JP2009215361A - Processed pigment, pigment dispersed composition, photosensitive resin composition, color filter, and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processed pigment having a low dispersion viscosity and excellent dispersion stability. <P>SOLUTION: The processed pigment is obtained by kneading a diketopyrrolopyrrole pigment together with a water-soluble inorganic salt and a water-soluble organic solvent in the presence of at least one compound represented by the formula [wherein A is a monovalent substituent; B and C are each independently a monovalent organic group; n, l and m are each an integer of 1-5; R1 and R2 are each H or a monovalent organic group; and Ar is an aromatic hydrocarbon group] and then removing the inorganic salt and the solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a processed pigment, a pigment dispersion composition, a photosensitive resin composition, and a color filter using the same, which are particularly suitable for producing a color filter used for a liquid crystal display device, a solid-state imaging device, and the like. Regarding the method.

Pigments exhibit vivid color tone and high coloring power, and are widely used in many fields. For example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like can be cited as applications, and these are important compounds that are indispensable in daily life. The general properties of pigments and the classification according to use are also disclosed in various documents (see, for example, Non-Patent Document 1).
Among these uses, pigments for color filters are mentioned as those requiring high performance. In the use of the color filter, the pigment is used as a pigment dispersion composition by being dispersed with a pigment derivative and a dispersion resin.

In recent years, color filters have been used not only for monitors but also for televisions in liquid crystal display (LCD) applications. As these applications expand, advanced color characteristics in chromaticity and contrast are required. Has reached. In addition, advanced color characteristics such as reduction in color unevenness and improvement in color resolution are also demanded for solid-state imaging devices (image sensors).

  In order to meet the above requirements, the pigment particles are required to have a finer particle size and higher dispersibility. To increase the dispersibility of the pigment, for example, the surface of the phthalocyanine pigment is usually applied to the surface. Using a dispersant such as a low molecular weight resin having a polar functional group that is easily adsorbed on the modified surface, the pigment surface is modified with a derivative compound, while dispersing or stabilizing the pigment, A pigment dispersion composition containing a surface modifier and a dispersant is obtained. The obtained pigment dispersion composition further contains an alkali-soluble resin, a photopolymerizable composition, a photopolymerization initiator, and other components to form a photocurable composition, which is used to form a color filter by a photolithography method or the like. It has gained.

  In order to obtain high color characteristics, it is an effective means to reduce the particle diameter of the pigment. However, when the size is reduced, the surface area of the pigment particles is increased, and the dispersibility of the pigment is deteriorated. For this improvement, a larger amount of a surface modifier or a dispersant for modifying the pigment surface is required. For example, in order to improve the contrast, the amount of the surface modifier and the dispersant is 10 to 20% by mass of the pigment amount. For this reason, the surface modifier and the dispersant are colored. The influence on the color characteristics of the filter cannot be ignored. Further, the surface modifier and the dispersant have a great influence on the coating property of the colored layer. It has become necessary to obtain a colored layer having a uniform film thickness by increasing the size of the screen and increasing the size of the coated substrate.

In order to improve the dispersibility of the pigment, it has been reported that various pigment derivatives are used (for example, see Patent Documents 1 and 2). However, even with these techniques, it is necessary to use a large amount of pigment derivative or dispersant in order to ensure the dispersibility of the fine pigment. Therefore, applicability was extremely deteriorated, and only a colored photocurable composition having no production suitability was obtained.
In addition, in order to suppress strong secondary aggregation of the refined pigment, a rosin or a rosin derivative is added during the salt milling process to treat the pigment, and a high-contrast color filter is formed using the pigment dispersion. A technique to obtain is proposed (see, for example, Patent Document 3).

However, even with these methods, it is impossible to meet market demands for improving color characteristics such as higher contrast, and higher dispersibility and dispersion stability in finer pigments have been desired. Development of a colored photocurable composition having a wide development latitude suitable for production is a high market need.
“Pigment dispersion stabilization and surface treatment technology / evaluation” 2001, pages 123-224, Technical Information Association Japanese Patent Laid-Open No. 2001-51112 JP 2007-79094 A Japanese Patent No. 3130217

  The present invention has been made in view of the above. That is, the problem to be solved by the present invention is to provide a processed pigment having a low dispersion viscosity and excellent dispersion stability, a pigment dispersion composition using the processed pigment, and a photosensitive resin composition. Another problem to be solved by the present invention is to provide an excellent color filter having a high contrast, no color unevenness and a high voltage holding ratio, and a method for manufacturing the same.

The above object is achieved by the present invention described below.
That is, the processed pigment of the present invention is
<1> (a) a diketopyrrolopyrrole pigment in the presence of (b) at least one selected from compounds represented by the following formula (1), the following formula (2), and the following formula (3); (C) Water-soluble inorganic salt and (d) The water-soluble inorganic salt and (d) water-soluble organic solvent are removed after kneading together with a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt. The processed pigment.

[In Formula (1), A represents the monovalent substituent comprised from a nonmetallic atom, and n represents the integer of 1-5. When n is an integer of 2 or more, the plurality of A may be the same or different. In formula (2), B and C each independently represent a monovalent organic group, and l and m each independently represent an integer of 1 to 5. When l and m are each an integer of 2 or more, a plurality of B or a plurality of C may be the same or different. In formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹ and R ² represents a monovalent organic group. Ar represents an aromatic hydrocarbon group which may have a substituent. ]

<2> The compound represented by the formula (1) is a compound that represents an alkyl group having 1 to 24 carbon atoms or an aryl group having 1 to 24 carbon atoms as the A,
The compound represented by the formula (2) is a compound representing an alkyl group having 1 to 24 carbon atoms or an aryl group having 1 to 24 carbon atoms as B and C independently of each other.
It is a processed pigment as described in said <1> characterized by the above-mentioned.

  <3> The compound represented by the formula (1), the formula (2), or the formula (3) is a compound that does not contain an acidic group and a basic group. 2>.

  <4> The diketopyrrolopyrrole pigment is C.I. I. The processed pigment according to any one of <1> to <3>, which is Pigment Red 254.

The pigment dispersion composition of the present invention comprises:
<5> A pigment dispersion composition comprising the processed pigment according to any one of <1> to <4>.

The photosensitive composition for color filter of the present invention is
<6> A photosensitive resin composition for a color filter using the pigment dispersion composition according to <5>.

The method for producing the color filter of the present invention includes:
<7> A method for producing a color filter using the photosensitive resin composition according to <6>.

The color filter of the present invention is
<8> A color filter containing the photosensitive resin composition according to <6>.

  Usually, when satisfying performance such as high contrast which is the object of the present invention, it is necessary to refine the pigment by a salt milling method or the like. However, if the milling conditions are severe, such as adding a large amount of salt such as sodium chloride, aiming at high contrast, the crystal form of the pigment collapses and the contrast is significantly reduced. An example of adding a pigment derivative capable of interacting with a dispersion resin during salt milling is generally known. In such a form, the pigment derivative has an acidic functional group or a basic functional group. In the case of an acidic functional group, since it has a hydrogen bonding interaction, the pigment cannot be efficiently refined. In the case of a basic functional group, a diketopyrrolopyrrole pigment having an active hydrogen atom It interacts and the pigment cannot be made finer efficiently. In contrast, the processed pigment of the present invention covers all or part of the diketopyrrolopyrrole pigment by adding a diaryl diketopyrrolopyrrole compound having a specific substituent when performing salt milling. . At this time, the diaryl diketopyrrolopyrrole compound having a specific substituent preferably has no acidic group or basic group, and in the case of no acidic group or basic group, acid-base interaction or hydrogen It is presumed that the inhibition by the binding interaction is reduced, the active surface of the pigment is efficiently covered, and a specific substituent can act as an effective steric repulsion group. Thus, it is considered that the pigment is refined without breaking the crystal form of the pigment, and when the pigment dispersion is formed, high dispersion stability is exhibited, contrast is improved, and color unevenness is improved. Thus, it is considered that a color filter with high contrast and no color unevenness can be obtained. Contrary to expectation, as a milling additive, a compound having no acidic group or basic group is used, so the interaction with metal ions is reduced and the voltage holding ratio is improved when a color filter is formed. As a result.

