TWI434887B - Coloring composition for color filter and color filter - Google Patents

Description

Coloring composition and color filter for color filter

The present invention relates to a coloring composition for a color filter, a color filter including a filter segment and/or a black matrix, a black resin composition, a black matrix, and a thin film transistor (TFT) type color liquid crystal display device. The substrate for the drive.

The liquid crystal display device is a display device that controls the degree of polarization of light passing through the first polarizing plate by controlling the liquid crystal layer sandwiched between the two polarizing plates, and controls the amount of light passing through the second polarizing plate. The type of twist nematic (TN) type liquid crystal is used as the mainstream. As another representative liquid crystal display device, there is an in-plane switching (IPS) method in which a pair of electrodes are provided on one substrate and an electric field is applied in a direction parallel to the substrate, so that a negative dielectric is provided. An orthogonal alignment (VA) method in which the nematic liquid crystal is aligned vertically, and an optically compensated bend (OCB) in which the optical axes of the uniaxial retardation films are orthogonal to each other. Modes, etc., and have been put into practical use.

The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. In recent years, it has been gradually used for televisions, personal computer monitors, etc., thereby improving high contrast and high brightness for color filters. Requirements.

The color filter is a fine band-like color filter segment in which two or more different hue are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine color filter segment is arranged in a constant length and width. And the formation. The color filter segments are finely divided to several micrometers to several hundreds of micrometers, and each hue is arranged neatly in a predetermined arrangement.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal on a color filter is formed by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the properties of the transparent electrode and the alignment film, the formation thereof is usually carried out at a high temperature of 200 ° C or higher, preferably 230 ° C or higher. Therefore, as a method for producing a color filter, a method called a pigment dispersion method in which a pigment excellent in light resistance and heat resistance is used as a colorant has been mainstream.

However, in general, a color filter in which a pigment is dispersed has a problem of light scattering due to a pigment, and the degree of polarization of liquid crystal control is disordered. That is, since light leakage occurs when the light is shielded (OFF state), and when the light must be transmitted (ON state), the transmitted light is attenuated, so there is a ratio of brightness on the display device in the ON state and the OFF state. Problems such as low (contrast).

In order to increase the brightness and contrast of the color filter, the pigment contained in the filter segment is often used for refining. However, the pigment (the so-called crude material having a particle diameter of 10 to 100 μm produced by a chemical reaction, by pigmentation treatment until the primary particles and their aggregation are obtained by simply using various microfabrication treatment methods) When the mixture of the particles is refined, the pigment which is made to refine the primary particles or the secondary particles is usually easily aggregated, and a large bulk pigment solid material is formed when excessively refined. Further, even if the finely pigmented pigment is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are stabilized as close as possible to the primary particles, it is difficult to obtain a stable colored composition.

In addition, it is known that it is difficult to stably and stably disperse a pigment in a coloring composition for a color filter which is formed by dispersing a pigment which is subjected to a refining treatment in a pigment carrier containing a resin or the like, and causes various problems in the production steps and the product itself. .

For example, a pigment composition containing a pigment composed of fine particles tends to exhibit high viscosity, and it is difficult to take out and transport a product from a disperser, and it is also difficult to cause gelation during storage to cause difficulty in use. Further, regarding the surface of the color developing material of the pigment composition, there are disadvantages such as a decrease in gloss and a poor leveling. Further, when a mixture of different types of pigments is used, color spots and coloring ability may be significantly lowered in the color developing matter due to phenomena such as color spots and sedimentation caused by aggregation.

Therefore, in order to keep the dispersion state good, a resin type dispersant is usually used. The resin-type dispersant has a structure in which a portion adsorbed to the pigment and a portion having a high affinity for a solvent as a dispersion medium, and the performance is determined by the balance of the two functional portions. The resin type dispersant can use various substances depending on the surface state of the pigment as the dispersion.

As the resin type dispersant, a resin type dispersant having a structure controlled by a block type structure (Patent Document 1) and a comb structure (Patent Document 2) is known as an excellent dispersibility of a pigment. In either case, since the development of the fineness of the pigment and the increase in the surface area have been progressed in recent years, a large amount of addition tends to be secured in order to secure the dispersion stability. Therefore, the solubility in the developing solution is lowered due to an increase in the dispersing agent, or the solubility of the dispersing agent itself to the developing solution is deteriorated, so that development is impossible in a predetermined time; or even in the non-image portion after development, even after development It is also easy to leave an undissolved product of the colored resin composition. Further, when the undissolved matter of the colored resin composition remains in the non-image portion on the substrate, the transmittance and contrast of the obtained color filter are lowered, and the remaining portion of the pattern remains at the edge portion of the pattern. In this case, peeling of the ITO film, deterioration of sealing property in the liquid crystal cell formation step, and the like may occur, which may affect the subsequent steps.

In the case of a comb structure, a polyamine compound having a primary or secondary amine group is grafted to form a comb-forming portion having a functional group such as a carboxyl group or an acrylonitrile group, thereby leaving a residual primary amine or secondary The amine becomes a method of adsorbing a functional group on the surface of the pigment, but the primary amine or the secondary amine has a reactive high hydrogen, which is not preferable.

Regarding the color filter, not only high contrast as described above but also high luminance is required. In order to obtain high brightness, when the pigment is usually dispersed in the pigment carrier, it is made close to the primary particles, thereby increasing the transparency of the dispersion, and high luminance is obtained because the spectral spectrum of the dispersion has a high transmittance.

In order to solve the above problems, attempts have been made to improve the structure, acid value, and the like of the acrylic block copolymer, and to improve the pigment dispersibility with a small amount of addition (see Patent Documents 3, 4, and 5).

In addition, in the gap portion of the red, green, and blue color filter segments of the color filter, a black matrix (hereinafter sometimes abbreviated as BM) having a light-shielding property is usually formed for the purpose of improving the contrast. pattern.

In terms of the black matrix, in order to optimize the image quality of the liquid crystal display, it is required to have excellent light blocking properties.

In addition, in recent years, in order to cope with higher definition and higher brightness, a method of forming a black matrix on a color filter substrate as in the prior art is performed on a substrate for driving a thin film transistor (TFT) color liquid crystal display device. Research on the BOA (Black Matrix on Array) method of forming a black matrix. This BOA method does not require a conventional pasting step for aligning with components, and since the pixel aperture ratio (opening ratio) can be greatly increased, the manufacturing process can be shortened, and display quality can be improved and cost can be reduced. There are more advantages than the BM formed on the color filter substrate.

Since these BMs also require high light-shielding properties, dispersion stabilization at a high pigment concentration is required, and it is also necessary to impart high resolution at the same time. In the same manner as the color resist, in the colored composition for a black matrix, there is a problem in that the solubility of the developer tends to be increased because the amount of the dispersant added tends to increase in order to obtain dispersion stability. The development is performed for a predetermined period of time; or even if it is developable, undissolved matter or the like of the colored resin composition is likely to remain in the non-pixel portion after development.

Further, when the BM is to be formed on the array substrate side, since the BM itself is directly exposed to the driving electric field of the liquid crystal, the display constant of the liquid crystal display panel is caused when the dielectric constant of the BM itself is high. Further, mask alignment is performed at the time of BM formation, and since an infrared camera is used, a certain degree of light transmittance in the near-infrared region is also required. Therefore, carbon black which has been mainly used as a BM material in the past not only exhibits a high dielectric constant, lacks insulation, but also has a low light transmittance in the near-infrared region, so that it is difficult to perform alignment, and it is difficult to use it for the BOA method. LCD panel.

As a method for solving such a problem, a method of combining carbon black and at least one organic pigment (see Patent Document 6) and a method of providing light-shielding properties by combining only organic pigments without using carbon black are disclosed (see Patent Document 7). 8) A method of using carbon black and a perylene black pigment as a black organic pigment (refer to Patent Documents 9 to 11), etc., but from a black matrix member, light blocking property, electrical characteristics, and mask alignment. The sufficient light transmittance of the near-infrared region of operation cannot be fully satisfied.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-31713

Patent Document 2: Japanese Patent Laid-Open No. 11-1515

Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-265528

Patent Document 4: Japanese Laid-Open Patent Publication No. 2006-321979

Patent Document 5: Japanese Patent Laid-Open Publication No. 2009-25813

Patent Document 6: Japanese Laid-Open Patent Publication No. 2005-215150

Patent Document 7: Japanese Laid-Open Patent Publication No. 2009-069822

Patent Document 8: JP-A-2009-282251

Patent Document 9: Japanese Patent Laid-Open No. Hei 6-289602

Patent Document 10: Japanese Patent Laid-Open No. 4-190362

Patent Document 11: Japanese Patent Laid-Open No. Hei 10-219167

In the first embodiment, it is an object of the invention to provide a coloring composition for a color filter which is excellent in dispersibility, has good fluidity, is stable, and has excellent developability, and a color filter region having high contrast using the coloring composition for the color filter. High quality color filter for segments or black matrix with high optical density.

The present inventors have repeatedly studied in order to solve the above problems, and as a result, found that a coloring agent containing a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1:1 to 1:3.5, and The above problem is solved by using an acrylic block copolymer as a resin type dispersant, which is composed of an A block having a solvophilic property and a B block having a functional group having a nitrogen atom. The block copolymer or the BAB block copolymer has an amine value of 10 mgKOH/g or more and 99 mgKOH/g or less in terms of an effective solid content.

In other words, the first embodiment relates to a coloring composition for a color filter, which is a coloring composition for a color filter containing a coloring agent, a resin type dispersing agent, and a solvent, wherein the coloring agent contains an average primary particle diameter. a pigment of 20 to 50 nm and having an aspect ratio of pigment particles of 1:1 to 1:3.5, the resin type dispersant containing an acrylic block copolymer, and the above acrylic block copolymer is A having solvophilicity An AB block copolymer or a BAB block copolymer composed of a block and a B block having a functional group containing a nitrogen atom, and an amine value of 10 mgKOH/g or more and 99 mgKOH/g or less in terms of an effective solid content.

In the above-mentioned acrylic block copolymer, 5 to 40 mol% of a repeating unit represented by the following formula (I) may be contained in the A block having solvophilicity, and a functional group having a nitrogen atom may be contained. The repeating unit represented by the following formula (II) may be contained in the B block of the group.

[In the formula (I), n represents an integer of 1 to 5, and R ₁ represents a hydrogen atom or a methyl group. ]

[In the general formula (II), R ₄ and R ₅ each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent, R ₃ It represents an alkylene group having 1 or more carbon atoms, and R ₂ represents a hydrogen atom or a methyl group. ]

Further, in the above-mentioned acrylic block copolymer, 50 parts to 90 mol% of the (block) other than the structural unit represented by the formula (I) may be further contained in the A block having solvophilicity. An acrylate type monomer is a constituent unit of a precursor.

Further, the aforementioned colorant may be a lanthanide black pigment.

Further, the above composition may further contain a pigment derivative of an acidic derivative of an organic pigment or a metal salt thereof.

Further, the above composition may further contain a photopolymerizable monomer and a photopolymerization initiator.

Further, the first embodiment relates to a color filter characterized in that a color filter segment and/or a black matrix formed of the coloring composition for the color filter are provided on a substrate.

The coloring composition for a color filter according to the first embodiment is a stable coloring composition for a color filter excellent in fluidity and developability, and the coloring composition for a color filter can be used to form high-contrast color filters of various colors. A black matrix pattern of sheet segments and high optical density. Therefore, a high-quality color filter can be obtained by using the coloring composition for the color filter.

In the second embodiment, it is an object of the invention to provide a black resin composition which is excellent in fluidity and stability of a black matrix, and black which is excellent in light blocking property, electric characteristics, and light transmittance in a near-infrared region. The matrix is, in particular, a black matrix used for a substrate for driving a thin film transistor (TFT) type color liquid crystal display device.

The second embodiment relates to a black resin composition which is a black resin composition containing a light-blocking black pigment, a resin, and a solvent, wherein the light-shielding black pigment has an average primary particle diameter of 50 nm or less and a primary particle length. a lanthanide black pigment having a width ratio of 1:1 to 1:2 and carbon black, and the content of the lanthanide black pigment is 78 to 95% by weight based on the total amount of the light-shielding black pigment (A), and The solid content concentration is 5% by weight or more and less than 40% by weight.

The aforementioned lanthanide black pigment may have an average primary particle diameter of 20 to 45 nm.

The foregoing composition may further contain a pigment dispersant.

The aforementioned pigment dispersant may comprise a pigment derivative having a parent skeleton of an organic pigment and a basic substituent.

The aforementioned pigment dispersant may further contain an acidic resin type dispersant.

The foregoing composition may further comprise an ethylenically unsaturated compound and a photopolymerization initiator.

Further, the second embodiment relates to a black matrix formed of the black resin composition described above.

The relative matrix constant of the black matrix at a dry film thickness of 1.0 μm may be 8.0 or less.

The black matrix may have a light transmittance of 15% or more and less than 99% at a wavelength of 780 nm when the dried film thickness is 1.0 μm.

The optical density of the black matrix at a dry film thickness of 1.0 μm may be 2.50 or more.

The second embodiment relates to a substrate for driving a thin film transistor type color liquid crystal display device including the black matrix.

Since the black matrix of the second embodiment is excellent in light-shielding property, the color liquid crystal display device has excellent display contrast and low dielectric constant characteristics, so that misalignment of liquid crystals or conduction between electrodes formed on the TFT substrate is less likely to occur. A poor condition caused by the electrical characteristics of the black matrix, and because of excellent light transmittance in the near-infrared region, it is also possible to perform a mask alignment operation, which is suitable for driving a thin film transistor (TFT) type color liquid crystal display device. Use a substrate.

