unit contained in the specific polymer compound is 100% by mass, The structural unit represented by the formula (1) is preferably contained in an amount of 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and more preferably 10% by mass to 20% by mass. It is particularly preferred.

  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 structural unit is preferably 5% by mass or more. Further, from the viewpoint of the strength of the image area when producing a color filter with 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 30% by mass or less.

  Here, although the specific example of the monomer which can form the structural unit represented by General formula (1) is enumerated, this invention is not limited to these compounds.

[Monomer having a heterocyclic structure in the side chain]
Furthermore, it is also a preferable aspect that the specific polymer compound of the present invention further includes a structural unit derived from a monomer represented by the following general formula (4), or maleimide or a maleimide derivative.

In general formula (4), R ⁴¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. ^R42 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.

The alkyl group corresponding to R ⁴¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ⁴¹ 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 preferable alkyl group represented by R ⁴¹ 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 ⁴¹ is most preferably a hydrogen atom or a methyl group.

In the general formula (4), the divalent linking group corresponding to R ^42, a substituted or unsubstituted alkylene group is preferable. 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.
Alkylene group represented by R ⁴² is a heteroatom (e.g., oxygen atom, nitrogen atom, or sulfur atom) or may be linked more through.
Specifically preferred alkylene groups represented by R ^42, for example, methylene group, ethylene group, propylene group, trimethylene group and a tetramethylene group.
If Preferred alkylene groups represented by R ⁴² has a substituent, examples of the substituent group, e.g., hydroxy groups, and the like.

Examples of the divalent linking group represented by R ⁴² include —O—, —S—, —C (═O) O—, —CONH—, and —C (═O) S at the end 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 the general formula (4), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, indanthrone series, 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 general formula (5), (6), or (7) is particularly preferable.

In the general formula (5), 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-, -N (R ^A )-And -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 (5), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (7), 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 enumerated above, Y and Z in the general formula (7) are particularly preferably —N═, —NH—, and —N (R ^B ) —. 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 (5), (6), and (7), 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 (5) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring C in the general formula (6) 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 (7) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.

  In the general formulas (5), (6) and (7), among the structures represented by ring A, ring B and ring C, from the viewpoint of dispersibility and stability over time of the dispersion, a benzene ring and a naphthalene ring In general formula (5) or (7), a benzene ring is more preferable, and in general formula (6), a naphthalene ring is more preferable.

  In the polymer compound having a heterocyclic ring in the side chain, preferred specific examples of the monomer, maleimide, and maleimide derivative represented by the general formula (4) are listed below, but the present invention is not limited thereto. .

When the specific polymer compound of the present invention includes the structural unit represented by the general formula (4), it may include only one type or two or more types.
In the specific polymer compound of the present invention, the content of the structural unit represented by the general formula (4) is not particularly limited, but when the total structural unit contained in the specific polymer compound is 100% by mass. The structural unit represented by the general formula (4) is preferably contained in an amount of 5% by mass or more, and more preferably 5% by mass or more and 50% by mass or less.
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 (4). The content of the structural unit is preferably 5% by mass or more. From the viewpoint of developability when producing a color filter with a photocurable composition containing a pigment dispersion composition, the content of the structural unit represented by the general formula (4) is 50% by mass or less. It is preferable.

[Polymerizable oligomer having an ethylenically unsaturated double bond at the end]
Furthermore, the specific polymer compound of the present invention may be a graft copolymer containing a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal from the viewpoint of imparting dispersion stability of the pigment. This is a preferred embodiment.

  Such a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the “polymerizable oligomer having an ethylenically unsaturated bond at the terminal” in the present invention may be appropriately referred to as “polymerizable oligomer” or “macromonomer”.

The macromonomer preferably has a polystyrene-equivalent number average molecular weight (Mn) in the range of 500 to 10,000, and particularly preferably in the range of 1000 to 9000.
If it is less than 500, the adsorptivity to the pigment will be low, dispersibility, dispersion stability, and contrast will be low, and if it exceeds 10,000, developability will deteriorate.
That is, from the viewpoint of the dispersibility and dispersion stability of the pigment contained in the pigment dispersion composition and the contrast of the color filter obtained by applying the pigment dispersion composition, the number average molecular weight (Mn) of the macromonomer is It is preferable that it is 500 or more. Moreover, from the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the number average molecular weight (Mn) of the macromonomer is preferably 10,000 or less.