  According to the present invention, a processed pigment having a low dispersion viscosity and excellent dispersion stability, a pigment dispersion composition using the processed pigment, and a photosensitive resin composition can be provided. In addition, it is possible to provide an excellent color filter with high contrast, no color unevenness, and high voltage holding ratio, and a method for manufacturing the same.

  Hereinafter, the processed pigment, the pigment dispersion composition, the photosensitive resin composition for a color filter, the color filter, and the production method thereof will be described in detail.

≪Processed pigment≫
The processed pigment of the present invention comprises (a) a diketopyrrolopyrrole pigment in the presence of at least one selected from (b) compounds represented by formula (1), formula (2) and formula (3). And (c) a water-soluble inorganic salt and (d) a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, and then (c) the water-soluble inorganic salt and (d) the water-soluble organic solvent are removed. It is characterized by. In the processed pigment of the present invention, if necessary, (e) a pigment derivative having at least one group selected from an acidic group and a basic group, (f) a pigment coating polymer compound, and the like, together with the above components May be used.

  Specifically, for example, (a) a diketopyrrolopyrrole pigment, and (b) at least one selected from compounds represented by formula (1), formula (2) and formula (3), After kneading c) a water-soluble inorganic salt and (d) a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, the kneaded product is added to an aqueous solvent (for example, water) and mixed and stirred. To do. Then, for example, the mixture is filtered and washed with water to remove (c) the water-soluble inorganic salt and (d) the water-soluble organic solvent. The processed pigment of the present invention is thus obtained. Further, (e) a pigment derivative having at least one group selected from an acidic group and a basic group, (f) a pigment coating polymer compound, and the like are added together with, for example, (a) a diketopyrrolopyrrole pigment And knead.

  Hereinafter, each component will be described.

<(A) Diketopyrrolopyrrole Pigment>
The (a) diketopyrrolopyrrole pigment that can be used in the processed pigment of the present invention is not particularly limited as long as it is a pigment having a diketopyrrolopyrrole skeleton. Among them, more preferably, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 270, C.I. I. Pigment red 272, and more preferably C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, particularly preferably C.I. I. Pigment Red 254.

In consideration of the high transmittance, it is preferable to use a finer one. In consideration of handling properties, the average particle size of the pigment is preferably 0.005 μm to 0.1 μm, and more preferably 0.005 μm to 0.05 μm. The average particle diameter is a particle diameter measured by the following method. The particle diameter of the pigment is determined by observing and measuring the obtained pigment with a transmission electron microscope (TEM).
The above (a) diketopyrrolopyrrole pigments may be used alone or in various combinations in order to increase color purity.

  In the processed pigment of the present invention, (a) an auxiliary pigment other than the diketopyrrolopyrrole pigment can be used in combination. As the sub-pigment, conventionally known various inorganic pigments or organic pigments can be used. In addition, considering that the inorganic pigment and the organic pigment preferably have a high transmittance, it is preferable to use finer ones. In consideration of handling properties, the average particle size of the sub-pigment is preferably 0.005 μm to 0.1 μm, and more preferably 0.005 μm to 0.05 μm. The average particle diameter can be measured by the method described above.

  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-mentioned metal oxides.

As an auxiliary pigment used in the pigment dispersion composition of the present invention, for example,
C. I. Pigment Yellow 1, 1, 1, 2, 3, 4, 5, 6, 9, 10, 11, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 17 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200 202, 203, 204, 205, 206, 207, 208
C. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 72, 74, 75, 77, 78, 79
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 150, 151, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 1 7, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 256, 257, 258, 259, 260, 262, 263, 265, 266, 267, 268, 269, 271, 273, 274, 275, 276
C. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50
C. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79
C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55
C. I. Pigment Brown 23, 25, 26
C. I. Pigment black 1, 7, carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black and the like.
As a more preferable sub-pigment,
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36
C. I. Pigment red 122, 150, 171, 175, 177, 209, 224, 242.

In the processed pigment of the present invention, a diketopyrrolopyrrole pigment may be used alone or in combination with an auxiliary pigment as described above. Specific examples of the combination include, for example, a mixture of a diketopyrrolopyrrole pigment and an anthraquinone pigment, at least one perylene pigment, a diketopyrrolopyrrole pigment and a disazo yellow pigment, an isoindoline yellow pigment, A mixture with at least one kind of quinophthalone yellow pigment can be used.
For example, diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and anthraquinone pigments include C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment red 224. In addition, C.I. I. Mixing with Pigment Yellow 139 is preferred.
The mass ratio of the red pigment to the yellow pigment is preferably in the range of 100: 5 to 100: 50. When the mass ratio of the yellow pigment to the red pigment is not less than the above lower limit, the light transmittance of 400 nm to 500 nm can be satisfactorily suppressed, and the color purity can be effectively increased. Moreover, by being below the said upper limit, it can suppress satisfactorily that a main wavelength becomes a short wavelength, and can suppress the shift | offset | difference from NTSC target hue. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

<(B) Compound which is at least one selected from compounds represented by the following formula (1), formula (2) and formula (3)>
(B) A compound that is at least one selected from the compounds represented by the following formula (1), the following formula (2), and the following formula (3) (hereinafter simply referred to as “specific diaryl diesters”). The compound (referred to as “ketopyrrolopyrrole compound”) is preferably a compound of the formula (1). The specific diaryl diketopyrrolopyrrole compound is preferably a compound containing no acidic group or basic group.

In formula (1), A represents a monovalent substituent composed of a nonmetallic atom, and n represents an integer of 1 to 5. When n is an integer of 2 or more, the plurality of A may be the same or different.
In formula (2), B and C each independently represent a monovalent organic group, and l and m each independently represent an integer of 1 to 5. When l and m are each an integer of 2 or more, a plurality of B or a plurality of C may be the same or different. In formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹ and R ² represents a monovalent organic group. Ar represents an aromatic hydrocarbon group which may have a substituent.

  In the formula (1), examples of the substituent represented by A include a monovalent organic group and other substituents. However, hydrogen atoms are not included. The substituent represented by A is preferably an organic group having no acidic group or basic group.

In the formula (1), the monovalent organic group represented by A includes an alkyl group, aryl group, heteroaryl group, alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl Group, heteroaryloxycarbonyl group, alkylaminocarbonyl group, arylaminocarbonyl group, heteroarylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylaminocarbonyl group, arylaminocarbonyl group, hetero Examples include an arylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heteroarylsulfonyl group. These groups may have a substituent.
Among the specific examples of A above, an alkyl group and an aryl group are preferable from the viewpoint of improving the flexibility of the (b) specific diaryl diketopyrrolopyrrole compound and the viewpoint of steric repulsion for suppressing pigment aggregation. Furthermore, as a magnitude | size of a substituent, a C1-C24 alkyl group and a C1-C24 aryl group are preferable.

  In the formula (2), examples of the substituent represented by B and C include a monovalent organic group and other substituents. Preferably, the substituent represented by B and C is an organic group having no acidic group or basic group. However, hydrogen atoms are not included.

In the formula (2), the monovalent organic groups represented by B and C are independently of each other an alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group. Group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylaminocarbonyl group, arylaminocarbonyl group, heteroarylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylaminocarbonyl group, aryl Examples include an aminocarbonyl group, a heteroarylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heteroarylsulfonyl group. These groups may have a substituent.
In addition, from the viewpoint of improving the flexibility of the (b) specific diaryl diketopyrrolopyrrole compound and the steric repulsion property for suppressing aggregation of the pigment, among the specific examples of the above B and C, an alkyl group and an aryl group are preferable. Furthermore, as a magnitude | size of a substituent, a C1-C24 alkyl group and a C1-C24 aryl group are preferable.