According to a third embodiment, it is an object of the invention to provide a black matrix which is excellent in light blocking property, electrical characteristics, and transmittance in a near-infrared region, and in particular, a black matrix for a driving substrate of a thin film transistor (TFT) color liquid crystal display device. And a black resin composition excellent in fluidity and stability for producing the black matrix.

The third embodiment relates to a black resin composition which is a black resin composition containing a light-blocking black pigment, a pigment dispersant, a resin, and a solvent, wherein the light-shielding black pigment has an average primary particle diameter of 50 nm or less. The pigment particles have an aspect ratio of 1:1 to 1:2 lanthanide black pigment.

The aforementioned lanthanide black pigment may have an average primary particle diameter of 20 to 45 nm.

The aforementioned pigment dispersant may be a pigment derivative having a matrix skeleton of an organic pigment and a basic substituent.

The precursor skeleton of the aforementioned organic pigment may be two Any one of a pigment or a diketopyrrolopyrrole pigment.

The aforementioned pigment dispersant may further contain a resin type dispersant.

The foregoing composition may further comprise an ethylenically unsaturated compound and a photopolymerization initiator.

Further, the third embodiment relates to a black matrix formed of the black resin composition described above.

The relative matrix constant of the black matrix at a dry film thickness of 1.0 μm may be 4.5 or less.

The transmittance of the black matrix at a wavelength of 1000 nm at a dry film thickness of 1.0 μm may be 60% or more and less than 99%.

The optical density of the black matrix at a dry film thickness of 1.0 μm may be 1.30 or more.

Further, the third embodiment relates to a substrate for driving a thin film transistor (TFT) type color liquid crystal display device including the black matrix.

According to the third embodiment, since the black matrix is excellent in light-shielding property, the color liquid crystal display device has excellent display contrast and low dielectric constant characteristics, so that misalignment of liquid crystals or conduction between electrodes formed on the TFT substrate is less likely to occur. Such a defect caused by the electrical characteristics of the black matrix, and because of the excellent light transmittance in the near-infrared region, it is also capable of performing a mask alignment operation, and is also suitable for a thin film transistor (TFT) type color liquid crystal display device. Driving substrate.

First, various constituent components of the coloring composition for a color filter of the present invention will be described.

<colorant>

As the coloring agent, there are a colorant for a color filter section and a coloring agent for a black matrix.

[Colorant for color filter section]

The pigment contained in the coloring agent for the color filter segment is not particularly limited. When the dispersibility of the pigment particles is considered, the average primary particle diameter is preferably 20 nm or more. Further, in consideration of contrast and brightness, the average primary particle diameter is preferably 50 nm or less. That is, as the average primary particle diameter increases, light scattering of the backlight and light leakage occur when the polarizing plates cross, resulting in a decrease in contrast. In addition, since the transmittance is lowered, the brightness is also lowered.

Further, the aspect ratio of the pigment particles is in the range of 1:1 to 1:3.5, which is preferable because the light scattering of the backlight and the decrease in the transmittance are sufficiently prevented.

The shape of the pigment particles is not a needle shape, and is preferably a spherical shape or an elliptical shape. In the case of a spherical shape, since the distance between the primary particles of each pigment is more uniform, scattering of light is less likely to occur, and contrast and brightness are extremely high.

As the coloring agent, in the case of forming various color filter segments, for example, pigments of various colors such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a violet pigment, an orange pigment, and a brown pigment can be used. Further, examples of the chemical structure thereof include an azo system, a phthalocyanine system, a quinacridone system, a benzimidazolone system, and an isoindolinone system. two Organic pigments such as linden, indanthrene, and lanthanide. In addition, various inorganic pigments and the like can also be used.

Specific examples of pigments that can be used are exemplified. The following "C.I." indicates a color index.

Examples of the red pigment include: CI 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, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 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, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among them, from the viewpoint of obtaining high contrast and high brightness, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferred, and CI Pigment Red is more preferred. 177, 209, 224, 242 or 254.

Examples of the blue pigment include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, and 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, etc. Among them, from the viewpoint of obtaining high contrast and high brightness, it is preferably CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 or 15:6, more preferably CI Pigment Blue 15: 6.

Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Or 58. Among them, from the viewpoint of obtaining high contrast and high brightness, C.I. Pigment Green 7, 7, or 58 is preferred.

Examples of the yellow pigment include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, and 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, 172, 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, and the like.

Among them, from the viewpoint of obtaining high contrast and high brightness, it is preferably CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185, more preferably CI Pigment Yellow 83, 138, 139, 150 or 180.

Examples of the violet pigment include C.1. 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, and the like. Among them, from the viewpoint of obtaining high contrast and high brightness, C.I. Pigment Violet 19 or 23 is preferable, and C.I. Pigment Violet 23 is more preferable.

Examples of the orange pigment include CI 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, 71, 72, 73, 74, 75, 77, 78, 79, and the like. Among them, from the viewpoint of obtaining high contrast and high brightness, C.I. Pigment Orange 38 or 71 is preferred.

A plurality of the above various pigments may be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment may be used in combination, or a blue pigment and a violet pigment may be used in combination as a pigment.

[Black matrix colorant]

In the present specification, a coloring composition containing a coloring agent for a black matrix is sometimes referred to as a "black coloring composition" or a "black resin composition".

When forming a black matrix, as a coloring agent, a black pigment or a mixed pigment of the above-mentioned red, purple, yellow, green, and blue pigments can be used.

The average primary particle diameter of the pigment is preferably 50 nm or less, more preferably 5 to 50 nm, most preferably 20 to 50 nm, and particularly preferably 20 to 45 nm, in view of the light-shielding property of the upper limit and the pigment dispersibility in consideration of the lower limit. . That is, as the average primary particle diameter increases, the filling of the particles becomes sparse, and a gap is generated, so that the masking property is lowered. On the other hand, by suppressing the average primary particle diameter to 50 nm or less, the filling of the particles is made dense, and the light shielding property is improved.

The length and width of the pigment particles are preferably from 1:1 to 1:3.5, more preferably from 1:1 to 1:2.0, most preferably from 1:1 to 1:1.5. When it is in the above range, since the filling of the particles is dense and the gap is small, the hiding property is improved.

The shape of the pigment particles is not a needle shape but a spherical shape or an elliptical shape. In particular, when it is spherical, since the distance between the primary particles of the respective pigments is more uniform, it is difficult to generate a gap, and the masking property is extremely high.

The black pigment which can be used may be a light-shielding black pigment, and examples thereof include an anthraquinone black pigment, carbon black, acetylene black, lamp black, bone charcoal, graphite, iron black, titanium black, and the above-mentioned red, purple, and yellow colors. A pigment color mixing system such as green or blue pigment. Among them, a pigment color mixing system such as an anthraquinone black pigment, carbon black, red, purple, yellow, green, or blue pigment is preferable. From the viewpoints of masking properties and electrical properties, it is more preferred to use a lanthanide black pigment alone or a lanthanide black pigment and carbon black.

When a lanthanoid black pigment is used alone, it is particularly excellent in relative dielectric constant, dispersibility, and developability.

When the lanthanide black pigment and carbon black are used together, the content of the lanthanide black pigment in the black pigment 100% by weight is preferably from 78 to 95% by weight, more preferably from 80 to 95% by weight. When the sufficient light blocking property is obtained at about 1.0 μm, the ratio of the lanthanoid black pigment is preferably 95% by weight or less. It is preferable to prevent the increase in the relative dielectric constant and increase the transmittance at a wavelength of 1000 nm so as to sufficiently recognize the aligned infrared sensor and prevent the liquid crystal molecules from being disordered by the driving voltage at the time of formation of the BM, and it is preferably 78% by weight or more.

In the case of the content of the black pigment, the sufficient dispersion stability is considered in the upper limit, and when the light-shielding property is sufficient in consideration of the lower limit, it is preferably 20 to 70% by weight based on 100% by weight of the total solid content of the coloring composition for a color filter. More preferably, it is 30 to 70% by weight, most preferably 30 to 60% by weight, particularly preferably 40 to 60% by weight.

Further, since the black matrix formed using the black coloring composition formed of the above-described fluorene-based black pigment or color mixing system is excellent in light-shielding property, the color liquid crystal display device is excellent in display contrast and is not easily produced due to low dielectric constant characteristics. The alignment of the liquid crystal is disordered or the electrical characteristics of the black matrix such as the conduction between the electrodes formed on the TFT substrate are inferior, and since the transmittance in the near-infrared region is excellent, the mask alignment operation can also be performed. A substrate for driving a thin film transistor (TFT) type color liquid crystal display device.

As a commercial item, carbon black may be, for example, #260, #25, #30, #32, #33, #40, #44, #45, #45L, manufactured by Mitsubishi Chemical Corporation. #47, #50, #52, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, PrIntex L, PrIntexP, PrIntex 30, PrIntex 35, PrIntex 40, PrIntex 45, PrIntex 55, PrIntex 60, manufactured by DEGUSSA PrIntex 300, PrIntex 350, SpecIal Black 4, SpecIal Black 350, SpecIal Black 550, etc. Among them, from the viewpoint of obtaining a high optical density (hereinafter sometimes referred to as OD), it is preferably #45. The carbon black may be used singly or in combination of two or more.

In the coloring agent of the present invention, when the pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of 1:1 to 1:3.5 is contained, the content is preferably 30 to 100% by weight based on 100% by weight of all the coloring agents. The weight %, more preferably 50 to 100% by weight.

When the coloring composition of the present invention contains a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of 1:1 to 1:3.5, the content is preferably preferably 1% by weight or more based on the total solid content. More preferably, it is 5% by weight or more, and is usually 95% by mass or less, particularly preferably 85% by weight or less. When it is 5% by weight or more, the film thickness with respect to the color density does not become excessively large, and there is no fear of adversely affecting the gap control or the like at the time of liquid crystal cell formation. On the other hand, when it is 95% by weight or less, sufficient dispersion stability can be obtained.

[fineness of pigment]

The pigment used in the present invention can be refined by a salt milling treatment or the like. By using a fine pigment, it is possible to form a color filter segment having a higher contrast and a black matrix having a high light-shielding property.

Salt grinding treatment refers to the use of a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, etc., for pigments and water-soluble inorganic salts and water-soluble organic solvents. The mixture is mechanically kneaded while being heated, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt acts as a pulverization aid, and the salt is pulverized by the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt to be subjected to the salt milling treatment, it is possible to obtain a pigment having a very small primary particle diameter and a narrow distribution range and a steep particle size distribution. As the water-soluble inorganic salt, sodium chloride, cesium chloride, potassium chloride, sodium sulfate or the like can be used, and from the viewpoint of price, sodium chloride (salt) is preferably used. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment, from the viewpoints of treatment efficiency and production efficiency.

The water-soluble organic solvent has a function of a wetting pigment and a water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and does not substantially dissolve the inorganic salt used. However, since the temperature of the salt is increased due to an increase in temperature during salt milling, it is preferred to use a high boiling point solvent having a boiling point of 120 ° C or higher from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, and the like can be used. Ethylene 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. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the pigment is subjected to a salt milling treatment, a resin may be added as needed. The type of the resin that can be used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin which can be used is preferably a solid at room temperature, water-insoluble, and more preferably partially soluble in the above organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by weight based on 100 parts by weight of the pigment.

<Dispersant> The coloring composition for a color filter of the present invention may contain a dispersing agent. Examples of the dispersant include a resin type dispersant, a pigment derivative, a surfactant, and the like. The dispersant is excellent in dispersion of the pigment and prevents re-aggregation of the dispersed pigment.

[Resin-type dispersant] As the resin-type dispersant, an acrylic block copolymer may be further contained, and the above-mentioned acrylic block copolymer is composed of an A-block having a solvophilic property and a B-incorporating functional group having a nitrogen-containing atom. The AB block copolymer or the BAB block copolymer composed of the segments, and the amine value is 10 mgKOH/g or more and 99 mgKOH/g or less in terms of effective solid content.

The resin type dispersant includes a coloring agent affinity portion adsorbed to the coloring agent property and a portion compatible with the coloring agent carrier, and has a function of adsorbing the coloring agent to stabilize the dispersion of the coloring agent into the coloring agent carrier, but Since the random dispersant pigment adsorbing groups are randomly disposed, it is easy to be thickened by crosslinking. On the other hand, since the pigment adsorbing groups in the block copolymer are arranged at a high density, the adsorption of the pigment is strong without cross-linking. Therefore, the block copolymer can ensure higher dispersion stability. In addition, as long as the amine value is 10 mgKOH/g or more and 99 mgKOH/g or less, the solubility in the developer is good, development can be performed in a predetermined time in the development step, and coloring does not remain in the non-image portion on the substrate. Undissolved material of the resin composition.

The monomer which is a precursor of the solvating A block is not particularly limited as long as it does not have a functional group containing a nitrogen atom such as an amino group and is copolymerizable with the monomer constituting the B block.

Examples of the A block include a polymer structure obtained by copolymerizing a comonomer: a styrene monomer such as styrene or α-methylstyrene; methyl (meth)acrylate; Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , glycidyl (meth)acrylate, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, glycidyl ethacrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (A (meth) acrylate monomer such as acrylate; (meth) acrylate monomer such as (meth) acrylonitrile chloride; vinyl acetate monomer; allyl glycidyl ether, crotonic acid shrinkage A glycidyl ether monomer such as glycerin ether.