  The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

  The polymer chain part in the macromonomer is substituted or unsubstituted alkyl (meth) acrylate, (meth) acrylamide, substituted or unsubstituted N-alkyl (meth) acrylamide, substituted or unsubstituted N, N′-dialkyl ( A homopolymer or copolymer formed from at least one monomer selected from the group consisting of (meth) acrylamide, substituted or unsubstituted styrene, (meth) acrylonitrile, vinyl acetate, and butadiene, or polyethylene oxide, polypropylene oxide Or polycaprolactone.

In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".
When the macromonomer is substituted or unsubstituted, examples of the substituent 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. Among such alkyl groups, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, an aryl group, or a hydroxyl group is preferable, and an unsubstituted alkyl group is particularly preferable.

  About the polymer chain part in the macromonomer, from the viewpoint of dispersion stability and developability, substituted or unsubstituted alkyl (meth) acrylate, (meth) acrylamide, substituted or unsubstituted N-alkyl (meth) acrylamide, A homopolymer or copolymer formed from at least one monomer selected from the group consisting of substituted or unsubstituted N, N′-dialkyl (meth) acrylamide, substituted or unsubstituted styrene, and (meth) acrylonitrile; Caprolactone, polyethylene oxide, and polypropylene oxide are preferable, and are composed of substituted or unsubstituted alkyl (meth) acrylate, substituted or unsubstituted N, N′-dialkyl (meth) acrylamide, substituted or unsubstituted styrene, and (meth) acrylonitrile. Chosen from the group Homopolymers or copolymers formed from at least one monomer, polycaprolactone is more preferable.

  Moreover, it is preferable that it is an oligomer represented by following General formula (8) as a structure of the whole macromonomer.

In General Formula (8), R ⁸¹ and R ⁸³ each independently represent a hydrogen atom or a methyl group.
R ⁸² represents a linking group containing an alkylene group having 1 to 12 carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups may be ester bonds or ethers. It may be linked via a bond, an amide bond or the like. The alkylene group for R ⁸² is preferably an alkylene group having 2 to 4 carbon atoms. The alkylene group for R ⁸² may further have a substituent (for example, a hydroxyl group).

Y ⁸¹ represents a substituted or unsubstituted phenyl group, —COOR ⁸⁴ , a cyano group, or —CONR ⁸⁵ R ⁸⁶ . Here, ^R84 represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. R ⁸⁵ and R ⁸⁶ represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. q represents an integer of 10 to 200.
Here, when the macromonomer of the general formula (8) is a copolymer formed from two or more types of monomers, R ⁸³ and Y ⁸¹ are present in two or more types at the same time.
Y ⁸¹ is preferably a phenyl group or —COOR ⁸⁴ . Here, ^R84 represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Y ⁸¹ is most preferably —COOR ^{84 or} a cyano group from the viewpoints of dispersion stability and developability.

Specific examples of the polymerizable oligomer include poly-2hydroxyethyl (meth) acrylate, polystyrene polymer, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, poly Acrylonitrile, polyacetoacetoxyethyl methacrylate, poly-2-methoxyethyl methacrylate, poly-2-methoxyethoxyethyl methacrylate, polyacrylamide, N, N′-dimethylacrylamide, and a copolymer thereof, A polymer having a meth) acryloyl group bonded thereto is preferable.
The polymerizable oligomer may be a commercially available product or may be appropriately synthesized. Examples of the commercially available product include a one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6). , Manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-n-butyl Acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AA-714) Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polybutyl methacrylate / -Hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated poly 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AY) -707S, AY-714S, manufactured by Toa Gosei Chemical Co., Ltd.), and the like.

The specific polymer compound of the present invention may contain only one type of copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, or may contain two or more types. .
As content of the said copolymerization unit in a specific high molecular compound, the said polymerizable oligomer is 20-80 mass%, Preferably it is 40-80 mass%. When the content of the polymerizable oligomer is less than 20% by mass, the solubility in the dispersion solvent is lowered, and it becomes difficult to sufficiently secure an adsorption layer necessary for stabilizing the dispersion. When it exceeds, developability will fall.