In formula (3), R ¹ and R ² include a hydrogen atom or a monovalent organic group or other substituent, and preferably represents a monovalent organic group having no acidic group or basic group. However, as described above, at least one of R ^{1 and} R ² is a monovalent organic group.
Examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hetero Examples include an aryloxycarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, a heteroarylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heteroarylsulfonyl group. These groups may have a substituent.
In addition, in order to improve the flexibility of the specific diaryl diketopyrrolopyrrole compound for improving the adsorptivity to the pigment, among the specific examples of R ¹ and R ² above, an alkyl group, an aryl group, a heteroaryl group, An alkylcarbonyl group, an alkoxycarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, and an alkylaminocarbonyl group are preferred. Furthermore, an alkyl group, an aryl group, an alkylcarbonyl group, and an alkoxycarbonyl group are more preferable. In particular, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms and / or a heteroaryl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and 2 to 24 carbon atoms. The alkoxycarbonyl group is preferable.

  In formula (3), specific examples of Ar include an aryl group and a heteroaryl group. These groups may have a substituent. Among these, an aryl group is preferable, in particular, an aryl group having 6 to 24 carbon atoms having an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms having an aryl group having 6 to 24 carbon atoms, and a carbon number. An aryl group having 6 to 24 carbon atoms and having 2 to 24 alkoxy groups is preferred.

The substituent that can be substituted with the groups represented by A, B, C, R ¹ , R ² and Ar is not particularly limited, but preferably a nitro group, an alkyl group, a fluoroalkyl group, an aryl Group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylaminocarbonyl group An arylaminocarbonyl group, a heteroarylaminocarbonyl group, an alkylcarbonylamino group, an arylcarbonylamino group, a heteroarylcarbonylamino group, an alkylsulfonyl group, an arylsulfonyl group, and a heteroarylsulfonyl group. Among these, a nitro group, an alkyl group, a fluoroalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group are preferable. In particular, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 3 to 24 carbon atoms, and an alkoxy group having 1 to 24 carbon atoms are preferable.

  Specific examples of the (b) specific diaryl diketopyrrolopyrrole compound that can be used in the present invention are listed below, but are not limited thereto.

  As content of (b) specific diaryl diketopyrrolopyrrole compound in this invention, 0.01-50 mass% is preferable with respect to (a) diketopyrrolopyrrole pigment, More preferably, it is 0.05-20 mass. %, And more preferably 0.1 to 10% by mass. It is preferable for the content to be in the above-mentioned range since the dispersion stability is high and the hue is not impaired. In addition, the said (b) specific diaryl diketopyrrolopyrrole compound may be used individually by 1 type, and may use 2 or more types together.

<(C) Water-soluble inorganic salt>
The inorganic salt 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. Of these, sodium chloride or sodium sulfate is preferably used from the viewpoint of cost. The amount of the inorganic salt used when the salt milling treatment is performed is preferably 1 to 30 times (mass ratio) of the organic pigment, particularly 5 to 25 times, in terms of both processing efficiency and production efficiency. . This is from the viewpoint that, as the mass ratio of the inorganic salt to the organic pigment is larger, the refinement efficiency is higher, while the processing amount of one pigment is reduced.

<Water-soluble organic solvent that does not substantially dissolve the inorganic salt of (d) and (c)>
The water-soluble organic solvent functions to wet the organic pigment and inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt of ii) used. . However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates.
Examples of the water-soluble organic solvent (d) 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 and the like are 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 in the above range, uniform kneading can be performed, the particle size can be made more uniform, and the kneaded composition can be kept at an appropriate hardness, which is favorable for the kneaded composition. Shear is applied, and a sufficient fine effect can be obtained.
The (d) water-soluble organic solvent may be added in the initial stage in the salt milling process, or may be added separately. Further, iii) water-soluble organic solvents may be used alone or in combination of two or more.

<(E) Pigment derivative having at least one group selected from an acidic group and a basic group>
(E) A pigment derivative having at least one group selected from an acidic group and a basic group (hereinafter simply referred to as “acidic / basic group-containing pigment derivative”) used in the present invention has a pigment core structure. And an organic linking group and at least one group selected from an acidic group and a basic group, and the structure thereof can be represented by the following formula (4-1) or formula (4-2).

[Pig]-(w-A) _n formula (4-1)
[Pig] _m −w−A _n formula (4-2)
(In the formulas (4-1) and (4-2), [Pig] represents a pigment nucleus structure. W represents a chain-like or branched-chain organic linking group composed of 3 or more elements (however, a hydrogen bond is represented by A represents at least one group selected from an acidic group and a basic group, n represents an integer of 1 to 10, and m represents an integer of 1 to 10.)

(Pigment core structure)
The pigment mother nucleus structure refers to a partial chemical structure of a pigment typified by a chromophoric group. In the present invention, it has a chemical structure similar to the partial chemical structure and can form an interaction with the partial structure. Such a similar chemical structure is also included in the pigment core structure.

The pigment mother nucleus structure is a portion represented by [Pig] in the formulas (4-1) and (4-2). Examples of the pigment core structure include Hansa yellow, disazo yellow, benzimidazolone, lake red, toluidine red, naphthol AS, isoindoline, isoindolinone, quinacridone, perylene, anthraquinone , Diketopyrrolopyrrole, dioxazine violet, phthalocyanine, azomethine, pteridine, naphthol, pyrazolone, indigo, thioindigo, xanthene, indazine, carbon black, etc. be able to. Specific examples of the pigment structure include the following structures (1-A-1) to (1-A-10), (1-B-1) to (1-B-3), and (1-C-1). ) To (1-C-4), (1-D-1) to (1-D-2), and (1-E-1) to (1-E-6) can be used. The pigment dye structure may be a pigment structure or a pigment partial structure, and is not limited to the following specific pigment structure.
(In the following formula, X represents a chain-like or branched-chain organic linking group composed of three or more elements (that is, “w” in the formula (4-1) and formula (4-2)). In the case where two or more Xs are included, each X may be different).

(Acidic group)
The acidic group of the (e) acidic / basic group-containing pigment derivative in the present invention corresponds to the portion A in the above (4-1) or the formula (4-2) and has a structure showing acidity. There is no particular limitation as long as it is present. Preferably, a sulfonic acid group, a sulfonate having a metal ion as a counter ion, a monoalkyl ammonium ion having 1 to 12 carbon atoms, a dialkyl ammonium ion having 1 to 24 carbon atoms, or a trialkyl ammonium ion having 1 to 36 carbon atoms. A sulfonate, carboxylic acid group, phosphoric acid group, hydroxyl group, and boric acid group having a counter ion are used, and a sulfonate salt and a carboxylic acid group having a sulfonic acid group and a metal ion as a counter ion are more preferably used. More preferably, a sulfonate having a sulfonic acid group or a metal ion as a counter ion is used. As said metal ion which is a counter ion of a sulfonate, the metal ion chosen from the 1st-13th group of a periodic table can be used, Preferably the metal ion chosen from the 1st-2nd group of a periodic table More preferably, they are potassium ion and sodium ion.
(E) The acidic functional group of the acidic / basic group-containing pigment derivative in the pigment dispersion composition of the present invention can be used by combining a plurality of types of acidic functional groups. For example, a sulfonate having a sulfonic acid group and a carboxylic acid group, a sulfonic acid group and a metal ion as a counter ion, and a sulfonic acid having a sulfonic acid group, a carboxylic acid group, and a trialkylammonium ion having 1 to 36 carbon atoms as a counter ion. Examples thereof include a salt, a sulfonate group having a sulfonic acid group, a carboxylic acid group, and a trialkylammonium ion having 1 to 72 carbon atoms as a counter ion, a hydroxyl group, and the like. However, the combination of acidic groups is not limited to these.