In particular, the A block preferably contains a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate or polypropylene glycol (meth) acrylate as a copolymerization component (that is, It is preferable to contain a partial structure derived from a polyalkylene glycol (meth) acrylate, in particular, a partial structure represented by the following general formula (I).

[In the formula (I), n represents an integer of 1 to 5, and R ₁ represents a hydrogen atom or a methyl group. The partial structure represented by the formula (I) particularly preferably contains 5 to 40 mol% in the A block.

Further, from the viewpoint of improving the dispersion stability, it is preferred that the A block contains 50 to 90 mol% of a (meth) acrylate monomer other than the partial structure represented by the general formula (I). More preferably, it is 60 to 80 mol% of the constituent unit of the precursor. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate The octyl ester is preferred as the (meth) acrylate monomer, and the coloring composition is excellent in dispersibility and stability.

In the A block, by containing the partial structure represented by the general formula (I), hydrophilicity is imparted and the solubility in the developer is improved. On the other hand, by further containing a constituent unit having a (meth) acrylate monomer as a precursor other than the partial structure represented by the general formula (I), compatibility with the binder resin is improved and dispersion stability is improved. rise.

As the B block having a functional group containing a nitrogen atom, it is preferred to have a primary to tertiary amine group as a functional group. The content ratio of the primary to tertiary amine groups is preferably 10 mol% or more, more preferably 40 mol% or more, based on the total of the nitrogen atom-containing functional groups.

The amine group is preferably -NR ₄ R ₅ (however, R ₄ and R ₅ each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent or may have a substituent The aralkyl group indicates that a structure having such a partial structure, for example, represented by the following formula is preferred.

[In the general formula (II), R ₄ and R ₅ each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent, R ₃ It represents an alkylene group having 1 or more carbon atoms, and R ₂ represents a hydrogen atom or a methyl group. ]

Wherein R ₄ and R _{5 are} preferably a methyl group, R _{3 is} preferably a methylene group or an ethyl group, and R _{2 is} preferably a methyl group. As such a partial structure, for example, a structure represented by the following formula is preferable.

The partial structure of the amine group as described above may be contained in one or more B blocks. In this case, the partial structure containing two or more kinds of amine groups may be contained in any one of random copolymerization or block copolymerization in the B block. Further, in the range which does not impair the effects of the present invention, a partial structure containing no amine group may be partially contained in the B block, and examples of such a partial structure include (meth)acrylate monomer. Part of the structure. The content of the relevant amino group-free partial structure in the B block is preferably from 0 to 60 mol%, more preferably from 0 to 20 mol%, most preferably no relevant amine group in the B block. Part of the structure.

In addition, when a quaternary ammonium salt group is used as a B block having a functional group containing a nitrogen atom, since it has a strong polarity and interacts with other resins, adsorption of the colorant is not performed, and there is a possibility that viscosity is increased or Gelatinized. Therefore, as the functional group containing a nitrogen atom, a primary, secondary or tertiary amine is preferred. Among them, the tertiary amine is preferred because it has both an adsorption force and a stability to the colorant.

That is, the acrylic block copolymer preferably contains 5 to 40 mol% of the formula (I) in the A block having solvophilicity from the viewpoint of improving dispersibility and developer solubility. The repeating unit shown contains a repeating unit represented by the formula (II) in a B block having a functional group containing a nitrogen atom.

In addition, when the acrylic block copolymer contains an acid group such as a carboxylic acid or a phosphoric acid, the acid-base interaction with the amine moiety in the B block causes a decrease in dispersion stability, and therefore it is preferably a substance having a low acid value. More preferably, it is 0 mgKOH/g.

The content of the acrylic block copolymer is preferably from 1 to 70 parts by weight, more preferably from 10 to 60 parts by weight, per 100 parts by weight of the colorant. The blending amount of the acrylic block copolymer is preferably 1 part by weight or more from the viewpoint of pigment dispersibility. In addition, when the coloring composition is used and the pixel pattern of the color filter is produced by photolithography, it is preferably 70 parts by weight or less from the viewpoint of obtaining high alkali developability.

Further, the coloring composition for a color filter of the present invention may be used singly or in combination with the above-mentioned resin type dispersing agent, and may further contain another resin type dispersing agent.

As the other resin type dispersant, a polycarboxylate such as a polyurethane or a polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a polycarboxylate can be used. a base amine salt, a polyoxyalkylene oxide, a long-chain polyamine phthalamide phosphate, a hydroxyl group-containing polycarboxylate and a modified substance thereof, a poly(lower alkylene imine), and a polyester having a free carboxyl group An oily dispersant such as guanamine or a salt thereof formed by the reaction, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, poly A water-soluble resin such as vinyl alcohol or polyvinylpyrrolidone, a water-soluble polymer compound, a polyester-based, a modified polyacrylate-based compound, an ethylene oxide/propylene oxide addition compound, or a phosphate ester system.

As a commercially available resin type dispersant which can be used in the present invention, DIsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162 manufactured by BYK Chemical Co., Ltd. 163, 164, 165, 166, 167, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 9076, 9077, or BYK-LPN 6919, 21324, 21407, or AntI-Terra-U , 203, 204, or BYK-P104, P104S, 220S, or LactImon, LactImon-WS, or Bykumen, etc., SOLSPERSE 3000, 9000, 13240, 13650, 13940, 17000, 18000, manufactured by Lubrizol, Japan. 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, 76500, etc., EFKA-46, 47, 48, 452 manufactured by EFKA Chemical Co., Ltd. LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, 4300, 4330, etc., Ajinomoto Fine Chemistry AJISPER PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno.

As the pigment dispersant for the black pigment, when a pigment derivative, preferably a pigment derivative having a parent skeleton of an organic pigment and a basic substituent, is used, it is preferable because electrical properties are better. It is preferable to further contain a resin type dispersant because it has improved electrical properties, fluidity and stability.

The resin type dispersant includes a pigment affinity site having a property of adsorbing to a light-shielding black pigment and a site compatible with a black pigment carrier, and has an effect of stabilizing dispersion of the black pigment carrier by adsorption to a black pigment. Similarly to the above-described dye derivative, the resin-type dispersant imparts affinity to the black pigment and the dye derivative, makes the molecular arrangement in the black resin composition more uniform, and further reduces the charge shift, thereby contributing to improvement in electrical characteristics. , by the better.

In particular, when a black pigment, a pigment skeleton having a matrix of an organic pigment, a pigment derivative of a basic substituent, and an acidic resin-type dispersant are used, since an excellent effect such as fluidity and electrical properties is exhibited, it is preferable. . This is because the charge can be neutralized by the interaction between the acid-base substituents of the acidic resin type dispersant and the pigment derivative having a basic substituent, and as a result, the local charge shift can be suppressed, so that electricity Improved features.

Among these, in order to enhance the interaction with the basic derivative, an acidic resin type dispersant is preferable, and the acid value of the resin type dispersant is preferably 129 mgKOH/g from the viewpoint of dispersion stability. Hereinafter, it is preferably from 13 to 53 mgKOH/g.

[pigment derivatives]

The coloring composition for a color filter of the present invention is preferably a pigment derivative containing an acidic derivative or a metal salt thereof as an organic pigment. The acidic derivative of the organic pigment or the metal salt thereof can further promote the pigment adsorption of the pigment and the resin-type dispersant and improve the dispersibility of the pigment, so that the effect of preventing re-aggregation of the pigment after dispersion is large. Therefore, when an acid derivative of an organic pigment or a metal salt thereof is used to disperse a pigment in a pigment carrier, a color filter excellent in stability can be obtained. Further, by using a resin type dispersant which is an AB block copolymer or a BAB block copolymer composed of a B block having a solvophilic A block and a B block having a functional group containing a nitrogen atom, Increase the dispersion. It is presumed that the pigment adsorption of the dispersant is promoted by the acid-base interaction of the acidic substituent of the derivative disposed near the pigment and the basic substituent of the dispersant.

The acidic derivative of the organic pigment or the metal salt thereof is a compound represented by the following formula (1).

P-Lx general formula (1)

(wherein P: organic pigment residue, L: acidic substituent, x: hydrogen atom or metal ion)

Examples of the organic pigment constituting the organic pigment residue of P include a diketopyrrolopyrrole pigment; an azo pigment such as azo, disazo or polyazo; and copper phthalocyanine; , phthalocyanine-based pigments such as copper phthalocyanine, zinc phthalocyanine, zinc halide phthalocyanine, and metal-free phthalocyanine; amine guanidine, diaminodifluorene, pyrimidine, flavanthrone, and ruthenium Anthraquinone, indanthrone, pyranthrone, violanthrone, etc.; quinacridone pigment; Pigment; perinone pigment; lanthanide pigment; thioindigo pigment; isoindoline pigment; isoindolinone pigment; ) pigment; quinophthalone pigment; A pigment; a metal complex pigment or the like.

Among them, the quinophthalone pigment, particularly the quinophthalone yellow pigment C.I. Pigment Yellow 138, is preferred because it is excellent in productivity, dispersion stability, heat resistance, light resistance, solvent resistance, and the like of the colored composition.

Examples of the substituent constituting the acidic substituent of L include a sulfonic acid, a carboxylic acid, a phosphoric acid, and the like.

Examples of the metal ion of x include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as magnesium, calcium, and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel. Among them, alkaline earth metal ions such as calcium and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel are preferable. Among them, aluminum ions are particularly preferred because of their high heat resistance and dispersibility.

As the acidic derivative of the organic pigment or a metal salt thereof, a sulfonic acid derivative of quinacridone or an aluminum salt thereof is particularly preferable. The sulfonic acid derivative of quinacridone or an aluminum salt thereof is excellent in dispersion of a colorant and has a large effect of preventing re-aggregation of the coloring agent after dispersion. Therefore, the coloring composition formed by dispersing a coloring agent in a coloring agent carrier such as a resin or an organic solvent using a sulfonic acid derivative of quinacridone or an aluminum salt thereof is excellent in stability.

For example, the sulfonic acid derivative of the quinophthalone consisting of the quinophthalone-based yellow pigment C.I. Pigment Yellow 138 is a compound represented by the following formula (2), and the aluminum salt is a compound represented by the following formula (3). Equation (2):

Equation (3):

The aluminum salt of the sulfonic acid derivative of quinacridone can be synthesized by a usual method, but the following method is industrially advantageous. That is, a pigment is added to concentrated sulfuric acid or fuming sulfuric acid, heated and sulfonated. Next, the reaction solution is poured into a large amount of ice water, and the precipitated sulfonic acid derivative is filtered and washed with water using a filter press or the like. The aqueous slurry of the obtained sulfonic acid derivative was redispersed in a large amount of water, and the pH was adjusted to be weakly alkaline using an aqueous sodium hydroxide solution, and then an aqueous solution of aluminum sulfate was gradually added to form a salt of the sulfonic acid to form an aluminum salt. Thereafter, the aluminum salt of the sulfonic acid derivative of the powdered quinacridone is obtained by filtration, washing with water, drying, and pulverization.

The pigment derivative which can be used in combination with the acidic derivative of the organic pigment or the metal salt thereof, for example, JP-A-63-305173, JP-A-57-15620, and JP-A-59-40172 The materials described in the Japanese Patent Publication No. Sho 63-9102, Japanese Patent Publication No. Hei 5-9469, and the like.

Further, the coloring composition for a color filter of the present invention can be used as a pigment derivative by the compound represented by the following formula (1'). It is particularly preferred to use as a pigment derivative for a black coloring composition.

P'-L'n formula (1')

[wherein P': organic pigment residue, anthracene residue, acridonone residue or three Residue, L': a basic substituent, an acidic substituent or a phthalimidomethyl group which may have a substituent, n: an integer of 1 to 4. Examples of the organic pigment residue constituting P' include diketopyrrolopyrrole pigments; azo pigments such as azo, diazo, and polyazo; copper phthalocyanine, copper halide phthalocyanine, and metal-free Phthalocyanine pigments such as phthalocyanine; anthraquinone pigments such as amine guanidine, diaminodiguanide, pyrimidine, flavonone, ruthenium osmium, indanthrene, ketone, anthrone ; quinacridone pigment; two Pigment; purple ring ketone pigment; lanthanide pigment; thioindole pigment; isoporphyrin pigment; isoindolinone pigment; quinacridone pigment; Shilin pigment; metal complex pigment Wait.

Among them, a pigment derivative in which the matrix skeleton is an organic pigment is preferable, and from the viewpoint of a low dielectric dissipation factor, it is preferable to use two. It is a pigment and a diketopyrrolopyrrole pigment.

A basic derivative in which L' in the formula (1') is a basic substituent is preferably used. Among them, a pigment derivative having a matrix of an organic pigment and a basic substituent imparts an affinity to a ruthenium-based black pigment to uniformize the molecular arrangement in the black resin composition, thereby reducing charge displacement, and is helpful. It is preferred to improve electrical characteristics. Further, it is preferred that L' is a substituent selected from the group represented by the general formulae (2'), (3') and (4').