[Copolymerizable vinyl monomer]
The specific polymer compound may further contain copolymer units derived from a copolymerizable vinyl monomer as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds.

  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, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

The preferred molecular weight of the specific polymer compound of the present invention is preferably in the range of 1,000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 400 to 50,000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 5000 to 50000, and the number average molecular weight (Mn) is in the range of 2000 to 30000.
In particular, the weight average molecular weight (Mw) is most preferably in the range of 8000 to 30000, and the number average molecular weight (Mn) is in the range of 4000 to 12000.
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 of the specific polymer The molecular weight (Mw) is preferably 1000 or more. Further, 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 specific polymer is preferably 30000 or less.

<Polymerization method of specific polymer compound>
The specific polymer compound of the present invention uses, for example, a structural unit represented by the general formula (1), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component, and a normal radical weight. It can be manufactured by law. In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used when synthesizing such a specific polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, etc. Can be mentioned. These solvents may be used alone or in combination of two or more.
In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

  In the processed pigment of the present invention, the content of the specific polymer compound is preferably a mass ratio of pigment: specific polymer = 1: 0.01 to 1: 2, more preferably 1: 0.05 to 1: 2. 1, more preferably 1: 0.1 to 1: 0.6.

The specific polymer compound desirably has a carboxyl group in the compound in the range of 50 mgKOH / g or more, and particularly preferably 50 to 200 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the carboxyl group content is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively reduce the cohesive force of the secondary aggregates, the carboxyl group content is 50 to 200 mgKOH / It is preferable that it is g. This carboxyl group is contained in the specific polymer compound, for example, as an acid group in the monomer having the acid group.
The acid value can be experimentally determined by titrating the synthesized specific polymer compound with an alkaline substance such as NaOH. Moreover, it can also obtain | require by calculating the quantity of acid groups, such as a carboxyl group, from the raw material monomer used for the synthesis | combination of a specific high molecular compound, and its structural ratio.

Here, the processed pigment of the present invention is characterized in that i), which is a pigment particle such as an organic pigment, is coated with iv), which is a specific polymer compound, and the specific polymer compound is a surface of the pigment particle. The effect of the present invention can be obtained by being firmly coated on a part or the whole, and is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (free rate) of the specific polymer compound by washing with an organic solvent shown below. That is, most of the specific polymer compound simply adsorbed is washed away with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a processed pigment whose surface is coated as in the present invention, The liberation 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 is put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Next, the pigment is allowed to settle for 8 hours at 80,000 rpm with a centrifuge, and the solid content of the supernatant is determined from the drying method. Then, the mass of the specific polymer compound released from the pigment is obtained, and the liberation rate (%) is calculated from the ratio with the mass of the specific 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 for dissolving the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), an organic solvent is used by utilizing the difference in solubility between the specific polymer compound and the pigment. Separated and calculated as “mass of the specific polymer compound used in the initial treatment”. Separately, the processed pigment is washed with 1-methoxy-2-propanol, and the obtained liberation amount is divided by this “mass of the specific polymer compound used in the initial treatment” to obtain a liberation rate (%). Ask for.
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. The 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. Preferably, it is 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 an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

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

  The processed pigment of the present invention thus obtained has a pigment surface that is firmly coated with a specific polymer compound and becomes a processed pigment having excellent dispersibility, and its application range is wide. In particular, the preparation of a pigment dispersion composition Useful for.

<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 pigment dispersant as needed suitably.

〔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; 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. A pigment derivative having an affinity for the dispersant or a polar group-introduced pigment is adsorbed on the surface of the processed pigment, and this is used as the adsorption point for the dispersant, whereby the pigment is incorporated into the photocurable composition as fine particles. It can be dispersed to prevent re-aggregation, and 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 processed pigment, and 3-20 mass% is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the 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) Pigment 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 acts to adsorb on the surface of the pigment and prevent reaggregation in the dispersion step. 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, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone 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, a vinyl monomer having a sulfonic acid group, a vinyl monomer having a phosphate group, a monomer having a basic nitrogen atom, and other monomers.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono ( A (meth) acrylate etc. can also be utilized. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable 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), phosphorus And acid mono (1-methyl-2-acryloyloxyethyl ester).