(Basic group)
The basic group of the (e) acidic / basic group-containing pigment derivative in the present invention corresponds to the part A in the formula (4-1) or the formula (4-2), and has a basic structure. There is no particular limitation as long as it is. Preferably -NR < ¹¹ > R < ¹² > and the heterocyclic ring containing a nitrogen atom are mentioned, More preferably, it is -NR < ¹¹ > R < ¹² >.
R ¹¹ and R ¹² each independently represents a monovalent organic group. Specifically, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, etc. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. R ¹¹ and R ¹² may be bonded to form a ring.
The heterocycle is preferably a heterocycle having 1 to 36 carbon atoms, and more preferably a heterocycle having 2 to 24 carbon atoms. Examples of the heterocyclic ring include pyrrolyl group, benzopyrrolyl group, pyrazolyl group, indazolyl group, imidazolyl group, benzoimidazolyl group, pyridyl group, quinolinyl group, isoquinolinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, quinazolinyl group, quinoxalinyl group, An acridinyl group, a phenanthridinyl group, a phthalazinyl group, a carbazolyl group, a carbolinyl group, a purinyl group, and a triazolyl group are preferable. Among these, 3-pyrazolyl group, 4-pyrazolyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 2-benzoimidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2 -Quinolinyl group, 4-quinolinyl group, 1-isoquinolinyl group, 3-isoquinolinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 2-pyrazinyl group preferable.
The basic group of the (e) acidic / basic group-containing pigment derivative in the present invention can be used in combination of a plurality of types of basic functional groups. Examples thereof include a dimethylamino group and an imidazolyl group, a dicyclohexylamino group and a 3-quinolinyl group, a methylamino group, a diphenylamino group, and a 5-pyridyl group. However, the combination of basic groups is not limited to these.

  Specific examples of the (e) acidic / basic group-containing pigment derivative that can be used in the present invention are listed below, but are not limited thereto.

  As content of (e) acidic / basic group containing pigment derivative in this invention, 0.1-50 mass% is preferable with respect to (a) diketopyrrolopyrrole pigment, More preferably, it is 0.5-30. It is mass%, More preferably, it is 1-20 mass%. It is preferable for the content to be in the above-mentioned range since the dispersion stability is high and the hue is not impaired. The (e) acidic / basic group-containing pigment derivative may be used alone or in combination of two or more.

<(F) Polymer compound for pigment coating>
In the soft milling process, in order to suppress crystal growth due to secondary aggregation of the refined pigment, (f) a pigment coating polymer compound is added before soft milling, during soft milling or after soft milling, Is preferably protected with a resin.
(F) The polymer compound for pigment coating may be added, preferably solid at room temperature, insoluble in water, and at least partially soluble in the water-soluble organic solvent used as a wetting agent during salt milling treatment It is preferable that Specifically, natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins are used. Moreover, i) When using the dried process pigment as a pigment and / or a sub-pigment, it is preferable that (f) the polymer compound for pigment coating is solid at room temperature.

The natural resin is typically rosin, and examples of the modified natural resin include 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.
The synthetic resin includes 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. A condensate is mentioned.
The timing for adding these resins may be added all at an early stage in the salt milling process, or may be added in divided portions.

  As content of the polymer compound for (f) pigment coating in this invention, 0.1-50 mass% is preferable with respect to (a) diketopyrrolopyrrole pigment, More preferably, it is 0.5-30 mass%. More preferably, it is 1-20 mass%. It is preferable for the content to be in the above-mentioned range since the dispersion stability is high and the hue is not impaired. The above (f) pigment coating polymer compound may be used alone or in combination of two or more.

≪Pigment dispersion composition and photosensitive resin composition for color filter≫
The pigment dispersion composition of the present invention includes the processed pigment. Specifically, the pigment dispersion composition of the present invention includes, for example, (g) at least a solvent together with the processed pigment, and (e) a pigment having at least one group selected from an acidic group and a basic group. Derivatives, and (h) resins can be included as necessary. The photosensitive resin composition for a color filter of the present invention may further comprise (i) a polymerizable compound, (j) a polymerization initiator, (k) a sensitizer, and the like in the pigment dispersion composition. it can.

<(G) Solvent>
The solvent (g) used in the present invention is basically as long as the solubility of each component of the pigment dispersion composition of the present invention and the applicability of the photosensitive resin composition for a color filter of the present invention are satisfied. Although not particularly limited, it is preferably selected in consideration of safety.
(G) Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl esters of 3-oxypropionic acid such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, 2 -Oxypropio 2-oxypropionic acid alkyl esters such as ethyl acetate, propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate) , Ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid Ethyl), 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, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl carbitol acetate, butyl carbitol acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene and xylene are preferred.

  Among 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, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

  As a ratio of the (g) solvent which occupies in the pigment dispersion composition of this invention, 20-95 mass% is preferable and 25-60 mass% is more preferable. When the amount of the solvent is within the above range, the pigment can be uniformly dispersed, which is advantageous in terms of dispersion stability after dispersion.

<(H) Resin>
Preferred examples of the structure of the resin (h) used in the present invention include linear polymers, graft polymers, block polymers, terminal-modified polymers, polyurethanes, polyesters, polyimides, and the like.

(Linear polymer)
Examples of the linear polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, Those described in JP-A-54-92723, JP-A-59-53836, JP-A-59-71048 and the like are preferable. Namely, a resin having a monomer having a carboxyl group alone or copolymerized; a resin having a monomer having an acid anhydride alone or copolymerized to hydrolyze, half-esterify or half-amide the acid anhydride unit; an epoxy resin And epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene. Examples of the monomer having an acid anhydride include maleic anhydride. Can be mentioned.
Similarly, acidic cellulose derivatives having a carboxylic acid group in the side chain are also preferred. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

In the case of using a copolymer, a monomer other than the above-described monomers can be used as the compound to be copolymerized. Examples of the other monomers include the following compounds (1) to (12).
(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters and methacrylic esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2 Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2 Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) Methacrylic acid monomers in which a hetero atom is bonded to the α-position (for example, compounds described in Japanese Patent Application Nos. 2001-115595 and 2001-115598 can be mentioned).
Among these, (meth) acrylic resin having an allyl group, a vinyl ester group and a carboxyl group in the side chain, or a double bond in the side chain described in JP-A Nos. 2000-187322 and 2002-62698 An alkali-soluble resin having an amide group in the side chain described in JP-A-2001-242612 is preferable because it has an excellent balance of film strength, sensitivity, and developability.

  Moreover, the monomer which has a functional group which can adsorb | suck to a pigment is also used suitably for the said linear polymer. A monomer having a functional group that can be adsorbed on the pigment is preferable because it can adsorb on the pigment and suppress reaggregation of the pigment, thereby improving the dispersion stability of the pigment. Specific examples include (a) a monomer having an organic dye structure or a heterocyclic structure, (b) a monomer having an acidic group, and (c) a monomer having a basic nitrogen atom.

(I) The monomer having an organic dye structure or a heterocyclic structure is not particularly limited, and examples thereof include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series and anthrapyridine. , Ansanthrone, Indanthrone, Flavanthrone, Perinone, Perylene, Thioindigo pigment structures; , Thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline Isoindolinone, benzimidazolone, benzothiazole, succinimide, may phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, be mentioned a monomer having a heterocyclic structure anthraquinone.
More specifically, monomers having the following structure can be exemplified.

(B) Examples of the 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, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly 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.

(C) Monomers having a basic nitrogen atom include heterocyclic monomers, (meth) acrylic acid esters, (meth) acrylamides, and styrenes.
Examples of the monomer having a heterocyclic ring include vinyl pyridine, vinyl imidazole, and vinyl triazole.
(Meth) acrylic acid esters include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and 1- (N, N-dimethylamino) (meth) acrylic acid. -1,1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, (meth) acryl N, N-di-n-butylaminoethyl acid, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, (meth) acrylic acid 1-pyrrolidinoethyl, (meth) acrylic acid N, N-methyl-2-pyrrolidylaminoethyl and (meth) acrylic acid N, - like methylphenylamino ethyl.
(Meth) acrylamides include 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) methacrylamide, 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 and the like can be mentioned.
Examples of styrenes include N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene.