General formula (2'):

General formula (3'):

General formula (4'):

[In the formulae (2') to (4'), X is -SO ₂ -, -CO-, -CH ₂ -, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ - or a direct bond a knot; Y is -NH-, -O- or a direct bond; n is an integer from 1 to 10; Y ¹ is -NH-, -NR ⁵⁸ -Z-NR ⁵⁹ - or a direct bond; R ⁵⁸ and R ⁵⁹ Each of which is independently a hydrogen bond, an alkyl group having 1 to 36 carbon atoms which may have a substituent, an alkenyl group having 2 to 36 carbon atoms which may have a substituent, or a phenyl group which may have a substituent; a pendant alkyl group having a substituent or an extended aromatic group which may have a substituent; and R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substituent An alkenyl group having 2 to 30 carbon atoms or a heterocyclic ring which may be substituted with R ⁵⁰ and R ⁵¹ as a whole and further containing a nitrogen, oxygen or sulfur atom; R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ are each independently The ground is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a carbon number of 6 to 20 which may have a substituent An aromatic group; R ⁵⁶ is a hydrogen atom, and the number of carbon atoms which may have a substituent is 1 to 2 An alkyl group of 0, an alkenyl group having 2 to 20 carbon atoms which may have a substituent; and R ⁵⁷ is a substituent represented by the above formula (2') or a substituent represented by the above formula (3'); Q is a hydroxyl group, an alkoxy group, a substituent represented by the above formula (2') or a substituent represented by the above formula (3'). ]

The amine component for forming the substituent represented by the general formulae (2') to (4') may, for example, be dimethylamine, diethylamine, methylethylamine or N,N-ethyl Propylamine, N,N-ethylpropylamine, N,N-methylbutylamine, N,N-methylisobutylamine, N,N-butylethylamine, N,N-tert-butylethylamine, two Isopropylamine, dipropylamine, N,N-t-butylpropylamine, dibutylamine, di-second butanamine, diisobutylamine, N,N-isobutyl 2,5-butylamine, diamylamine, diiso) Pentylamine, dihexylamine, dicyclohexylamine, bis(2-ethylhexyl)amine, dioctylamine, N,N-methyloctadecylamine, diamine, diallylamine, N,N- Ethyl-1,2-dimethylpropylamine, N,N-methylhexylamine, dioleylamine, distearate, N,N-dimethylaminomethylamine, N,N-dimethylamino Ethylamine, N,N-dimethylaminopentylamine, N,N-dimethylaminobutylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, N,N- Diethylaminohexylamine, N,N-diethylaminobutylamine, N,N-diethylaminopentylamine, N,N-dipropylaminobutylamine, N,N-dibutylaminopropylamine, N , N-dibutylaminoethylamine, N,N-dibutylaminobutylamine, N,N-diisobutylaminopentylamine, N,N-methyl-lauranamine propylamine, N,N- Ethyl-hexylaminoethylamine, N,N-distearate, ethylamine, N,N-dioleylamine, N,N-distearate, piperidine ), pipecholine, 3-pipecolline, 4-piperonphyrin, 2,4-dimethylpiperidine, 2,6-dimethylpiperidine, 3,5- Dimethylpiperidine, 3-piperidinemethanol, pipecolic acid, 4-piperidinic acid, methyl 4-piperidinecarboxylate, ethyl 4-piperidinecarboxylate, 2-piperidineethanol, pyrrolidine (pyrrolidine), 3-hydroxypyrrolidine, N-amineethylpiperidine, N-amineethyl-4-piperonphyrin, N-amine ethylmorpholine, N-aminopropylpiperidine, N-aminopropyl Base-2-piperonphyrin, N-aminopropyl-4-piperonphyrin, N-aminopropylmorpholine, N-methylpiperidone N-butylperidazole N-methylhomopel (N-methylhomopiperazine), 1-cyclopentylperidine 1-amino-4-methylper 1-cyclopentylperidazole Wait.

Pigment derivatives having an alkaline substituent, an anthracene derivative, and an acridone derivative can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the formula (5') to (8') into an organic dye, hydrazine or acridone, the formula (2') to (4' are formed by reacting with the above substituent. The above amine component of the substituent represented by, for example, N,N-dimethylaminopropylamine, N-methylpiperidin , diethylamine or 4-[4-hydroxy-6-[3-(dibutylamino)propylamino]-1,3,5-three It is obtained by a reaction such as 2-ylamino]aniline.

Formula (5'): -SO ₂ Cl

Formula (6'): -COCl

Formula (7'): -CH ₂ NHCOCH ₂ Cl

Formula (8'): -CH ₂ Cl

When the substituent of the formula (5') to (8') is reacted with the above amine component, a substance obtained by hydrolyzing a substituent moiety of the formula (5') to (8') and substituting chlorine for a hydroxyl group may be mixed. . In this case, the formula (5') and the formula (6') respectively become a sulfonic acid group and a carboxylic acid group, which may each form a free acid, and may also be formed with a metal having 1 to 3 valence or the above monoamine. salt.

Further, when the organic dye is an azo dye, the substituent represented by the general formulae (2') to (4') may be introduced into a diazo component or a coupler component in advance, and then a coupling reaction may be carried out to produce an even A nitrogen-based pigment derivative. In view of preventing a decrease in contrast and obtaining good electrical characteristics, the total amount of the pigment derivative is preferably 0, 5 parts by weight or more, more preferably 1 part by weight or more, based on 100 parts by weight of the coloring agent. It is 3 parts by weight or more. Further, in consideration of sufficient light resistance and good electrical properties in a black matrix, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and most preferably 20 parts by weight or less. The pigment derivative may be used singly or in combination of two or more.

[Surfactant]

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, an alkali metal salt of a styrene-acrylic acid copolymer, sodium stearate, and an alkane. Sodium naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, styrene-acrylic acid Anionic surfactants such as monoethanolamine and polyoxyethylene alkyl ether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl Nonionic surfactants such as ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate: alkyl quaternary ammonium salts, ethylene oxide adducts thereof, etc. a cationic surfactant; an amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as an alkyldimethylaminoacetate betaine; these surfactants may be used singly or in combination of two or more, but not necessarily Limited to these surfactants. When the dispersibility is good, the amount of the resin-type dispersant and the surfactant added is preferably from 0.1 to 55 parts by weight, more preferably from 0.1 to 45 parts by weight, per 100 parts by weight of the colorant.

<Resin>

The coloring composition for a color filter of the present invention may contain a resin. The resin contained in the coloring composition for a color filter of the present invention is a dispersing coloring agent, and a thermoplastic resin, a thermosetting resin, or the like can be used. The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. Further, when it is used in the form of an alkali-developing photosensitive coloring composition, an alkali-soluble vinyl-based resin formed by copolymerization of an acidic group-containing ethylenically unsaturated monomer is preferred. Further, in order to further increase the sensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain, the stability of the photoresist can be improved, which is preferable. Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and poly Vinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin. The vinyl alkali-soluble resin which is formed by copolymerizing an acidic group-containing ethylenically unsaturated monomer may, for example, be a resin having an acidic group such as a carboxyl group or a sulfo group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrenesulfonic acid copolymer, and an ethylene/(meth)acrylic acid. Copolymer or isobutylene/maleic acid (anhydride) copolymer, and the like. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, is suitable for use because it has high heat resistance and transparency.

The active energy ray-curable resin having an ethylenic unsaturated double bond may, for example, be a resin obtained by introducing an ethylenically unsaturated double bond by the method (i) or (ii) shown below.

[Method (i)] As the method (i), for example, there is a method in which a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and another monomer is copolymerized The addition reaction is carried out with a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group. Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and 2-epoxypropoxy (meth)acrylate. Ethyl ester, (meth)acrylic acid-3,4-epoxybutyl acrylate, and (meth)acrylic acid -3,4-epoxycyclohexyl ester, these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred. Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl group of (meth)acrylic acid, alkoxy group, halogen, a monocarboxylic acid such as a nitro group or a cyano substituent. These may be used singly or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used singly or in combination of two or more. The tricarboxylic acid anhydride such as trimellitic anhydride or the tetracarboxylic dianhydride such as pyromellitic acid dianhydride may be used to hydrolyze the residual acid anhydride group, etc., depending on the number of carboxyl groups to be added. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.

As a similar method of the method (i), for example, there is a method in which a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and another one or more monomers has an epoxy group. The ethylenically unsaturated monomer undergoes an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)] As the method (ii), there is a method in which a copolymer is obtained by copolymerizing a monomer having an ethylenically unsaturated monomer having a hydroxyl group and another monomer having an unsaturated monobasic acid having a carboxyl group or another monomer. Further, the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid-2 or 3 or a hydroxyalkyl (meth)acrylate such as 4-hydroxybutyl ester, glyceryl (meth)acrylate or cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more. And use it. Further, a polyether mono(meth)acrylate formed by addition polymerization of the above (meth)acrylic acid hydroxyalkyl ester with ethylene oxide, propylene oxide, and/or butylene oxide, or the like, or (Poly)ester mono(meth)acrylate formed by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid. From the viewpoint of suppressing the foreign matter of the coating film, 2-hydroxyethyl (meth)acrylate or glyceryl (meth)acrylate is preferred.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloxyethyl isocyanate or 1,1-bis[(meth)acryloxy]ethyl isocyanate. It is not limited to these substances, and two or more types may be used together.

In order to disperse the colorant well, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less. With respect to the acid value of the resin, from the viewpoints of dispersibility, stability, developability, and heat resistance of the colorant, a carboxyl group acting as a coloring agent adsorption group and an alkali soluble group at the time of development is considered. When the equilibrium of the aliphatic group and the aromatic group which act on the affinity group of the colorant carrier and the solvent, the acid value is preferably from 20 to 300 mgKOH/g. When the solubility in the developer and the formation of the fine pattern are considered, the acid value is preferably 20 mgKOH/g or more. Further, in consideration of the degree of retention of the fine pattern, it is preferably 300 mgKOH/g or less.

From the viewpoint of good film formability and various kinds of resistance, the resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant, and exhibits good color characteristics due to an increase in colorant concentration. It is preferred to use an amount of 500 parts by weight or less.

<Solvent> The coloring composition for a color filter of the present invention may contain a solvent. In order to facilitate the dispersion of the colorant in the resin, the coloring agent composition of the present invention is applied to a transparent substrate such as a glass substrate so that the dried film thickness is preferably 0.1 to 10 μm, more preferably 0.2 to 20 μm. The color section is used while the solvent is used.

Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol diacetate, and 1,4-two. Alkane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone , 3-ethoxypropionic acid ethyl ester, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl Butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, dichlorobenzene, N,N-dimethyl Acetamide, N,N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o- Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, t-butylbenzene, t-butylbenzene, γ-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol Dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene glycol monoisopropyl ether Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, two Propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, Tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ethyl propyl ester, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid esters.

These solvents may be used singly or in combination of two or more kinds in an arbitrary ratio as needed. Among them, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. are preferably used from the viewpoint of good dispersibility of the coloring agent of the present invention. An aromatic alcohol such as a glycol acetate or a benzyl alcohol or a ketone such as cyclohexanone. In view of the color filter segment capable of adjusting the coloring composition to an appropriate viscosity and forming a uniform film thickness as the target, the solvent is preferably used in an amount of 800 to 4000 parts by weight based on 100 parts by weight of the colorant. Further, a coloring agent composition for a color filter of the present invention may be further added with a photopolymerizable monomer and/or a photopolymerization initiator to be used as a coloring composition (photoresist) for a color filter.

<Photopolymerizable monomer>

The coloring composition for a color filter of the present invention may contain a photopolymerizable monomer. The photopolymerizable monomer contains a monomer or an oligomer which is formed by curing by ultraviolet rays or heat, and these may be used singly or in combination of two or more kinds. The amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability, and most preferably 10 to 200 parts by weight. The photopolymerizable monomer is preferably a compound having one or two or more ethylenically unsaturated double bonds.

Examples of the photopolymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol Alcohol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, Dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanol (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy Various acrylates and methacrylates such as (meth) acrylate and urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, and hydroxyethyl Vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide, acrylonitrile, etc. It is not necessarily limited to these.

<Photopolymerization initiator> The coloring composition for a color filter of the present invention may contain a photopolymerization initiator. When the composition is cured by ultraviolet irradiation and a color filter segment or a black matrix is formed by photolithography, a photopolymerization initiator or the like is added, and a solvent development type or an alkali development type photosensitive coloring composition can be used. modulation.

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl group) can be used. Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl Propane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Or an acetophenone compound such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one; benzoin, benzoin methyl ether, benzene A benzoin compound such as diethyl ether, benzoin isopropyl ether or biphenyl dimethyl acetal; benzophenone, benzoquinone benzoic acid, methyl benzoquinone, 4-phenylbenzophenone, Hydroxybenzophenone, benzoated benzophenone, 4-phenylmercapto-4'-methyldiphenyl sulfide or 3,3',4,4'-tetra(peroxidized tert-butylcarbonyl) a benzophenone compound such as benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone or 2 , 4-diethylthioxanthone and other thioxanthone compounds; 2,4,6-trichloro-all three 2-phenyl-4,6-di(trichloromethyl)-all three , 2-(p-methoxyphenyl)-4,6-di(trichloromethyl)-all three , 2-(p-tolyl)-4,6-di(trichloromethyl)-all three , 2-piperidin-4,6-di(trichloromethyl)-all three , 2,4-di(trichloromethyl)-6-styryl-all three , 2-(naphtho-1-yl)-4,6-di(trichloromethyl)-all three , 2-(4-methoxy-naphtho-1-yl)-4,6-di(trichloromethyl)-all three 2,4-trichloromethyl-(piperidinyl)-6-three Or 2,4-trichloromethyl-(4'-methoxystyryl)-6-three Wait three a compound; 1,2-octanediol, 1-[4-(phenylthio)-2-(O-benzamide)] or O-(ethinyl)-N-(1-phenyl- 2-oxo-2-(4'-methoxy-naphthyl)ethyl)hydroxylamine, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H An oxime ester compound such as oxazol-3-yl]-1-(O-acetamidine); bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6 a phosphine compound such as trimethylbenzhydryldiphenylphosphine oxide; an anthraquinone compound such as phenanthraquinone, camphorquinone or ethyl hydrazine; a borate ester compound; Carbazole-based compound; imidazole-based compound; or ferrocene-based compound. These photopolymerization initiators may be used alone or in combination of two or more kinds in an arbitrary ratio as needed. The content of the photopolymerization initiator is preferably 5 to 200 parts by weight based on 100 parts by weight of the colorant, and more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer> Further, the coloring composition for a color filter of the present invention may further contain a sensitizer.