  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 diesters (Meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like. These monomers may be used independently and may use 2 or more types together. When applied to a pigment dispersion composition (colored photosensitive element 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, (meth ) 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, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono ( A (meth) acrylate etc. can also be utilized. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable 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.
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, when radically polymerizing a monomer having a pigment adsorbing group or a monomer having no pigment adsorbing group, thiolcarboxylic acid or 2-acetylthioethyl A polymer obtained by polymerizing a compound containing a thioester and a thiol group in a molecule such as ether or 10-acetylthiodecanethiol is treated with an alkali such as sodium hydroxide or ammonia, There is also known a method in which a polymer having a thiol group is used, and the monomer component of the other block is radically polymerized in the presence of the obtained polymer having a thiol group at one end. 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, but the structural unit represented by the following general formula (9) is a branch part. More preferred is a graft polymer having at least

In the general formula (9), R ⁹¹ 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 ⁹² (where, R ⁹² 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 (9), the alkyl group represented by R ⁹¹ 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 ⁹¹ , a hydrogen atom and a methyl group are preferable.

  In general formula (9), 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 ⁹² represented by Q in the general formula (9), the alkyl group represented by R ⁹² 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. Among such alkyl groups, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, an aryl group, or a hydroxyl group is preferable, and an unsubstituted alkyl group is particularly preferable.

The aryl group represented by R ⁹² in —COOR ⁹² represented by Q in the general formula (9) may have a substituent, preferably an aryl group having 6 to 20 carbon atoms, particularly carbon. An aryl group having 6 to 12 atoms is preferred. Examples of the substituent for the aryl group include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, and an acylamino group. Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Phenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodeciloylamidophenyl group, Etc. Among such aryl groups, an unsubstituted aryl group or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferable, and an aryl group substituted with an alkyl group is particularly preferable.

Of such R ⁹² , 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 (9) 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 synthesizing the graft polymer having at least the structural unit represented by the general formula (9) in the branch.
Specific examples include copolymerization of a macromonomer having at least a structural unit represented by the general formula (9) and an ethylenically unsaturated monomer copolymerizable with the macromonomer.

  Of the macromonomers having at least the structural unit represented by the general formula (9), preferred are those represented by the following general formula (10).

In General Formula (10), R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A represents a group having at least the structural unit represented by General Formula (9). W represents a single bond or the following linking group.

Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a hydroxyl group, and Z ³ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Or an aryl group having 6 to 20 carbon atoms. ) Represents a single linking group selected from atomic groups such as linking groups or any combination thereof.
Specific examples of the macromonomer represented by the general formula (10) include those shown below.

A in the structure is synonymous with A in the general formula (10).
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 groups introduced here are organic dye structures, heterocyclic structures, acidic groups, groups having basic nitrogen atoms, urea groups, urethane groups, coordination groups 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-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2- Propanol, 3-mercapto-2-buta , Mercaptophenol, 2-mercaptoethylamine, 2-mercapruimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or oxidized products of these mercapto compounds Certain disulfide compounds and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) can be mentioned.

  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).
As the dispersant, a specific polymer compound, a graft polymer, or a terminal-modified polymer is preferable, and among them, a graft polymer or a terminal group containing a copolymer unit derived from a monomer having an organic dye structure or a heterocyclic structure. Particularly preferred are 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.

In the case of a polymer dispersant, the addition amount of the dispersant is preferably 0.5 to 100% by mass, more preferably 3 to 100% by mass, and more preferably 5 to 80% with respect to the processed pigment. Mass% 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 specific polymer compound coated with the pigment and the dispersant is not particularly limited, but when the dispersant is a polymer dispersant (specific polymer compound / dispersant), 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 the processed pigment with a solvent and, if necessary, a dispersant or an alkali-soluble resin.

  The pigment dispersion composition is prepared, for example, by a method of kneading and dispersing by adding the processed pigment of the present invention, a solvent and, if necessary, a dispersant or an alkali-soluble resin. 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 pigment dispersion of the present invention is suitably used for a colored photocurable composition used for producing a color filter.

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

  The photosensitive composition of the present invention contains, for example, a processed pigment coated with the specific polymer compound described above containing a photopolymerizable compound and a photopolymerization initiator (preferably together with a solvent). Then, it can be prepared by mixing and dispersing additives such as alkali-soluble resins and mixing and dispersing using various mixers and dispersers.