  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 for the linear polymer. Examples of the ionic vinyl monomer include an anionic vinyl monomer and a cationic vinyl monomer.
Examples of the anionic vinyl monomer include (b) alkali metal salts of vinyl monomers in monomers having an acidic group, salts with organic amines (for example, tertiary amines such as triethylamine and dimethylaminoethanol), and the like.
As the cationic vinyl monomer, the vinyl monomer in the monomer having a basic nitrogen atom (c) is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl chloride Benzyl halides such as 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) Quaternized with dialkyl sulfate (alkyl group: C1-4) and the like, and dialkyl diallylammonium salts.

  The monomer having a functional group that can be adsorbed to the pigment containing the monomers (a) to (c) 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. May be used in combination.

(Block polymer)
The block polymer is not particularly limited in the type of monomer, but various block polymers synthesized using monomers used for the synthesis of the linear polymer can be used. Preferably, a block polymer comprising a block having a functional group capable of adsorbing to a pigment (pigment adsorbing group), a block having an alkali-soluble group, and a block not adsorbing to the pigment, a block not adsorbing to the pigment, and an alkali-soluble And a block polymer comprising a block having a group.

  As a method for obtaining the block polymer, a conventionally known method can be used. For example, living polymerization, iniferter method and the like are known. As still 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 ether, 10-acetylthiodecanethiol, etc. A compound containing a thioester and a thiol group in the molecule is polymerized, and the resulting polymer is treated with an alkali (such as sodium hydroxide or ammonia) to obtain a polymer having a thiol group at one end. Also known is a method of radical polymerization of the monomer component of the other block in the presence of the obtained polymer having a thiol group at one end. Among these, living polymerization is preferable.

  Commercially available products can be used as the block polymer. Specific examples include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.

(Graft polymer)
The graft 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, and JP-A-9-169821. Preferred examples include compounds obtained by modifying the side chain amino group of polyallylamine with polyester with a polyester polyol-added polyurethane described in JP-A-60-166318, and further, JP-A-9-171253 and The graft type polymer having a polymerizable oligomer (hereinafter referred to as “macromonomer”) as a copolymerization component described in Macromonomer Chemistry and Industry (IPC Publishing Department, 1989) and the like is also preferable. it can.

  Preferred examples of the branch (side chain) of the graft polymer include polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, and the like, but the structural unit represented by the following general formula (5) Is more preferable.

[In General Formula (5), R ⁷⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Q is a cyano group, an aryl group having 6 to 30 carbon atoms, —COOR ⁷⁵ (where R ⁷⁵ Represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 30 carbon atoms) or a group having an alkali-soluble group in the cyclic structure. ]

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

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

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

The aryl group represented by R ⁷⁵ in —COOR ⁷⁵ represented by Q in the general formula (5) may have a substituent, 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. Is mentioned. 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 aryl group substituted with an alkyl group is particularly preferred.

Of such R ⁷⁵ , a hydrogen atom and an alkyl group having 1 to 22 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are particularly preferable.

  Specific examples of the branch part of the graft polymer having at least the structural unit represented by the general formula (5) in the branch part include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly -I-butyl (meth) acrylate, poly (methyl (meth) acrylate-co-benzyl (meth) acrylate), poly (methyl (meth) acrylate-co-styrene), poly (methyl (meth) acrylate-co- ( (Meth) acrylic acid), poly (methyl (meth) acrylate-co-acrylonitrile) and the like.

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

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

[In General Formula (6), R ⁷⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W is a single bond, or

Represents a single selected from atomic groups linking group or an optional linking group composed of a combination of (Incidentally, in the above atomic group, Z _1, Z ₂ is a hydrogen atom, a halogen atom, an alkyl of 1 to 6 carbon atoms A group, a cyano group, and a hydroxyl group, and Z ₃ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms). A represents a group having at least the structural unit represented by the general formula (5). ]
Specific examples of the macromonomer represented by the general formula (6) include the following.

[In the specific example of the macromonomer represented by the general formula (6), A has the same meaning as A in the general formula (6). ]
Examples of such commercially available macromonomers include one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-end methacryloylated poly-n. -Butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, Toa Gosei Chemical Co., Ltd.) ) Made).

The molecular weight of the macromonomer is preferably a polystyrene-equivalent number average molecular weight (Mn) of 1000 to 20000, and more preferably 2000 to 15000. When the number average molecular weight is within the above range, the steric repulsion effect as a pigment dispersant can be more effectively obtained.
The number average molecular weight can be measured by the following method.
The weight average molecular weight of the macromonomer can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
The number average molecular weight in this specification can be measured by the same method.

  Examples of the ethylenically unsaturated monomer copolymerizable with the macromonomer described above include various monomers used in the above-described linear polymer synthesis (particularly, (a) monomers having an organic dye structure or a heterocyclic structure, ( (B) a monomer having an acidic group, (c) a monomer having a functional group capable of adsorbing to a pigment, such as a monomer having a basic nitrogen atom).

  Examples of commercially available graft polymers include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.

(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 chain transfer agent containing a functional group The functional group introduced here includes an adsorption site (that is, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, urea Group, urethane group, group having a coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxysilyl group, epoxy group, isocyanate group, hydroxyl group and 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 (functional group-containing chain transfer agent) capable of introducing a functional group at the polymer terminal include, for example, mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid). 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino ] Propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propane Diol, 1-mercapto-2-propanol, -Mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mecarpurimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.), or these mercapto Examples thereof include disulfide compounds which are oxidants of compounds, and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

  Examples of the polymerization initiator (functional group-containing polymerization initiator) capable of introducing a functional group at the polymer terminal include 2,2′-azobis (2-cyanopropanol) and 2,2′-azobis (2-cyano). Pentanol), 4,4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis [2- (5-methyl-2-imidazoline) -2-yl) propane], 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidine- 2-yl) propane], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propyl Pion'amido] and the like, and derivatives thereof.

As a monomer used for polymerization, a monomer used in the synthesis of the above-described linear polymer can be used.
Examples of commercially available terminal-modified polymers include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol.

  When the above (d) resin is used as a dispersant, a graft polymer and a terminal-modified polymer are preferable, and among them, a copolymer unit derived from a monomer having an organic dye structure or a heterocyclic structure (that is, (i) above) is contained. Particularly preferred are graft polymers, terminal-modified polymers having an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, or a urethane group as terminal groups.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. No. 271741 and Japanese Patent Application No. 10-116232, a urethane-based binder polymer containing an acid group, and a urethane having an acid group and a double bond in the side chain described in JP-A No. 2002-107918. Binder polymers and the like are also useful.
In addition, an acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in EP993966, EP1204000, JP-A-2001-318463, etc. is preferable because of its excellent balance of film strength and developability. is there.
Furthermore, polyvinyl pyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the resin is preferably 5,000 or more, more preferably 10,000 or more, in order to realize a viscosity range that is easy to use in the process such as coating a color resist, and to ensure film strength. The range is 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably 2,000 to 250,000.
The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
The weight average molecular weight can be measured by the following method.
The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

  The (h) resin used in the present invention is preferably a polymer having a large acid value from the viewpoint of developability. On the other hand, the viewpoint of maintaining a moderate solubility in alkali and widening the appropriate development range (development latitude). From this, it is preferable not to make the acid value too large. Therefore, the polymer acid value is preferably in the range of 20 to 300 (mg KOH / g polymer), more preferably in the range of 30 to 150 (mg KOH / g polymer), and even more preferably 35 to 120 (mg KOH / g polymer). Range.

The resin (h) can be synthesized by a conventionally known method. Solvents that can be used for the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1- Examples include methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
(D) As a radical polymerization initiator that can be used when synthesizing a resin, known compounds such as an azo initiator and a peroxide initiator can be used.

  The (h) resin used in the present invention can also be used as the above-mentioned (f) pigment coating polymer compound.