Examples of the sensitizer include unsaturated ketones typified by chalcone derivatives, dibenzylideneacetone derivatives, and the like, and 1,2- represented by biphenyl hydrazine and camphorquinone. Diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthen derivatives, xanthone derivatives , thioxanthone derivatives, coumarin derivatives, coumarin derivatives, cyanin derivatives, merocyanine derivatives, oxonol derivatives Polymethine pigment, acridine derivative, hydrazine (azine) derivative, thio (thiazine) derivative, (oxazine) derivative, porphyrin derivative, azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin Derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyridyl Tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetra(quinoxalino)porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative , pyrylium derivative, thiopyran derivative, tetraphyllin derivative, annulene derivative, spiropyran derivative, spiro (spiroxazine) derivative, Thio Spiropyran derivative, metal aromatic hydrocarbon complex, organic ruthenium complex, or Michlerketone derivative, α-methoxyl ester, biguanide Phosphate phosphine, methyl benzoate, biphenyl hydrazine, 9,10-phenanthrenequinone, camphorquinone, ethyl hydrazine, 4,4'-diethyl meta-phenyl dimethyl ketone, 3, 3'- or 4,4'-tetra(peroxybutoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, and the like.

These sensitizers may be used alone or in combination of two or more kinds in an arbitrary ratio as needed.

More specifically, the "Pigment Handbook" (1986, Kodansha), and the "Chemistry of Functional Pigments" (1981, CMC) prepared by Okawa Shinko, etc., and Chisato Chsaburo, etc. The sensitizer described in "Special Functional Materials" (1986, CMC) is not limited thereto. In addition, other sensitizers which exhibit absorption of light from the ultraviolet to the near-infrared region may also be contained.

The content of the sensitizer is 0.1 to 60 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the photopolymerization initiator contained in the coloring composition, from the viewpoint of photocurability and developability. More preferably, it is 5 to 50 parts by weight.

<Leveling Agent> In order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethyloxane having a polyether structure or a polyester structure in the main chain is preferred. Specific examples of the dimethyloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd., BYK-333 manufactured by BYK Chemical Co., Ltd., and the like. Specific examples of the dimethyl siloxane having a polyester structure in the main chain include BYK-310, BYK-370, and the like manufactured by BYK Chemical Co., Ltd. Dimethyl decane having a polyether structure in the main chain and dimethyl methoxy alkane having a polyester structure in the main chain may also be used in combination. In terms of the content of the leveling agent, it is usually used in an amount of from 0.003 to 0.5% by weight based on 100% by weight of the total weight of the coloring composition.

As a particularly preferable substance for the leveling agent, a substance which is a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which is characterized in that it has a hydrophilic group but dissolves in water, is preferably used. It is small, and when it is added to a coloring composition, its ability to lower the surface tension is low, and in addition, although the ability to lower the surface tension is low, the wettability to the glass plate is good, and it does not occur. When the addition amount of the defect of the coating film by the foam is added, the chargeability can be sufficiently suppressed. As the leveling agent having such excellent characteristics, a dimethyl polyoxyalkylene having a polyalkylene oxide unit can be preferably used. As the polyalkylene oxide unit, it may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethyl polyoxyalkylene may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the combination of the polyalkylene oxide unit and the dimethyl polyoxyalkylene may be any of the following: a suspension type in which a polyalkylene oxide unit is bonded to a repeating unit of dimethyl polyoxyalkylene, A linear block polymer type which is bonded to the terminal end of the dimethyl polysiloxane and which is alternately repeatedly bonded to dimethyl polyoxyalkylene. The dimethyl polyoxyalkylene having a polyalkylene oxide unit may be, for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ- sold by Toray Dow Corning Corporation. 2203, FZ-2207, but is not limited to these. In the leveling agent, an anionic, cationic, nonionic or amphoteric surfactant may also be added. The surfactant may be used in combination of two or more kinds.

Examples of the anionic surfactant added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, an alkali metal salt of a styrene-acrylic acid copolymer, and an alkyl naphthalene. Sodium sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, twelve Sodium alkyl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

As the cationic surfactant added to the leveling agent, an alkyl quaternary ammonium salt and an ethylene oxide adduct thereof can be given. Examples of the nonionic surfactant added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene phenylene ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene. Sorbitan monostearate monostearate, polyethylene glycol monolaurate, etc.; alkyl betaine such as alkyl dimethylaminoacetate betaine, alkyl imidazoline, etc., and fluorine and organic oxime The surfactant of the system.

<Amine compound> In addition, the coloring composition for a color filter of the present invention may contain an amine compound having an action of reducing dissolved oxygen. Examples of such an amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, and the like.

In the coloring composition for a color filter of the present invention, a curing agent, a curing accelerator, and the like may be contained as needed. The phenol resin, the amine compound, the acid anhydride, the active ester, the carboxylic acid compound, the sulfonic acid compound, or the like is effective as the curing agent, but is not particularly limited thereto, and as long as it can react with the thermosetting resin, Any hardener can be used. Further, among these curing agents, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferably used. As the hardening accelerator, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy- can be used. N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compound (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate a compound (for example, dimethylamine or the like), an imidazole derivative bicyclic guanidine compound, and a salt thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-benzene) Pyrimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (for example, three Phenylphosphine, etc., guanamine compounds (for example, melamine, guanamine, acetamide, benzoguanamine, etc.), all three a derivative (for example, 2,4-diamino-6-methacryloxyethyl) 2-vinyl-2,4-diamino group , 2-vinyl-4,6-diamino--three ‧Isocyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl ‧ Isocyanuric acid adducts, etc.). These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on the total weight of the thermosetting resin (100 parts by weight).

<Other Additive Component> In order to stabilize the viscosity of the composition over time, the coloring composition for a color filter of the present invention may contain a storage stabilizer. Further, in order to improve the adhesion to the transparent substrate, an adhesion improving agent such as a decane coupling agent may be further contained. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, methyl ethers thereof, and tert-butyl catechol. An organic phosphine such as tetraethylphosphine or tetraphenylphosphine, or a phosphite. The storage stabilizer may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the colorant.

Examples of the adhesion enhancer include vinyl decane such as vinyl tris(β-methoxyethoxy)decane, vinyl ethoxy decane, and vinyl trimethoxy decane; γ-methyl propylene oxime (meth) propylene decyl oxane such as propyl trimethoxy decane; β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, β-(3,4-epoxycyclohexyl)methyl Trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltriethoxy decane, β-(3,4-epoxycyclohexyl)methyltriethoxydecane, γ-epoxy An epoxy decane such as propoxypropyltrimethoxydecane or γ-glycidoxypropyltriethoxydecane; N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-β (aminoethyl) γ-aminopropyl triethoxy decane, N-β (aminoethyl) γ-aminopropyl methyl diethoxy decane, γ-aminopropyl Triethoxy decane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, etc. a decane coupling such as an oxane decane or a thiononane such as γ-mercaptopropyltrimethoxydecane or γ-mercaptopropyltriethoxydecane Agents, etc. The adhesion enhancer may be used in an amount of from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, per 100 parts by weight of the total amount of the colorant.

<Method for Producing Colored Composition> The coloring composition for a color filter of the present invention can be used together with various dispersing devices such as a three-roll mill, a two-roll mill, a sand mill, a kneader or an attritor. Fine dispersion is carried out to produce (pigment dispersion). Further, when it is used as a photosensitive coloring composition (photoresist material) for a color filter, it can be prepared into a solvent developing type or an alkali developing type coloring composition. The solvent developing type or the alkali developing type coloring composition may be obtained by mixing the above pigment dispersion, photopolymerizable monomer, and/or photopolymerization initiator, and if necessary, a solvent, other pigment dispersant, and additives. modulation. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added after the coloring composition is prepared.

In view of viscosity, film thickness, fluidity, and paintability, the solid content concentration of the coloring composition for a color filter is preferably 5% by weight or more and less than 40% by weight.

The coloring composition for a color filter is preferably a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a coarse particle of 0.5 μm or more, by a method such as centrifugal separation, a sintered filter or a membrane filter. The mixed dust is removed. The coloring composition for a color filter obtained as above preferably contains no coarse particles. More preferably, it is 0.3 μm or less. Further, when the coloring composition for a color filter according to the first embodiment is produced, the following may be mixed: as the coloring agent, the average primary particle diameter is 20 to 50 nm and the aspect ratio of the pigment particles is 1:1 to 1: a pigment of 3.5; as a resin type dispersant, an AB block copolymer or a BAB block copolymer composed of a blister-soluble A block and a B block having a nitrogen atom-containing functional group, and the amine value is An acrylic block copolymer having an effective solid content of 10 mgKOH/g or more and 99 mgKOH/g or less; a solvent; and other components as needed.

In addition, when the coloring composition for a color filter of the present invention is formed into a black resin composition as a black coloring composition (second embodiment), the following may be mixed: as a light-shielding black pigment, it is an average primary particle. a lanthanide black pigment and carbon black having a diameter of 50 nm or less and an aspect ratio of primary particles of 1:1 to 1:2; a resin; a solvent; and other components as needed, and shading the content of the lanthanide black pigment The total weight of the black pigment (A) is 78 to 95% by weight based on the total weight of the black resin composition, and the solid content concentration of the black resin composition is 5% by weight or more and less than 40% by weight.

When the black resin composition which is a black coloring composition is formed by the colored composition for a color filter of the present invention (third embodiment), the following components can be mixed: as a light-shielding black pigment, the average primary particle diameter is An anthraquinone black pigment having an aspect ratio of 50 nm or less and a primary particle of 1:1 to 1:2; a pigment dispersant; a resin, a solvent; and other components as needed.

<Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention includes a color filter segment and/or a black matrix formed of the coloring composition for a color filter of the present invention on a substrate, and for example, a black matrix and a color filter segment of red, green, and blue may be provided.

The formation of the color filter segments and/or the black matrix by photolithography is carried out as follows. That is, a coloring resin prepared by a solvent developing type or an alkali developing type colored resin composition (photoresist material) is applied onto a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. Composition. For the film which is dried as necessary, the active energy ray exposure is performed by a mask having a predetermined pattern which is provided in contact with or in contact with the film. Thereafter, it is immersed in a solvent or an alkaline developing solution or sprayed with a developing solution by spraying or the like to remove the uncured portion, whereby a color filter segment and/or a black matrix having a desired pattern can be formed. Further, in order to promote the polymerization of the photosensitive black resin composition, heating may be carried out as needed. Photolithography can be used to form color filter segments and/or black matrices that are more precise than printing.

As the substrate of the color filter, a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free borosilicate glass, or polycarbonate or polymethyl methacrylate, which has high visible light transmittance, can be used. A resin plate such as polyethylene terephthalate. Further, in order to drive the panelized liquid crystal, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate. At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide can be used as the alkaline developing solution, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer. As the development treatment method, a shower development method, a spray development method, an impregnation (impregnation) development method, a stirring (liquid) development method, or the like can be used. Further, in order to increase the ultraviolet exposure sensitivity, the coloring composition for a color filter may be coated and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied and dried to prevent the formation of the coloring composition. After blocking the polymerized film by oxygen, active energy ray exposure is performed.

As the active energy ray, electron rays, ultraviolet rays, and visible light of 400 to 500 nm can be used. As the radiation source of the electron beam irradiated from the side where the composition is coated, a hot electron emission gun, an electric field emission gun, or the like can be used. Further, as the radiation source (light source) of ultraviolet rays and visible light of 400 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp or the like can be used. Specifically, an ultrahigh pressure mercury lamp or a mercury mercury lamp is often used because it is a point source and the brightness is stable. The energy of the active energy ray irradiated from the side of the coated surface of the composition can be set in the range of 5 to 1000 mJ in a timely manner, preferably in the range of 20 to 300 mJ which is easily manageable in steps.

When the black matrix is formed in advance before the color filter segments are formed on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further improved. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed can be used, but it is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a color filter segment may be formed. By forming the color filter segments and/or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be improved and the brightness can be improved.

Here, a method of forming a coloring layer on a TFT substrate will be described. First, on the surface of the TFT substrate or on the surface of the substrate on which the passivation film such as a tantalum nitride film is formed on the surface of the drive substrate, a light shielding layer is formed as needed to divide the portion where the pixel is formed, and then the substrate is coated and dispersed. After the pigmented coloring composition, prebaking is performed to evaporate the solvent to form a coating film. Next, after exposure on the coating film via a photomask, development is carried out using an alkaline developing solution, and the unexposed portion of the coating film is dissolved and removed, and then a pixel array in which pixel patterns are arranged in a predetermined arrangement is formed by post-baking. . At this time, on the reticle used, in addition to the pattern for forming the pixels, a through hole or The pattern of the pits of the font. As the TFT substrate used for forming the coloring layer, the same substrate as the substrate of the color filter may be used, or chemical treatment such as a decane coupling agent, plasma treatment, ion plating, or sputtering may be previously performed on the substrates. Suitable pretreatments such as plating, gas phase reaction, vacuum evaporation, and the like. When the coloring composition is applied onto the substrate, a method similar to the substrate of the color filter described above can be used.