<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) xanthone or acridine compounds described in Fr-2456541, coumarin or biimidazole compounds described in JP-A-10-62986, JP-A-8 Sulfonium organoboron complexes such as 015521 , Etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (triazine, halomethyloxadiazole, coumarin), acridine, biimidazole An oxime ester type is preferable.

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

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

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

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

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

  Examples of the active halogen compound (triazine-based, oxadiazole-based, coumarin-based) 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-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (di) Ethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl -5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl-5 -A No-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl- Preferable examples include 5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

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

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

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

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

  As content in the 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<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.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
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, and 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.

(solvent)
In general, the colored photosensitive composition of the present invention can be suitably prepared using a solvent together with the above components.
Solvents 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, 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 it independently.

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

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

(Fluorine organic compounds)
By containing a fluorinated organic compound, 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 object to be coated and the coating liquid is reduced to improve the wettability to the object to be coated, and the coating property to the object to be coated is improved, so a thin film of about several μm can be formed with a small amount of liquid. Even if it is formed, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

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

Examples of the fluorine-based 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 fluorine-based surfactant as the fluorine-based compound, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be preferably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (Manufactured by JEMCO).

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

  0.001-2.0 mass% is preferable with respect to the total mass of a 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 colored photosensitive composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

(Thermal polymerization component)
It is also effective to contain a thermal polymerization component in the colored photosensitive composition of the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. The epoxy compound is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and 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 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical) and their similar The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UCB) can 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 Toto 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 be used.

(Surfactant)
The colored photosensitive composition of the present invention is preferably constituted using various surfactants from the viewpoint of improving coatability. As the surfactant, various nonionic, cationic and anionic surfactants can be used in addition to the above-mentioned fluorosurfactant. Among these, the above-described nonionic surfactants are preferably fluorine-based surfactants having a perfluoroalkyl group and nonionic surfactants.

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

  The colored photosensitive composition of the present invention can be used for various purposes, for example, to form a colored region of a color filter.

<Color filter>
The color filter of the present invention is characterized by having a colored region formed on the substrate using the above-mentioned colored photosensitive composition of the present invention. Here, the colored region includes both a two-color, three-color, or four-color coloring pattern (pixel portion) and a black matrix.

A method for producing the color filter of the present invention will be described.
First, the colored photosensitive composition of the present invention is applied directly or via another layer to a substrate by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc. The coating film which consists of an adhesive composition is formed (application | coating process). Then, it exposes with respect to a coating film through a predetermined mask pattern (exposure process). After the exposure, the uncured portion of the coating film is developed and removed with a developer (development process). By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

[Coating process]
First, the substrate used in the coating process will be described.
Examples of the substrate used in the color filter of the present invention include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, used for liquid crystal display elements and the like. And a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate.
On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, 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 disposed is used. In addition, a color pattern using the colored photosensitive composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, 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 the TFT liquid crystal driving substrate can be used.

In the coating step, the method for applying the colored 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, Slit nozzle coating method) is 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, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored photosensitive composition from the slit nozzle is usually 500 to 2000 microliters / second, preferably 800 to 1500 microliters / second, and the coating speed is usually 50 to 300 mm. / Sec, preferably 100 to 200 mm / sec.
Moreover, as solid content of the coloring photosensitive composition used at an application | coating process, it is 10-20% normally, Preferably it is 13-18%.

When forming the coating film by the coloring photosensitive composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is generally 0.3-5.0 micrometers, Desirably 0.5-4 0.0 μm, most preferably 0.5 to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking treatment) is preferably in the range of 0.5 to 5.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking.
As the conditions for vacuum drying, 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 in 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. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. High frequency processing can be used alone.

[Exposure process]
In the exposure step, the coating film made of the colored photosensitive composition formed as described above is exposed through a predetermined mask pattern.
The radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
In manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
Further, when manufacturing a color filter for a solid-state imaging device, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

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

Examples of the organic solvent used for development include the solvents described above that can be used when preparing the colored photosensitive composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 An alkaline aqueous solution dissolved so as to be ˜1 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. It is also possible to prevent uneven development by previously moistening the surface to be developed with water or the like before touching the developer. In addition, development can be performed with the substrate inclined.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.

After rinsing, draining and drying are usually performed at about 200 ° C. to 250 ° C.
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 steps for each color in accordance with the desired number of hues, a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed can be produced.