  Since the structure of the resin (h) easily affects the solubility in propylene glycol monomethyl ether acetate (PGMEA), the resin structure preferably has a higher solubility in PGMEA. Specifically, linear polymers, graft polymers, and terminal-modified polymers are preferably used, and terminal-modified polymers are more preferably used.

As content in the pigment dispersion composition of this invention of the said (h) resin, 0.1-50 mass% is preferable with respect to the total mass of a pigment dispersion composition, More preferably, it is 0.5-40 mass%. Yes, more preferably 1 to 30% by mass. It is preferable for the content to be in the above range since the dispersion stability is high and the hue is not impaired.
(H) resin in this invention may be used individually by 1 type, and may use 2 or more types together.

  The pigment dispersion composition of the present invention can further constitute a photosensitive resin composition using other components such as (i) a polymerizable compound, (j) a polymerization initiator, and (k) a sensitizer.

<(I) Polymerizable compound>
The photosensitive resin composition of the present invention is preferably constituted using (i) a polymerizable compound.
(I) As the polymerizable compound, a compound widely known as a compound having an ethylenically unsaturated double bond in the color filter-related industrial field can be used without particular limitation. For example, the compound which has chemical forms, such as a monomer, a prepolymer, ie, a dimer, a trimer, and an oligomer, or mixtures thereof, and those copolymers is mentioned.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer. Moreover, the EO modified body of these compounds, or PO modified body is also mentioned.

  As methacrylic acid esters, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

As itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, There is sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  Also suitable are urethane-based addition polymerizable compounds produced using an addition reaction of isocyanate and hydroxyl groups. As such a specific example, for example, a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708 has a hydroxyl group represented by the following general formula (E). Examples thereof include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer is added.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (E)
(In general formula (E), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group.)

  Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B 58-49860, JP-B 56-17654, JP-B Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photosensitive resin composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7 (300-308, 1984), those introduced as photocurable monomers and oligomers can also be used.

  In the present invention, when (f) a polymerizable compound is added, from the viewpoint of curing sensitivity, it preferably contains two or more ethylenically unsaturated bonds, and more preferably contains three or more. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D Le) isocyanurate, pentaerythritol tetraacrylate EO-modified product, dipentaerythritol hexaacrylate EO-modified products thereof as preferred. As commercially available products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) are preferable.

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di More preferred are pentaerythritol hexaacrylate EO modified products, and commercially available products include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI- 600 (manufactured by Kyoeisha Chemical Co., Ltd.) is more preferable.

  The above (i) polymerizable compound can be arbitrarily selected from an appropriate structure, blending, and addition amount from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface tackiness, and the like.

<(J) Polymerization initiator>
<Photopolymerization initiator>
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. 4,318,791 and European Patent Publication EP-88050A, benzophenones described in US Pat. No. 4,199,420 Aromatic thiol compounds, etc., (thio) xanthone-based or acridine-based compounds described in French Patent No. 2456741, coumarin-based or biimidazole-based compounds described in JP-A-10-62986, JP-A-8 Sulfonium organic boron complexes, etc. disclosed in Japanese Patent No. 0155521, etc. It 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.

  Preferred 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.

<(K) Sensitizer>
In the present invention, it is preferable to add (k) a sensitizer (sensitizing dye) as necessary. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the polymerization initiator component and polymerization reaction of the polymerizable compound thereby. 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)
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg 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, center 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 as defined 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, 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 (It can be a monovalent non-metallic atomic group or 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 examples of the heteroaryl ring in the particularly preferred heteroaryl group include 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 hetero ring which may have a substituent, and specific examples of the aromatic ring or hetero 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 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) A dye having a structure represented by the formula is particularly preferable because it provides a photosensitive resin composition having high sensitization 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 the general formula (XVIII-3), which is a preferred embodiment of the compound represented by the general 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.

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

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

The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass with respect to the total solid content of the photosensitive resin composition for a color filter of the present invention. Preferably it is 0.1-5 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.

<Other ingredients>
If necessary, the colored photosensitive resin composition of the present invention includes 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. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent can be contained.

(Chain transfer agent)
Examples of the chain transfer agent that can be added to the photosensitive resin composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
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.

  If it is the photosensitive resin composition which has the above preferable compositions, it is highly sensitive, is hardened | cured favorably with a low exposure amount, and favorable storage stability is obtained. Moreover, when it is applied (for example, applied) to the surface of a hard material such as a substrate, it exhibits high adhesion with the substrate or the like, and a fine and well-shaped pattern can be formed. Therefore, the photosensitive resin composition can be preferably used as a color filter.

≪Color filter and its manufacturing method≫
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is configured by providing a coloring pattern formed using the above-described photosensitive resin composition for a color filter of the present invention (preferably on a support).
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention comprises a photosensitive resin layer forming step of forming a photosensitive resin layer by coating a photosensitive resin composition for a color filter on a support, and a photosensitive resin layer formed by coating. An exposure process for exposing through a mask and a development process for forming a pattern by developing the exposed photosensitive resin layer are provided, and the formed pattern is cured by heating and / or exposure as necessary. Other steps such as a curing step to be performed and a post-baking step to perform heat treatment at a high temperature can be further provided.

Hereafter, each process in the manufacturing method of this invention is demonstrated.
(Photosensitive resin layer forming step)
In the photosensitive resin layer forming step, the photosensitive resin composition for a color filter of the present invention is applied on a support to form a photosensitive resin layer.
As the support, for example, soda glass used for liquid crystal display elements, Pyrex (registered trademark) glass, quartz glass and those obtained by attaching a transparent conductive film to these, photoelectric conversion element substrates used for imaging elements, For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.
If necessary, an undercoat layer may be provided on the support to improve adhesion with the formed layer, prevent diffusion of substances, or planarize the substrate surface.

As a coating method of the photosensitive resin composition, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied.
The coating thickness of the color filter photosensitive resin composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and still more preferably 0.2 to 3 μm.
The photosensitive resin composition coated on the support is preferably dried at 70 to 110 ° C. for about 2 to 4 minutes to form a photosensitive resin layer.

(Exposure process)
In the exposure step, the photosensitive resin layer formed in the photosensitive resin layer forming step is exposed in a pattern through a mask.
In the exposure, light is irradiated through a predetermined mask pattern, and only the irradiated portion is cured. By a development process in a development process described later, a cured film remains in a pattern shape (preferably three colors or four colors or more), and a colored film including colored pixels is obtained.

  As radiation used for exposure, ultraviolet rays such as g-line and i-line are preferable, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

(Development process)
In the development step, the exposed photosensitive resin layer is developed to elute the unexposed portion (uncured portion) into the developer (for example, an alkaline aqueous solution), leaving only the exposed portion (cured portion).
As the developer, an organic alkali developer that does not cause damage to a circuit or the like provided on the support is desirable. The development temperature is preferably 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkali include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7. An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so that the concentration is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass is preferably used. When a developer composed of an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  After the development, the excess developer is washed away and dried, followed by further heat treatment (post-bake).

  By repeating the above-described photosensitive resin layer forming step, exposing step, and developing step (further, if necessary, a curing step and a post-baking step) for a desired number of hues, a color filter having a desired hue can be produced.

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

<Synthesis of Pigment Derivative (I)>
The pigment derivative (I) shown below was synthesized by the method described in paragraphs [0105] to [0107] of JP-A-7-173406.

[Synthesis Example 1]
(Synthesis of Compound (1))
In a 500 ml three-necked flask, C.I. I. Pigment Red 255 (20 mmol, 1.0 eq) and N-methylpyrrolidinone (NMP) (200 ml) were added and stirred. Potassium carbonate (50 mmol, 2.5 eq) was added thereto and stirred for 30 minutes, and bromoethane (45 mmol, 2.25 eq) was further added thereto and stirred at 140 ° C. for 2 hours. Thereafter, the mixture was poured into ice water, and the precipitated red solid was collected by filtration and washed with 300 ml of acetone to obtain the following compound (1) (specific diaryl diketopyrrolopyrrole compound (3-A-41)). Yield 98%.