The coating film thickness of the color filter section is preferably from 0.1 to 10 μm, more preferably from 0.5 to 6.0 μm, as the film thickness after drying. The coating film thickness of the black matrix is preferably in the range of 0.2 to 10.0 μm, more preferably in the range of 0.2 to 5.0 μm, as the film thickness after drying. Further, it is more preferable that the coating property and the light-shielding property are easily balanced in the range of 0.5 to 2.5 μm. Further, from the viewpoint of the insulating property, the relative dielectric constant of the dried film thickness per 1.0 μm of the black matrix is preferably 8.0 or less, more preferably 4.5 or less. Further, in order to perform alignment using infrared rays, the light transmittance at a wavelength of 780 nm is preferably 15% or more and less than 99% for a black matrix having a dry film thickness of 1.0 μm. The transmittance at a wavelength of 1000 nm is preferably 60% or more and less than 99%.

Further, from the viewpoint of high light-shielding property, the optical density of the black matrix having a dry film thickness of 1.0 μm is preferably 1.30 or more, and more preferably 2.50 or more. The higher the optical density, the better. However, when the active energy ray is ultraviolet light or visible light, it is difficult to obtain a cured coating film, and therefore it is preferably about 4.5 or less.

When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like can be used. A protective film or a columnar gasket, a transparent conductive film, a liquid crystal alignment film, or the like can be formed on the color filter as needed. By bonding the color filter to the counter substrate by using a sealant, the liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed, and if necessary, the polarizing film or the retardation film is bonded to the outside of the substrate. Manufacturing a liquid crystal display panel.

The related liquid crystal display panel can be used for coloring using color filters such as twisted nematic (TN), super twisted nematic (STN), plane conversion (IPS), vertical alignment (VA), and optical compensation bending (OCB). LCD mode. <Substrate for Driving a Thin Film Transistor (TFT) Color Liquid Crystal Display Device> A substrate for driving a thin film transistor (TFT) color liquid crystal display device can be spin-coated and narrow on a substrate of a thin film transistor (TFT). A coating method such as slit coating or roll coating is formed by forming a color filter segment of, for example, red, blue, and green, and then forming a black matrix. Alternatively, a black matrix may be formed on the substrate of the thin film transistor (TFT), and a color filter segment may be formed thereon.

[Examples]

The invention is illustrated below based on the examples, but the invention is not limited by the examples. In addition, in the examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively. Further, the weight average molecular weight (Mw) of the resin, the acid value of the resin or resin type dispersant, the amine value of the resin type dispersant, the specific surface area of the pigment, the average primary particle diameter and the aspect ratio of the pigment, and the contrast ratio of the coating film, The method for measuring the film thickness of the coating film is as follows. <The weight average molecular weight (Mw) of the resin> The weight average molecular weight (Mw) of the acrylic resin is a TPCgel column (manufactured by Tosoh Corporation), a GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), The eluate was a polystyrene-equivalent weight average molecular weight (Mw) measured using THF.

<Acid Value of Resin or Resin Type Dispersant> The acid value was determined by potentiometric titration using a 0.1 N sodium hydroxide ‧ ethanol solution. The acid value indicates the acid value of the solid component. <Amine value of resin-type dispersing agent> The amine value was determined by a potentiometric titration method using a 0.1 N aqueous hydrochloric acid solution, and then converted into an equivalent amount of potassium hydroxide. The amine value indicates the amine value of the solid component.

<Specific Surface Area of Pigment> The measurement of the specific surface area of the pigment was carried out by an automatic vapor adsorption amount measuring apparatus ("BELSORP18" manufactured by BEL Corporation, Japan) using a BET method of nitrogen adsorption.

<Average primary particle diameter and aspect ratio of the pigment> The average primary particle diameter and aspect ratio of the pigment were measured by a method of directly measuring the primary particle size from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was used as the particle diameter of the pigment particles. Next, the volume (weight) of each particle is determined by approximating the cube of the particle diameter by approximately 100 pigment particles, and the volume average particle diameter is made into the average primary particle diameter. Further, as described above, the ratio of the minor axis diameter of the primary particles of each pigment to the average value of the minor axis diameter and the major axis diameter when the major axis diameter is measured is determined as the length and width when the minor axis diameter is set to 1. ratio. In addition, the electron microscope uses a transmission type (TEM).

<Contrast of Coating Film> The light emitted from the liquid crystal display backlight unit is deflected by the polarizing plate, and is then passed through a dried coating film of the colored composition coated on the glass substrate to reach the polarizing plate. If two polarizing plates are parallel, light passes through the polarizing plate, and when the polarizing surface is perpendicular, the light is blocked by the polarizing plate. However, when the light deflected by the polarizing plate is dried by the colored coating film, scattering due to the pigment particles occurs, and if a shift occurs in a part of the polarizing surface, the amount of light transmitted through the polarizing plate when the polarizing plate is parallel is obtained. When the polarizing plate is vertical, a part of the light transmits the polarizing plate. The transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast) of the luminance when the polarizing plates were parallel to the luminance at the vertical direction was calculated.

(Contrast) = (brightness in parallel) / (brightness in vertical) In addition, a chromaticity luminance meter ("BM-5A" manufactured by Topcon) was used as a luminance meter, and a polarizing plate (manufactured by Nitto Denko Corporation) was used. "NPF-G1220DUN") is used as a polarizing plate. At the time of measurement, in order to block unnecessary light, a black mask having a hole of 1 cm square was placed on the measurement portion.

<Thickness of Coating Film> The film thickness of the coating film was measured using a surface shape measuring device (Dektak 6M manufactured by Aiko Co., Ltd.). First, the first embodiment will be described using an embodiment and a comparative example.

<Method for Producing Resin-Type Dispersant> (Resin-type Dispersant Solution A) 80 parts of methyl ethyl ketone and butyl acrylate 86.7 were placed in a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler. A portion, 11.8 parts of Blenmer PME-200 (methoxypolyethylene glycol methacrylate), 2.8 parts of oleolin, and 1.9 parts of ethyl bromoisobutyrate were heated to 40 ° C under a nitrogen gas flow. 1.1 parts of cuprous chloride was charged, and the temperature was raised to 75 ° C to start polymerization. After the polymerization for 3 hours, the polymerization solution was sampled, and the polymerization yield was confirmed to be 95% or more, the weight average molecular weight (Mw) was 6,860, and 1.4 parts of dimethylaminoethyl methacrylate and methyl ethyl ketone were added. 20.0 parts, further polymerization was carried out. The solid content of the polymerization solution after 2 hours was confirmed to be 97% or more, and the mixture was cooled to room temperature to terminate the polymerization. 100 parts of methyl ethyl ketone was diluted with respect to 100 parts of the obtained resin solution, 60 parts of cation exchange resin "DIAION PK228LH (made by Mitsubishi Chemical Corporation)" was added, and it stirred at room temperature for 1 hour, and further added 6 parts of Kyowaad. 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was used as a neutralizing agent and stirred for 30 minutes. The residue of the polymerization catalyst is removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin type dispersant solution was concentrated and the solvent was replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant solution A (dispersant A) having a solid content ratio of 50% by weight (amine value: 5 mgKOH/ g, the acid value is 0 mgKOH/g).

(Resin type dispersant solution B) 80 parts of methyl ethyl ketone, 85.5 parts of butyl acrylate, and Blenmer PME-200 (methoxyl) were placed in the 4-port separable flask equipped with the thermometer, the mixer, the distillation tube, and the cooler. 11.7 parts of a base polyethylene glycol methacrylate, 2.8 parts of oleolin, and 1.9 parts of ethyl bromoisobutyrate were heated to 40 ° C under a nitrogen gas flow. 1.1 parts of cuprous chloride was charged, and the temperature was raised to 75 ° C to start polymerization. After the polymerization for 3 hours, the polymerization solution was sampled, and the polymerization yield was confirmed to be 95% or more, the weight average molecular weight (Mw) was 6,860, and 2.9 parts of dimethylaminoethyl methacrylate and methyl ethyl ketone were added. 20.0 parts, further polymerization was carried out. The solid content of the polymerization solution after 2 hours was confirmed to be 97% or more, and the mixture was cooled to room temperature to terminate the polymerization. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, and 60 parts of a cation exchange resin "DIAION PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added thereto, and the mixture was stirred at room temperature for 1 hour, and further 6 parts of Kyowaad 500SN ( As a neutralizer, Concord Chemical Industries Co., Ltd. was stirred for 30 minutes. The residue of the polymerization catalyst is removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin type dispersant solution was concentrated and the solvent was replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant solution B (dispersant B) having a solid content ratio of 50% by weight (amine value: 10 mgKOH/ g, the acid value is 0 mgKOH/g).

(Resin type dispersant solution C) 80 parts of methyl ethyl ketone, 71.0 parts of butyl acrylate, and Blenmer PME-200 (methoxyl) were placed in a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler. 9.0 parts of polyethylene glycol methacrylate), 2.8 parts of oleolin, and 1.9 parts of ethyl bromoisobutyrate were heated to 40 ° C under a nitrogen gas flow. 1.1 parts of cuprous chloride was charged, and the temperature was raised to 75 ° C to start polymerization. After the polymerization for 3 hours, the polymerization solution was sampled, and the polymerization yield was confirmed to be 95% or more, the weight average molecular weight (Mw) was 6,860, and dimethylaminoethyl methacrylate 20.0 parts and methyl ethyl ketone were added. 20.0 parts, further polymerization was carried out. The solid content of the polymerization solution after 2 hours was confirmed to be 97% or more, and the mixture was cooled to room temperature to terminate the polymerization. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, and 60 parts of a cation exchange resin "DIAION PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added thereto, and the mixture was stirred at room temperature for 1 hour, and further 6 parts of Kyowaad 500SN ( As a neutralizer, Concord Chemical Industries Co., Ltd. was stirred for 30 minutes.

The residue of the polymerization catalyst is removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin type dispersant solution was concentrated and the solvent was replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant solution C (dispersant C) having a solid content ratio of 50% by weight (amine value: 70 mgKOH/ g, the acid value is 0 mgKOH/g).

(Resin type dispersant solution D)

In a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 80 parts of methyl ethyl ketone, 64.1 parts of butyl acrylate, and Blenmer PME-200 (methoxypolyethylene glycol methacrylic acid) were placed. The ester was 8.7 parts, 2.8 parts of oleolin, and 1.9 parts of ethyl bromoisobutyrate, and the temperature was raised to 40 ° C under a nitrogen gas flow. 1.1 parts of cuprous chloride was charged, and the temperature was raised to 75 ° C to start polymerization. After the polymerization for 3 hours, the polymerization solution was sampled, and the polymerization yield was confirmed to be 95% or more, the weight average molecular weight (Mw) was 6,860, and the dimethylaminoethyl methacrylate was added to 27.1 parts and methyl ethyl ketone. 20.0 parts, further polymerization was carried out. The solid content of the polymerization solution after 2 hours was confirmed to be 97% or more, and the mixture was cooled to room temperature to terminate the polymerization. 100 parts of methyl ethyl ketone was diluted with respect to 100 parts of the obtained resin solution, 60 parts of cation exchange resin "DIAION PK228LH (made by Mitsubishi Chemical Corporation)" was added, and it stirred at room temperature for 1 hour, and further added 6 parts of Kyowaad. 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was used as a neutralizing agent and stirred for 30 minutes. The residue of the polymerization catalyst is removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin type dispersant solution was concentrated and the solvent was replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant solution D (dispersant D) having a solid content ratio of 50% by weight (amine value: 95 mgKOH/ g, the acid value is 0 mgKOH/g).

(Resin type dispersant solution E)

In a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 80 parts of methyl ethyl ketone, 57.8 parts of butyl acrylate, and Blenmer PME-200 (methoxypolyethylene glycol methacrylic acid) were placed. The ester was 7.9 parts, 2.8 parts of oleolin, and 1.9 parts of ethyl bromoisobutyrate, and the temperature was raised to 40 ° C under a nitrogen gas stream. 1.1 parts of cuprous chloride was charged, and the temperature was raised to 75 ° C to start polymerization. After the polymerization for 3 hours, the polymerization solution was sampled, and the polymerization yield was confirmed to be 95% or more, the weight average molecular weight (Mw) was 6,860, and 34.3 parts of dimethylaminoethyl methacrylate and methyl ethyl ketone 20.0 were added. Further, the polymerization was carried out. The solid content of the polymerization solution after 2 hours was confirmed to be 97% or more, and the mixture was cooled to room temperature to terminate the polymerization. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, and 60 parts of a cation exchange resin "DIAION PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added thereto, and the mixture was stirred at room temperature for 1 hour, and further 6 parts of Kyowaad 500SN ( As a neutralizer, Concord Chemical Industries Co., Ltd. was stirred for 30 minutes. The residue of the polymerization catalyst is removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin type dispersant solution was concentrated and the solvent was replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant solution E (dispersant E) having a solid content ratio of 50% by weight (amine value: 120 mgKOH/ g, the acid value is 0 mgKOH/g).