As for the use of the colored photosensitive composition of the present invention, the description has mainly focused on the use for the color pattern of the color filter. However, it is also used for the formation of a black matrix that isolates the color pattern (pixels) constituting the color filter. Can be applied.
The black matrix on the substrate is a colored curable composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

<Liquid crystal display device, solid-state imaging device>
The liquid crystal display element and the solid-state image sensor of the present invention are provided with the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap with liquid crystal and sealing, a panel which is the liquid crystal display element of the present invention is obtained. . For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.

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

[Example 1, Comparative Example 1]
(Synthesis of specific polymer compound 1)
A-1 (monomer capable of forming a structural unit represented by the general formula (1)) 15.0 g, MMA 135.0 g and 1-methoxy-2-propanol 350.0 g were introduced into a nitrogen-substituted three-necked flask. The mixture is stirred with 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 stirred with heating 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% solution of the specific polymer compound 1 (mass ratio of A-1 to MMA of 1: 9) was obtained.
As a result of measuring the weight average molecular weight of the obtained specific polymer compound by a gel permeation chromatography method (GPC) using polystyrene as a standard substance, it was 20,000.

(Synthesis of Specific Polymer Compound 5)
A-20 (monomer capable of forming a structural unit represented by the general formula (1)) 22.5 g, MMA 127.5 g and 1-methoxy-2-propanol 350.0 g were introduced into a nitrogen-substituted three-necked flask. The mixture is stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor) and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 2.10 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, 2.10 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of the specific polymer compound 5 (mass ratio of the A-20 and MMA of 15:85) was obtained.
As a result of measuring the weight average molecular weight of the obtained polymer compound by a gel permeation chromatography method (GPC) using polystyrene as a standard substance, it was 20,000.

(Synthesis of specific polymer compounds 2-4 and 6-15)
Specific polymer compounds 2 to 4 and 6 to 15 were synthesized in the same manner as in the specific polymer compound 1 with the composition according to Table 1.

Abbreviations in Table 1 are as follows.
MMA: Methyl methacrylate BzMA: Benzyl methacrylate M-1 to M-11: Used to make the specific polymer compound have a heterocyclic ring in the side chain, and shown in the above [Chemical Formula 13] to [Chemical Formula 15].
MM-1 was used in the same applications as M-1 to M-11 and shown in [Chemical Formula 26].

(Creation of processed pigment)
50 g of the pigment described in Table 2, Table 3 and Table 4, 600 g of sodium chloride, 25 g of the specific polymer compound solution, and 100 g of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 10 hours. Next, the 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 average primary particle diameter of processed pigment)
The average primary particle diameter of the obtained processed pigment was obtained by observing with a transmission electron microscope (TEM), measuring 100 particle sizes at a portion where the particles were not aggregated, and calculating the average value. .

(Evaluation of pigment coverage)
10 g of the obtained processed pigment was put into 100 mL of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was precipitated with a centrifugal separator at 80,000 rpm for 8 hours. The solid content of the supernatant was determined from the drying method. The amount of the 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.

  The details of the pigments and polymer compounds described in Tables 2 to 4 are as follows.

-Pigment-
PR254; C.I. I. Pigment Red 254
PG36; C.I. I. Pigment Green 36
PB15: 6; C.I. I. Pigment Blue 15: 6
PV23; C.I. I. Pigment Violet 23

-Polymer compound-
P-1; Methyl methacrylate / methacrylic acid = 90/10 mass% copolymer 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

  From the above results, it can be seen that this example is a processed pigment having a lower liberation rate than the comparative example.

[Example 2, Comparative Example 2]
<Preparation of pigment dispersion composition>
In accordance with the composition of Table 5, the components of the following composition (1) were mixed, and using a homogenizer, the rotational speed was 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (1)]
• 95 parts of processed pigments listed in Tables 2 to 4 • Pigment derivative A (described in the following structure “Chemical Formula 47”) 10 parts • Dispersant (30% of the dispersant described in Table 5 1-methoxy-2-propyl Acetate solution), amount shown in Table 5, 1-methoxy-2-propyl acetate 750 parts Subsequently, the mixed solution obtained above was further dispersed into a bead disperser disperse mat (GETZMANN) using 0.4 mmφ zirconia beads. For 6 hours, and further using a high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.) at a flow rate of 500 g / cm under a pressure of 2,000 kg / cm 3. Dispersion processing was performed as min. This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
As shown in Table 5, in Comparative Examples 2-4 to 2-5, the processed pigment was 82.7 parts.