[Synthesis Example 2]
(Synthesis of Compound (2-1))
3-Cyanophenol (20 mmol, 1.0 eq) and N-methylpyrrolidinone (NMP) (200 ml) were added to a 500 ml three-necked flask and stirred on an ice bath. Potassium carbonate (24 mmol, 1.2 eq) was added thereto and stirred for 30 minutes, and bromoethane (24 mmol, 1.2 eq) was further added thereto, followed by stirring at 140 ° C. for 2 hours. Thereafter, the mixture was poured into ice water, the mixed solution was extracted (ethyl acetate), the organic solution was concentrated under reduced pressure, and further subjected to column chromatography (ethyl acetate / hexane) to give the compound (2-1) shown below. Got. Yield 95%.

(Synthesis of Compound (2))
To a 1 L three-necked flask, 300 ml of t-amyl alcohol and potassium t-butoxy (0.21 mol, 1.05 eq) were charged. After cooling to 5 ° C., the compound (2-1) (0.2 mol, 1.0 eq) was added and stirred at room temperature for 30 minutes. The reaction solution was heated to 100 ° C., and diisopropyl succinate (0.1 mol, 0.5 eq) was added dropwise over 2 hours. After the dropwise addition, the mixture was further stirred for 2 hours, and 20 ml of acetic acid was added to the reaction solution at 50 ° C., and the reaction solution was returned to room temperature. This was added dropwise to 1 L of acetone, and the resulting red solid was collected by filtration and further washed with 500 mL of distilled water. The following compound (2) (specific diaryl diketopyrrolopyrrole compound (3-A-42)) was obtained by heating and drying under reduced pressure at 50 ° C. for 5 hours. Yield 23%.

[Synthesis Example 3]
(Synthesis of Compound (3-1))
The compound (3-1) shown below was obtained in the same manner as the compound (2-1) except that bromoethane was changed to iodobutane in the synthesis of the compound (2-1). Yield 92%.

(Synthesis of Compound (3))
Compound (3) (specific diaryl diketo) shown below in the same manner as Compound (2) except that Compound (2-1) was changed to Compound (3-1) in the synthesis of Compound (2). A pyrrolopyrrole compound (3-A-43)) was obtained. Yield 21%.

[Synthesis Example 4]
(Synthesis of Compound (4-1))
The compound (4-1) shown below was obtained in the same manner as the compound (2-1) except that bromoethane was changed to benzyl bromide in the synthesis of the compound (2-1). Yield 98%.

(Synthesis of Compound (4))
Compound (4) (specific diaryl diketo) shown below in the same manner as Compound (2) except that Compound (2-1) was changed to Compound (4-1) in the synthesis of Compound (2). A pyrrolopyrrole compound (3-A-44)) was obtained. Yield 19%.

[Synthesis Example 5]
(Synthesis of Compound (5-1))
The compound (5-1) shown below was synthesized by the method described in US Pat. No. 4,778,899.

(Synthesis of Compound (5))
After charging 300 ml of t-amyl alcohol and the compound (5-1) (0.2 mol, 1.0 eq) into a 1 L three-necked flask, potassium t-butoxy (0.21 mol, 1.05 eq) was added to room temperature. Stirred under for 30 minutes. Thereafter, the compound (4-1) (0.21 mol, 1.05 eq) was added, and the reaction solution was heated to 100 ° C. and stirred for 2 hours. Thereafter, 20 ml of acetic acid was added to the reaction solution at 50 ° C., and the reaction solution was returned to room temperature. This was added dropwise to 1 L of acetone, and the resulting red solid was collected by filtration and further washed with 500 mL of distilled water. The following compound (5) (specific diaryl diketopyrrolopyrrole compound (3-A-18)) was obtained by heating and drying under reduced pressure at 50 ° C. for 5 hours. Yield 47%.

[Example 1]
A photosensitive resin composition containing a pigment was prepared for forming a color filter for use in a liquid crystal display device.

[A1. Preparation of photosensitive resin composition]
A1-0. Preparation of processed pigments C.I. I. 50 g of Pigment Red 254 (BT-CF manufactured by Ciba Specialty Chemicals), 5 g of Compound (1), 500 g of sodium chloride, and 100 g of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to obtain a coated processed pigment 1. .

A1-1. Preparation of Pigment Dispersion 40 parts of the processed pigment prepared as described above, Dispersbyk-161 (manufactured by BYK) (30% solution) 50 parts as a dispersion resin, 5 parts of pigment derivative (I), and 3-ethoxy as a solvent A mixed liquid consisting of 100 parts of ethyl propionate was mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).

A1-2. Preparation of photosensitive resin composition (coating liquid) Using the pigment dispersion liquid (P1) subjected to the dispersion treatment, the mixture was stirred and mixed so as to have the following composition ratio, thereby preparing a photosensitive resin composition coating liquid.
-Colorant (the pigment dispersion (P1)) 600 parts-Photopolymerization initiator (2,2'-bis (2-chlorophenyl) -4,4 '
, 5,5'-tetraphenyl-1,2'-biimidazole) 25 parts Pentaerythritol tetraacrylate 50 parts Alkali-soluble resin (benzyl methacrylate / methacrylic acid)
/ Hydroxyethyl methacrylate copolymer,
Molar ratio: 80/10/10, Mw: 10000) 5 parts Solvent: PGMEA 900 parts Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part Sensitizer (compound represented by the following chemical formula α) ) 15 parts ・ Co-sensitizer (2-mercaptobenzimidazole) 15 parts

[A2. (Production of color filter)
A2-1. Formation of photosensitive resin layer A photosensitive resin composition containing the above pigment as a resist solution was slit-coated on a glass substrate of 550 mm × 650 mm under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a photosensitive resin composition coating film.

(Slit application conditions)
・ Gap of the opening at the tip of the coating head: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
・ Dry film thickness 1.75μm
・ Application temperature: 23 ℃

A2-2. Exposure and development Thereafter, the photosensitive resin composition coating film was exposed in a pattern using a 2.5 kW ultra-high pressure mercury lamp using a test photomask having a line width of 20 μm, and after the exposure, the entire surface of the coating film was exposed. The sample was covered with a 10% aqueous solution of an organic developer (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds.

A2-3. Heat treatment After stationary, pure water was sprayed in a shower to wash away the developer, and the coating film subjected to the exposure (photocuring) treatment and the development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, the color filter formed by forming the photosensitive resin layer (colored layer) on the glass substrate was obtained.

[Examples 2 to 5]
In Example 1, color filters corresponding to each were obtained in the same manner as in Example 1 except that the compounds (2) to (5) were used instead of the compound (1).

[Comparative Example 1]
A corresponding color filter was obtained in the same manner as in Example 1 except that the compound (1) was not added.

[Comparative Example 2]
In Example 1, except that the pigment derivative (I) was used instead of the compound (1) (that is, the pigment derivative (I) was increased by 5 g without adding the compound (1) at the time of preparing the processed pigment), A corresponding color filter was obtained in the same manner as in Example 1.

[Performance evaluation]
The performance of each obtained pigment dispersion, photosensitive resin composition, and color filter was measured according to the following method. The results are shown in Table 1.
(1. Viscosity)
The viscosity at 25 ° C. of the pigment dispersions in each Example and Comparative Example was measured with an E-type viscometer (trade name RE-810, manufactured by Toki Sangyo Co., Ltd.) and listed in Table 1.

(2. Contrast)
-Preparation of measurement substrate The photosensitive resin composition in each Example and Comparative Example was applied to a film thickness of 2.5 μm on a 100 mm × 100 mm glass substrate (trade name: 1737, manufactured by Corning). Then, it was dried (prebaked) for 60 seconds in a 90 ° C. oven. Thereafter, the entire surface was exposed to 200 mj / cm ² (illuminance was 20 mW / cm ² ) and exposed with a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.). The coated film was covered and allowed to stand for 60 seconds. Thereafter, pure water was sprayed in a shower to wash away the developer. As described above, the coating film subjected to the exposure (photocuring) treatment and the development treatment is subjected to a heat treatment (post-bake) for 1 hour in an oven at 220 ° C. to form a photosensitive resin layer for a color filter on the glass substrate. did.