(Resin-type dispersant solution F) 80 parts of methyl ethyl ketone, 70.4 parts of butyl acrylate, Blenmer PME-200 (methoxyl) was placed in the 4-port separable flask equipped with the thermometer, the mixer, the distillation tube, and the cooler. 9.6 parts of polyethylene glycol methacrylate), 2.8 parts of oleolin, 1.9 parts of ethyl bromoisobutyrate, 20.0 parts of dimethylaminoethyl methacrylate, and heated to 40 ° C under a nitrogen gas stream . 1.1 parts of cuprous chloride was charged, and the temperature was raised to 75 ° C to start polymerization. After the polymerization for 3 hours, the polymerization solution was sampled, and the solid content of the polymerization solution was confirmed to be 97% or more, and the mixture was cooled to room temperature to terminate the polymerization. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, and 60 parts of a cation exchange resin "DIAION PK228LH (manufactured by Mitsubishi Chemical Corporation)" was added thereto, and the mixture was stirred at room temperature for 1 hour, and further 6 parts of Kyowaad 500SN ( As a neutralizer, Concord Chemical Industries Co., Ltd. was stirred for 30 minutes. The residue of the polymerization catalyst is removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin type dispersant solution was concentrated and the solvent was replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant solution F (dispersant F) having a solid content ratio of 50% by weight (amine value: 70 mgKOH/ g, the acid value is 0 mgKOH/g).

The resin structure of each resin type dispersant and the amine value in terms of effective solid content are summarized in Table 1.

<Method for Producing Pigment Derivative> (Pigment Derivative 1 (Metal Salt of Quinone Ketone Sulfonic Acid)) 30 parts of a quinophthalone-based yellow pigment (CI Pigment Yellow 138) was dissolved in 300 parts of 98% sulfuric acid, The mixture was stirred at 70 ° C for 8 hours to carry out a sulfonation reaction.

The end point of the reaction is a point at which no spectral change is observed when the spectroscopic spectrum of the sulfuric acid solution is measured. Then, the reaction solution was poured into 3,000 parts of ice water, and the precipitated sulfonated dye derivative was filtered, washed with water, and dried to obtain a structure represented by the formula (4) as a sulfonated derivative of CI Pigment Yellow 138. Quinone skeleton sulfonic acid. The yield after drying was 334 parts, and the yield was 99%. Formula (4)

The slurry of quinacridone skeleton sulfonic acid was redispersed in 10,000 parts of water (pH 2.5). Subsequently, it was adjusted to pH 11 with an aqueous sodium hydroxide solution, and dissolved to form a red solution. To the solution, 278 parts of an aqueous solution of aluminum sulfate (liquid aluminum sulfate) was slowly added. Precipitates gradually appeared from the dropping point, and as the pH was added, the pH was lowered, and the pH at the end of the addition was 3.6. No fading was observed. The slurry containing the precipitate is filtered and washed with water to obtain a pigment derivative of a metal salt of a quinophthalone skeleton sulfonic acid having a structure represented by the formula (5) as an aluminum salt of a sulfonated derivative of CI Pigment Yellow 138. Matter 1. The yield after drying was 334 parts, and the yield was 99%. Formula (5)

<Method for Producing Micronized Pigment> (Green Pigment PG-1) 500 parts of phthalocyanine-based green pigment CI Pigment Green 36 ("Lionol green 6YK" manufactured by Toyo Ink Co., Ltd.), 1500 parts of sodium chloride, and 2 250 parts of the diol was placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 80 ° C for 8 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, the green pigment PG-1 was obtained.

(Green Pigment PG-2) 500 parts of phthalocyanine-based green pigment CI Pigment Green 36 ("Lionol green 6YK" manufactured by Toyo Ink Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in stainless steel. A one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) was prepared and kneaded at 80 ° C for 2 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, I got green pigment PG-2.

(green pigment PG-3)

500 parts of phthalocyanine green pigment CI Pigment Green 36 ("Lionol green 6YK" manufactured by Toyo Ink Manufacturing Co., Ltd.), 1500 parts of sodium chloride and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue The company made by the company, and kneaded at 40 ° C for 12 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, I got the green pigment PG-3.

(Green Pigment PG-4) 500 parts of phthalocyanine-based green pigment CI Pigment Green 36 ("Lionol green 6YK" manufactured by Toyo Ink Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in stainless steel. A one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) was prepared and kneaded at 80 ° C for 2 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, I got green pigment PG-4.

(Green Pigment PG-5) 500 parts of phthalocyanine-based green pigment CI Pigment Green 36 ("Lionol green 6YK" manufactured by Toyo Ink Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in stainless steel. A 1 gallon kneader (manufactured by Inoue Co., Ltd.) was prepared and kneaded at 80 ° C for 4 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, the green pigment PG-5 was obtained.

(yellow pigment PY-1)

200 parts of a nickel complex yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue Manufacturing Co., Ltd.) The company manufactures) and kneads at 80 ° C for 8 hours. Next, the kneaded product was poured into 8000 parts of warm water, and stirred while heating to 80 ° C for 2 hours to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. A yellow pigment PY-1 was obtained overnight.

(Yellow Pigment PY-2) 200 parts of quinophthalone-based yellow pigment CI Pigment Yellow 138 ("K0961HD" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel. (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 80 ° C for 8 hours. Next, the kneaded product was poured into 8000 parts of warm water, and stirred while heating to 80 ° C for 2 hours to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. One night, the yellow pigment PY-2 was obtained.

(Yellow Pigment PY-3) 200 parts of an isoporphyrin-based yellow pigment CI Pigment Yellow 185 ("PalIotol Yellow L1155" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a gallon of stainless steel. The kneading machine (manufactured by Inoue Co., Ltd.) was kneaded at 80 ° C for 8 hours. Next, the kneaded product was poured into 8000 parts of warm water, and stirred while heating to 80 ° C for 2 hours to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. A yellow pigment PY-3 was obtained overnight.

(Black pigment PBLK-2) 500 parts of a lanthanide black pigment CI Pigment Black 32 ("PalIogen Black L0086" by BASF Corporation), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel. (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 80 ° C for 12 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, the black pigment PBLK-2 was obtained.

(Black pigment PBLK-3) 500 parts of a lanthanide black pigment ("Lumogen Black FK4281" manufactured by BASF Corporation), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (Inoue Co., Ltd.) Manufactured), kneaded at 40 ° C for 12 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, the black pigment PBLK-3 was obtained.

(Black pigment PBLK-4) 500 parts of lanthanum black pigment CI Pigment Black 31 ("PalIogen Black S0084" manufactured by BASF Corporation), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel. (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 80 ° C for 5 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, the black pigment PBLK-4 was obtained.

(black pigment PBLK-5)

500 parts of lanthanide black pigment ("Lumogen Black FK4281" manufactured by BASF Co., Ltd.), 2500 parts of sodium chloride and 250 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.) and mixed at 80 ° C. Refining for 5 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, the black pigment PBLK-5 was obtained.

PY-4: Nickel complex yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by LANXESS) PY-5: Quinoneone yellow pigment CI Pigment Yellow 138 ("K0961HD" manufactured by BASF Corporation) PY-6: Isoporphyrin yellow pigment CI Pigment Yellow 185 ("PalIotol Yellow L1155" manufactured by BASF Corporation) PBLK-1: Lanthanide black pigment ("Lumogen Black FK4281" manufactured by BASF Corporation) PBLK-6: Carbon system "#45" PBLK-7 manufactured by Mitsubishi Chemical Co., Ltd.: carbon black pigment "MA220" manufactured by Mitsubishi Chemical Corporation

<Method for Producing Acrylic Resin Solution> (Preparation of Acrylic Resin Solution 1) 70.0 parts of cyclohexanone was placed in a reaction vessel in which a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device were attached to a separable four-necked flask, and the temperature was raised. After the reaction vessel was purged with nitrogen at 80 ° C, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and isopropylidene were added dropwise over 2 hours using a burette. Phenylphenol ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) 7.4 parts, and a mixture of 2,2'-azobisisobutyronitrile 0.4 parts. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled, and the non-volatile component was measured by heating and drying at 180 ° C for 20 minutes, and propylene glycol monoethyl ether acetate was added to the previously synthesized resin solution so that the nonvolatile content became 20% by weight. Thus, an acrylic resin solution 1 was obtained.

(Preparation of Acrylic Resin Solution 2) 370 parts of cyclohexanone was placed in a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a burette, and a stirring device, and the temperature was raised to 80 ° C, and the inside of the flask was purged with nitrogen. Thereafter, 18 parts of p-cumylphenol oxirane modified acrylate ("AR0NIX M110" manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, and methyl group were added dropwise with a burette for 2 hours. A mixture of 18.2 parts of glycidyl acrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C for 1 hour. Next, the inside of the container was replaced with air replacement, and 9.3 parts of acrylic acid (100% of glycidyl group), 0.5 part of tris-dimethylaminophenol, and 0.1 part of hydroquinone were placed in the container, and the reaction was continued at 120 ° C for 6 hours. When the acid value of the solid component was 0.5, the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the produced hydroxyl group) and 0.5 part of triethylamine were further added, and the mixture was reacted at 120 ° C for 3.5 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 19,000. After cooling to room temperature, about 2 g of the resin solution was sampled, and the non-volatile component was measured by heating and drying at 180 ° C for 20 minutes, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20% by weight. An acrylic resin solution 2 as an active energy ray curable resin.

[Example 1] (Pigment Dispersion (D-1)) After the following mixture was stirred and mixed uniformly, zirconia beads having a diameter of 0.5 mm were used, and Eiger mill ("MINI MODEL M-250 MKII" manufactured by Eiger Japan Co., Ltd. was used. After dispersing for 3 hours, it was filtered with a 5.0 μm filter to prepare a pigment dispersion (DP-11).

Green pigment PG-1:10.0 parts

Acrylic resin solution 1: 35.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

Resin type dispersant solution C (dispersant C): 6.0 parts

[Examples 2 to 14, Comparative Examples 1 to 16]

In the following, the pigment dispersion (D-2 to 30) was prepared in the same manner as in the pigment dispersion (D-1), except that the pigment and the pigment derivative were changed to the compositions and the amounts shown in Tables 3 and 4.

<Evaluation of Pigment Dispersion>

The viscosity characteristics, contrast (CR) or optical density (OD) of the obtained pigment dispersion were evaluated by the following methods. The results are shown in Tables 5 and 6.

(viscosity characteristics)

The viscosity of the pigment dispersion was measured at 25 ° C using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.). Further, 25 g of the pigment dispersion was allowed to stand in a glass container at a temperature of 40 ° C for 7 days, and then the viscosity was measured by the same method as above to obtain the viscosity as a function of time. In addition, it is divided into three levels of evaluation according to the following criteria.

○: viscosity is less than 20mPa‧s

△: viscosity is 20mPa‧s or more and less than 40mPa‧s

×: viscosity is 40 mPa‧s or more

(contrast (CR))

The pigment dispersion (D-1 to 17) obtained by coating the number of revolutions was changed by a spin coater to a dry film thickness of about 1 μm to prepare a three-point coated substrate. After coating, the film was dried at 80 ° C for 30 minutes in a hot air oven, and each film thickness and contrast were measured, and the contrast (CR) at a film thickness of 1 μm was determined from the data of three points using a linear correlation method. In addition, it is divided into three levels of evaluation according to the following criteria.

○: CR is 8000 or more

△: CR is 6000 or more and less than 8000

×: CR does not reach 6000

(Optical Density (OD))

The obtained pigment dispersion was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, and then a coating film having a dried film thickness of 1.0 μm was formed, and heated at 230 ° C for 20 minutes. The optical density (OD) of the pigment dispersion-coated substrate obtained above was measured by a Macbeth concentration meter (GRETAG D200-II), and the optical density (OD) at a film thickness of 1.0 μm was determined.

Also. The OD is divided into three levels of evaluation according to the following criteria.

○: OD is 1.5 or more

△: OD is 1.3 or more and less than 1.5

×: OD is less than 1.3

The coloring composition for a color filter of the present invention contains a coloring agent and a resin-type dispersing agent, and the coloring agent contains a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of the pigment particles of 1:1 to 1:3.5. The resin type dispersant contains an acrylic block copolymer which is an AB block copolymer or BAB composed of a solvophilic A block and a B block having a functional group containing a nitrogen atom. In the block copolymer, and the amine value is from 10 mgKOH/g to 99 mgKOH/g in terms of the effective solid content, the coloring composition for a color filter of the present invention has good results of low viscosity, high stability, and high CR (Examples) 1 to 8).

Among them, the pigment dispersion (D-3) of Example 3 in which the metal salt of quinacridone skeleton sulfonic acid was further added to the pigment dispersion (D-1) of Example 1 was compared with Example 1, CR and viscosity. Better.

On the other hand, Comparative Example 1 in which the average primary particle diameter of the pigment particles was 15 nm was greatly increased in viscosity. In Comparative Example 2 in which the average primary particle diameter of the pigment particles was 95 nm, and in Comparative Example 3 in which the aspect ratio of the pigment particles was 1:4.5, the CR greatly deteriorated.

Further, the pigment dispersion (D-13) of Comparative Example 5 having an amine value of the resin-type dispersant of not more than 10 mgKOH/g and the pigment dispersion (D-12) of Comparative Example 4 of 99 mgKOH/g or more were highly viscous. In particular, the pigment dispersion (D-13) of Comparative Example 5 of less than 10 mgKOH/g had a low CR, and the pigment dispersion (D-14) of Comparative Example 6 using a random dispersant had a high viscosity.