(Evaluation of pigment dispersion composition)
The following evaluation was performed about the obtained pigment dispersion composition. The results are shown in Table 5.
(1) Measurement and Evaluation of Viscosity For the obtained pigment dispersion composition, using an E-type viscometer (20 rpm, 30 ° C., manufactured by Tokyo Keiki Co., Ltd.), the viscosity η1 of the pigment dispersion composition immediately after dispersion, and The viscosity η2 of the pigment dispersion composition after 1 week after dispersion (at room temperature) was measured to evaluate the degree of thickening. Here, the low viscosity indicates that the increase in viscosity due to the dispersant is suppressed, and the dispersibility and dispersion stability of the pigment are good.

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

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

  From the above results, it can be seen that this example is a pigment dispersion composition having higher contrast, less likely to precipitate by post-baking, and less thickening with time than the comparative example.

[Example 3, Comparative Example 3]
<Preparation of pigment dispersion composition>
In accordance with the composition of Table 6, the components of the following composition (2) were mixed, and the rotational speed was 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (2)]
Processed pigment (processed pigment described in Table 6) 100 parts Dispersant (30% 1-methoxy-2-propylacetate solution of dispersant described in Table 6), amount described in Table 6 1-methoxy-2 -Propyl acetate 750 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
As shown in Table 6, in Comparative Examples 3-4 and 3-7, the processed pigment was 82.7 parts.

<Evaluation of pigment dispersion composition>
The following evaluation was performed about the obtained pigment dispersion composition. The evaluation method is the same as in the case of composition (1). The results are shown in Table 6.
(1) Viscosity measurement and evaluation (2) Contrast measurement and evaluation (3) Precipitation evaluation

  Since the absolute value of contrast differs depending on the hue, the green and blue comrades are compared. From the above results, it can be seen that in this example, compared to the comparative example, the photosensitive composition is suppressed in thickening with time, has a high contrast, and does not easily precipitate by post-baking.

[Example 4, Comparative Example 4]
<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 7) 120 parts-Dispersant (30% 1-methoxy-2-propyl acetate solution of dispersant described in Table 7) 250 parts-1-methoxy-2-propyl acetate ... 750 parts

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain pigment dispersion compositions shown in Table 7.

<Preparation of colored photosensitive composition>
Using the obtained pigment dispersion composition, the following colored photosensitive composition was prepared.
-Pigment dispersion described in Table 8 ... 2000 parts-Dipentaerythritol pentahexaacrylate ... 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)
1-methoxy-2-propyl acetate (solvent) 390 parts

<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) in Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-4. Is applied so that the x value as an index of color density is 0.650, and in Examples 4-8 to 4-11 and Comparative Examples 4-5 to 4-8, the y value as an index of color density is 0. In Examples 4-12 to 4-17 and Comparative Examples 4-9 to 4-10, the y value serving as an index of color density was applied to be 0.100. It was dried in an oven at 60 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heat-treated in a 220 ° C. oven 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.
In addition, the said x value and y value were adjusted by the measurement using color luminance meter BM-5 (made by Topcon Co., Ltd.).

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 8.

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

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

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

(3) Precipitation evaluation A 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 is 20 mW / cm ² ), and 1 of an alkali 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

  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. From the above results, it can be seen that this example is a color filter that has higher contrast, better alkali developer solubility than the comparative example, and is less likely to deposit by post-baking.