・ Measurement of contrast The photosensitive resin layer for the color filter formed on the glass substrate is sandwiched between the polarizing plates, and the luminance when the polarizing plate is parallel and the luminance when the polarizing plate is perpendicular are measured with (BM-5, manufactured by Topcon Corporation). , And contrast (= luminance when parallel / luminance when orthogonal) was obtained.

(3. Voltage holding ratio)
Each colored curable composition was applied on a glass substrate on which a 10 mm square ITO electrode was formed so that the film thickness after pre-baking was 2.0 μm, and pre-baked with a hot plate at 90 ° C. for 60 seconds. After that, the exposure amount 100 mJ / cm ² (illuminance 20 mW / cm ² ) was exposed without using a mask by a proximity exposure machine using a high-pressure mercury lamp as a light source. The exposed coating film was sprayed with a 1% aqueous solution of alkaline developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 28 ° C. Thereafter, it was washed with pure water, dried and then post-baked in an oven at 220 ° C. for 1 hour to obtain a glass substrate having a colored layer. After spraying a 5 μm spacer on the colored layer of this substrate, a substrate on which a 10 mm square ITO electrode was formed on the opposing side was bonded to form an evaluation cell. Liquid crystal MJ971189 manufactured by Merck Co., Ltd. was poured into this cell, and after aging at 70 ° C. for 48 hours, the voltage holding ratio was measured with a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica. The measurement conditions for the voltage holding ratio were applied voltage: 5 V and measurement time 16.7 msec.
-Evaluation criteria-
A: Voltage holding ratio 96% or more B: Voltage holding ratio 94% or more 95% or less Δ: Voltage holding ratio 91% or more 93% or less X: Voltage holding ratio 90% or less

  From the results shown in Table 1, in the formation of color filters for liquid crystal display elements, the processed pigment of this example has a low dispersion viscosity and excellent dispersion stability, which is used to provide high contrast and high voltage holding ratio. It can be seen that a color filter having the following can be formed.

[Example 6]
Next, a photosensitive resin composition containing a processed pigment was prepared for forming a color filter for use in a solid-state imaging device.

[B1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
-Composition of resist solution-
Propylene glycol monomethyl ether acetate 19.20 parts
(PGMEA: solvent)
-36.67 parts of ethyl lactate-Resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)) 33.51 parts Unsaturated double bond-containing compound (dipentaerythritol hexaacrylate)
12.20 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.0061 parts ・ Fluorosurfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
0.83 parts, photopolymerization initiator (trihalomethyltriazine photopolymerization initiator) 0.586 parts (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

[B2. Production of silicon substrate with undercoat layer]
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer Got.

[B3. Preparation of pigment dispersion
C. I. 50 g of Pigment Red 254 (BT-CF manufactured by Ciba Specialty Chemicals), 5 g of Compound (1), 500 g of sodium chloride, and 100 g of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to obtain a coated processed pigment.

  From 40 parts of the processed pigment prepared as described above, 50 parts of Disperbyk-161 (manufactured by BYK), 30% solution) as a dispersant, 5 parts of the pigment derivative (I), and 110 parts of propylene glycol monomethyl ether as a solvent The resulting mixture was mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P2).

[B4. Preparation of photosensitive resin composition (coating solution)]
Using the pigment dispersion (P2) subjected to the dispersion treatment, the mixture was stirred and mixed so as to have the following composition ratio to prepare a coating solution for the photosensitive resin composition.
-Colorant (Pigment dispersion (P2)) 600 parts-Photopolymerization initiator (oxime photopolymerization initiator)
(CGI-124, manufactured by Ciba Specialty Chemicals) 30 parts ・ TO-1382 (manufactured by Toagosei Co., Ltd.) 25 parts ・ Dipentaerythritol hexaacrylate 30 parts ・ Solvent (PGMEA) 900 parts ・ Board adhesive (3 -Methacryloxypropyltrimethoxysilane) 1 part

[B5. (Production of color filter)
-Pattern formation-
The photosensitive resin composition prepared as described above was used in the above [B2. ] Was applied on the undercoat layer of the silicon wafer with the undercoat layer obtained in the above to form a photosensitive resin composition coating film. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is showered from an ejection nozzle above the rotation center. The product was supplied in the form of a rinse and then spray-dried.

[Examples 7 to 8]
In Example 6, color filters corresponding to the respective compounds were obtained in the same manner as in Example 6 except that the compound (4) and the compound (5) were used instead of the compound (1).

[Comparative Example 3]
A corresponding color filter was obtained in the same manner as in Example 6 except that the compound (1) was not added.

[Performance evaluation]
For evaluation of color unevenness, create a substrate for evaluation in the same way as the solid-state image sensor coloring pattern formation method, except that a glass substrate is used instead of a wafer with an undercoat layer, and a solid exposure is performed without using a mask. did. The luminance distribution was analyzed by the following method, and the luminance distribution was determined based on the ratio of pixels with a deviation from the average within ± 5% to the total number of pixels.
A method for measuring the luminance distribution will be described. First, an image obtained by photographing the luminance distribution of a glass plate with a colored layer with a microscope MX-50 (manufactured by Olympus) was analyzed.
In the luminance distribution, the luminance with the largest number of pixels is defined as the average luminance.
-Evaluation criteria-
A: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels. O: Pixels whose deviation from the average is within ± 5% is 95% or more and less than 99% of the total number of pixels. : Pixels whose deviation from the average is within ± 5% is less than 95% of the total number of pixels

  From the results in Table 2, in the formation of color filters for solid-state imaging devices, the processed pigment in the present invention has a low dispersion viscosity and excellent dispersion stability, which is used to prevent color unevenness and voltage holding ratio. It can be seen that a high color filter can be formed.

  From the above results, the processed pigment of this example has a low dispersion viscosity and an excellent dispersion stability in both the liquid crystal display device and the solid-state imaging device. Using this, the contrast is high and the color unevenness is high. It can be seen that a color filter having a high voltage holding ratio can be formed.

Claims (8)

(A) a diketopyrrolopyrrole pigment in the presence of (b) at least one selected from compounds represented by the following formula (1), the following formula (2) and the following formula (3); After kneading together with a water-soluble inorganic salt and (d) a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, (c) the water-soluble inorganic salt and (d) the water-soluble organic solvent are removed. Processed pigment.
[In Formula (1), A represents the monovalent substituent comprised from a nonmetallic atom, and n represents the integer of 1-5. When n is an integer of 2 or more, the plurality of A may be the same or different. In formula (2), B and C each independently represent a monovalent organic group, and l and m each independently represent an integer of 1 to 5. When l and m are each an integer of 2 or more, a plurality of B or a plurality of C may be the same or different. In formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹ and R ² represents a monovalent organic group. Ar represents an aromatic hydrocarbon group which may have a substituent. ] The compound represented by the formula (1) is a compound representing an alkyl group having 1 to 24 carbon atoms or an aryl group having 1 to 24 carbon atoms as the A,
The compound represented by the formula (2) is a compound representing an alkyl group having 1 to 24 carbon atoms or an aryl group having 1 to 24 carbon atoms as B and C independently of each other.
The processed pigment according to claim 1,   The processing according to claim 1 or 2, wherein the compound represented by the formula (1), the formula (2) and the formula (3) is a compound which does not contain an acidic group and a basic group. Pigments.   The diketopyrrolopyrrole pigment is C.I. I. The processed pigment according to any one of claims 1 to 3, which is Pigment Red 254.   The pigment dispersion composition containing the processed pigment of any one of Claims 1-4.   A photosensitive resin composition for a color filter using the pigment dispersion composition according to claim 5.   The manufacturing method of the color filter using the photosensitive resin composition of Claim 6.   A color filter containing the photosensitive resin composition according to claim 6.