[Example 5, Comparative Example 5]
<Preparation of pigment dispersion composition>
The components of the following composition (4) 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 (4)]
110 parts of processed pigments listed in Table 9 250 parts of dispersant D-3 (30% 1-methoxy-2-propyl acetate solution) 20 parts of pigment derivative B (see below) 1-methoxy-2-propyl acetate ... 750 parts

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

<Preparation of colored photosensitive composition>
Using the obtained pigment dispersion composition, the following colored photosensitive composition was prepared.
-Pigment dispersion described in Table 9 ... 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)
1-methoxy-2-propyl acetate (solvent) 390 parts

<Preparation of color filter using colored photosensitive composition>
The obtained colored photosensitive composition (color resist solution) was placed on a glass substrate (1737, manufactured by Corning) of 100 mm × 100 mm in Examples 5-1 to 5-3 and Comparative Examples 5-1 to 5-3. Is applied so that the x value as an index of color density is 0.650, and in Examples 5-4 to 5-7 and Comparative Examples 5-4 to 5-6, the y value as an index of color density is 0. In Examples 5-8 to 5-13 and Comparative Examples 5-7 to 5-8, the y value serving as an index of color density was applied to be 0.100. It was dried in an oven at 60 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heat-treated in a 220 ° C. oven for 1 hour (post-baking) to form a color pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.
In addition, the said x value and y value were adjusted by the measurement using color luminance meter BM-5 (made by Topcon Co., Ltd.).

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated for contrast and alkali developer solubility in the same manner as described above. The results are shown in Table 9.
(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). Thereafter, exposure is performed at 100 mJ / cm ² without using a mask (illuminance is 20 mW / cm ² ), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) is used. The coating film was developed at 25 ° C. and subjected to heat treatment (post-baking) for 30 minutes in an oven at 230 ° C. Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 μm glass beads, and then 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: 60Hz
-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

  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. From the above results, it can be seen that this example is a color filter having higher contrast, better alkali developer solubility and higher voltage holding ratio than the comparative example.

<Other compounds in Examples>

D-1: M-1 / A-1 / MAA = 20/65/15% by mass, weight average molecular weight 23,000, acid value 100 mg KOH / g of polymer D-2: M-2 / A-1 / BzMA / MAA = 10/58/20/12% by 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%, weight average molecular weight 2,000, polymer having an acid value of 100 mgKOH / g D-5: M-1 / BzMA / MAA = 20/65/15 mass%, Polymer D-6 having a weight average molecular weight of 20,000 and an acid value of 100 mgKOH / g: St / A-1 / MAA = 30/55/15% by mass, a weight average molecular weight of 25,000 and an acid value of 100 mgKOH / g Polymer

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

Claims (16)

A processed pigment obtained by coating a pigment with a polymer compound containing at least a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom or —NR ² —, R ² represents a hydrogen atom or a monovalent organic group, and L represents an organic linking group. N represents an integer of 1 to 4.) The processed pigment according to claim 1, wherein the general formula (1) is represented by the following general formula (2).

(In General Formula (2), Y represents an alkylene group having 2 to 4 carbon atoms. L ¹ is an alkylene group having 2 to 10 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, or 6 to 20 carbon atoms. Any one of aromatic groups, which may have a substituent, m represents an integer of 1 to 20, and R ¹ represents a hydrogen atom or a methyl group.) The processed pigment according to claim 1, wherein the general formula (1) is represented by the following general formula (3).

(In general formula (3), k represents an integer of 2 to 10. i represents an integer of 1 to 20. R ¹ represents a hydrogen atom or a methyl group.) The processed pigment according to any one of claims 1 to 3, wherein L ¹ in the general formula (2) represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms. .   The processed pigment according to any one of claims 1 to 4, wherein k in the general formula (3) is 5 and i is an integer of 1 to 10. The processed pigment according to any one of claims 1 to 5, wherein the polymer compound has a weight average molecular weight of 1,000 or more and 100,000 or less.   The processed primary pigment according to any one of claims 1 to 6, wherein the average primary particle diameter is 5 to 25 nm.   The processed pigment according to any one of claims 1 to 7, 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.   The processed pigment according to any one of claims 1 to 8, wherein the polymer compound is produced by adding in the step of refining the pigment.   A pigment dispersion composition comprising the processed pigment according to any one of claims 1 to 9 dispersed in an organic solvent.   The pigment dispersion composition according to claim 10, further comprising a pigment dispersant.   The pigment dispersion composition according to claim 10 or 11, which is used for forming a colored region in a color filter.   A colored photosensitive composition comprising the pigment dispersion composition according to any one of claims 9 to 12, a photopolymerizable compound, and a photopolymerization initiator.   A color filter comprising a colored region formed of the colored photosensitive composition according to claim 13 on a substrate.   A liquid crystal display device comprising the color filter according to claim 14.   A solid-state imaging device comprising the color filter according to claim 14.