The coloring composition for a color filter of the present invention contains a coloring agent and a resin-type dispersing agent, and the coloring agent contains a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of the pigment particles of 1:1 to 1:3.5. The resin type dispersant contains an acrylic block copolymer which is an AB block copolymer or BAB composed of a solvophilic A block and a B block having a functional group containing a nitrogen atom. In the block copolymer, and the amine value is from 10 mgKOH/g to 99 mgKOH/g in terms of the effective solid content, the coloring composition for a color filter of the present invention has good results of low viscosity, stability, and high OD (Examples) 9 to 14).

In particular, the pigment dispersion (D-20) of Example 11 in which the metal salt of quinacridone skeleton sulfonic acid was added to the pigment dispersion (D-18) of Example 9 was more excellent in viscosity.

On the other hand, the pigment dispersion (D-24) of Comparative Example 10 containing the pigment particles having an average primary particle diameter of 15 nm was greatly thickened. The OD of the pigment dispersion (D-25) of Comparative Example 11 containing the pigment particles having an average primary particle diameter of 100 nm was greatly deteriorated. The OD of the pigment dispersion (D-26) of Comparative Example 12 further containing the pigment particles having an aspect ratio of 1:4.0 was greatly deteriorated.

In addition, the pigment dispersion (D-28) of Comparative Example 14 having an amine value of less than 10 mgKOH/g of the resin type dispersant and the pigment dispersion (D-127) of Comparative Example 13 having a purity of 99 mgKOH/g or more become high. . In particular, the pigment dispersion (D-28) of Comparative Example 14 of less than 10 mgKOH/g had a low OD, and the pigment dispersion (D-29) of Comparative Example 15 using a random type of dispersant had a high viscosity.

[Example 15]

(Photosensitive coloring composition (R-1))

The mixture was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a photosensitive colored composition (R-1).

(Pigment dispersion) (50 total)

Pigment Dispersion 1: Pigment Dispersion (D-1): 30.0 parts

Pigment Dispersion 2: Pigment Dispersion (D-6): 20.0 parts

Acrylic resin solution 2: 10.6 parts

Trimethylolpropane triacrylate: 4.2 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)

Photopolymerization initiator ("IRGACURE 907" manufactured by Ciba Specialty Chemicals Co., Ltd.): 1.2 parts

Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts

Decane coupling agent ("KBM-803" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.4 parts

Ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 16 to 31, Comparative Examples 17 to 31]

(Photosensitive coloring composition (R-2 to 32))

A photosensitive coloring composition (R-2 to 32) was obtained in the same manner as the photosensitive coloring composition (R-1) except that the pigment dispersion was changed to the type and amount of the pigment dispersion shown in Tables 7 and 8. ). In the photosensitive coloring composition, the pigment dispersions 1 and 2 were used in combination, but the total amount of the pigment dispersion was 50 parts in the entire photosensitive coloring composition.

<Evaluation of photosensitive coloring composition>

The viscosity characteristics, contrast (CR), optical density (OD), and development speed of the obtained photosensitive colored composition were evaluated by the following methods. The results are shown in Tables 9 to 10.

(viscosity characteristics)

The viscosity of the photosensitive coloring composition was measured at an initial viscosity at 25 ° C using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.). Further, 25 g of the pigment dispersion was allowed to stand in a glass container for 7 days at 40 ° C, and then the viscosity was measured by the same method as above to obtain a viscosity with time.

○: Viscosity is less than 4.0mPa‧s

△: viscosity is 4.0 mPa‧s or more and less than 7.0 mPa‧s

×: viscosity is 7.0 mPa·s or more

(contrast (CR))

The photosensitive coloring composition (R-1 to 18) obtained by coating the number of revolutions was changed by a spin coater to a dry film thickness of about 2 μm to prepare a coated substrate of three points. After coating, the film was dried at 80 ° C for 30 minutes in a hot air oven, and each film thickness and contrast were measured, and the contrast (CR) at a film thickness of 1 μm was determined from the data of three points by a linear correlation method. In addition, it is divided into three levels of evaluation according to the following criteria.

○: CR is 8000 or more

△: CR is 6000 or more and less than 8000

×: CR does not reach 6000

(Optical Density (OD))

The obtained photosensitive coloring composition (R-19 to 32) was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, and then a coating film having a dried film thickness of 1.0 μm was formed, and heated at 230 ° C for 20 minutes. The optical density (OD) of the pigment dispersion-coated substrate obtained above was measured by a Macbeth concentration meter (GRETAG D200-II), and the optical density (OD) at a film thickness of 1.0 μm was determined.

Also. The OD is divided into three levels of evaluation according to the following criteria.

○: OD is 1.5 or more

△: OD is 1.3 or more and less than 1.5

×: OD is less than 1.3

(developing speed)

The photosensitive coloring composition was applied onto a 10 cm × 10 cm glass substrate by a spin coating method, and then heated at 70 ° C for 15 minutes in a clean oven to remove the solvent to obtain a coating film of about 2 μm. Next, the substrate was exposed to light at 60 mJ/cm ² through a mask pattern using a high-pressure mercury lamp, and then spray-developed at a pressure of 0.25 MPa using a 0.04 wt% potassium hydroxide aqueous solution (developing solution temperature of 26 ° C) to measure a colored coating. The time during which the film dissolves until the surface of the substrate is exposed (developing dissolution time). The development dissolution time of each photosensitive coloring composition was measured, and it was evaluated in three grades according to the following criteria.

○: less than 20 seconds

△: 20 seconds or more and less than 30 seconds

×: 30 seconds or more

The coloring composition for a color filter of the present invention contains a coloring agent and a resin-type dispersing agent, and the coloring agent contains a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of the pigment particles of 1:1 to 1:3.5. The resin type dispersant contains an acrylic block copolymer which is an AB block copolymer or BAB composed of a solvophilic A block and a B block having a functional group containing a nitrogen atom. In the block copolymer, and the amine value is 10 mgKOH/g or more and 99 mgKOH/g or less in terms of effective solid content, the coloring composition for a color filter of the present invention has low viscosity and stability, high CR, and fast development speed. Good results (Examples 15 to 19 and 23 to 24).

Among them, the photosensitive coloring composition (R-3) of Example 17 in which the metal salt of quinacridone skeleton sulfonic acid was further added to the photosensitive colored composition (R-1) of Example 15 had better CR and viscosity. And therefore for better results.

On the other hand, the photosensitive coloring composition (R-11) of Comparative Example 17 in which the average primary particle diameter of the pigment particles was 15 nm and 150 nm had a high initial viscosity and greatly increased in viscosity over time. On the other hand, the CR of the photosensitive coloring composition (R-12) of Comparative Example 18 in which the average primary particle diameter of the pigment particles was 95 nm and 150 nm was greatly deteriorated. Further, the CR of the photosensitive coloring composition (R-13) of Comparative Example 19 in which the aspect ratio of the pigment particles was 1:4.5 and 1:4.3 was greatly deteriorated.

As described above, neither of the comparative examples satisfies all of CR, viscosity, and development speed.

The coloring composition for a color filter of the present invention contains a coloring agent and a resin-type dispersing agent, and the coloring agent contains a pigment having an average primary particle diameter of 20 to 50 nm and an aspect ratio of the pigment particles of 1:1 to 1:3.5. The resin type dispersant contains an acrylic block copolymer which is an AB block copolymer or BAB composed of a solvophilic A block and a B block having a functional group containing a nitrogen atom. The block copolymer, and the amine value is 10 mgKOH/g or more and 99 mgKOH/g or less in terms of effective solid content, and the coloring composition for a color filter of the present invention has low viscosity and stability, high OD, and fast development speed. Good results (Examples 25 to 31).

Among them, the photosensitive coloring composition (R-21) of Example 27 in which the metal salt of quinacridone skeleton sulfonic acid was added to the photosensitive colored composition (R-19) of Example 25 had a better viscosity, and therefore Better results.

On the other hand, the photosensitive coloring composition (R-26) of Comparative Example 25 in which the average primary particle diameter of the pigment particles was 15 nm was greatly increased in viscosity. The OD of the photosensitive coloring composition (R-27) of Comparative Example 26 in which the average primary particle diameter of the pigment particles was 100 nm was greatly deteriorated. Further, the OD of the photosensitive coloring composition (R-28) of Comparative Example 27 in which the aspect ratio of the pigment particles was 1:4.0 was greatly deteriorated.

In addition, the photosensitive coloring composition (R-30) of Comparative Example 29 having an amine value of the resin-type dispersing agent of less than 10 mgKOH/g, and the photosensitive coloring composition (R-29) of Comparative Example 28 of 99 mgKOH/g or more High viscosity. Further, since the photosensitive coloring composition (R-29) of Comparative Example 28 had a high amine value, the development speed was slow. Further, the photosensitive coloring composition (R-31) of Comparative Example 30 using a random dispersing agent had a high viscosity.

<Manufacture of color filter>

First, 5.0 parts of the total of the green pigment and the yellow pigment in the photosensitive coloring composition (R-1) were replaced: the black photosensitive coloring composition 1 was replaced with 5.0 parts of the carbon black pigment (PBLK-7), and red. The photosensitive coloring composition 1 was replaced by CI Pigment Red 254/CI Pigment Red 177=3.0 parts/2.0 parts, and the green photosensitive coloring composition 1 was replaced by CI Pigment Green 58/CI Pigment Yellow 150=3.0 parts/2.0 parts. In the same manner as in the photosensitive coloring composition (R-1), a photosensitive coloring composition of each color was prepared in the same manner as in the case of the photosensitive coloring composition (R-1), and a black color was obtained. Photosensitive coloring composition 1, red photosensitive coloring composition 1, green photosensitive coloring composition 1, and blue photosensitive coloring composition 1.

[Manufacture of Color Filter 1]

A black photosensitive coloring composition 1 of about 1.0 μm thick was applied onto a 100 mm × 100 mm glass substrate by a squeeze coater, and dried in an oven at 70 ° C for 20 minutes to remove the solvent. Next, the stripe pattern exposure is performed using ultraviolet rays using an exposure device. The exposure amount was set to 100 mJ/cm ² . Further, the developer was subjected to spray development using a developing solution containing an aqueous solution of sodium carbonate, and the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a black matrix having a line width of about 10 μm.

Next, a red photosensitive coloring composition 1 having a thickness of about 2 μm was applied onto a glass substrate on which a black matrix was formed, and dried in an oven at 70 ° C for 20 minutes to remove the solvent. Next, the stripe pattern exposure is performed using ultraviolet rays using an exposure device. The exposure amount was set to 100 mJ/cm ² . Further, the developer was subjected to spray development using a developing solution containing an aqueous solution of sodium carbonate, and the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 30 minutes to form a red color filter segment having a line width of about 50 μm. Next, by the same operation, a green color filter segment is formed next to the red color filter segment using the photosensitive coloring composition (R-1), and then a blue color filter composition 1 is used to form a blue color filter region. In the segment, the color filter 1 having the three color filter segments on the same glass substrate was obtained.

[Manufacture of Color Filter 2]

A photosensitive colored composition (R-24) having a thickness of about 1.0 μm was applied onto a 100 mm × 100 mm glass substrate by a squeeze coater, and dried in an oven at 70 ° C for 20 minutes to remove the solvent. Next, the stripe pattern exposure is performed using ultraviolet rays using an exposure device. The exposure amount was set to 100 mJ/cm ² . Further, the developer was subjected to spray development using a developing solution containing an aqueous solution of sodium carbonate, and the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a black matrix having a line width of about 10 μm.

Next, a red photosensitive coloring composition 1 having a thickness of about 2 μm was applied onto a glass substrate on which a black matrix was formed, and dried in an oven at 70 ° C for 20 minutes to remove the solvent. Next, the stripe pattern exposure is performed using ultraviolet rays using an exposure device. The exposure amount was set to 100 mJ/cm ² . Further, the developer was subjected to spray development using a developing solution containing an aqueous solution of sodium carbonate, and the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 30 minutes to form a red color filter segment having a line width of about 50 μm. Then, by the same operation, a green color filter segment is formed by using the green photosensitive coloring composition 1 next to the red color filter segment, and then a blue color filter segment is formed using the blue photosensitive coloring composition 1, thereby A color filter 2 having a three-color filter segment on the same glass substrate was obtained.

Since at least one of the color filter segments and the black matrix formed of the coloring composition for a color filter of the present invention is provided in the color filters 1 and 2, it is possible to form a pattern in a short time without leaving a residue in the developing step. Further, since the contrast is high and the color reproduction area is wide, the liquid crystal display device using the color filter can exhibit a bright color with enhancement and weakness.

Further, although the color filter 2 of the present invention forms BM on the TFT, it has excellent electrical characteristics and no image sticking. Further, since the manufacturing process can be simplified, the liquid crystal display device using the color filter has a fast response speed, low cost, and can reproduce vivid colors.

Next, the second embodiment will be described using an embodiment and a comparative example.

First, the preparation of the acrylic resin used in the examples and the comparative examples, the physical property value of the fluorene-based black pigment, the structural formula of the pigment derivative, and the production of the black pigment dispersion will be described.

[Modulation of Acrylate Solution]

In a separable four-necked flask, 70.0 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and the temperature was raised to 80 ° C. After the inside of the reaction vessel was purged with nitrogen, the burette was used. Adding 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and isopropyl phenol phenol ethylene oxide modified acrylate (East Asia Synthetic Co., Ltd.) "ARONIX M110" manufactured by the company) 7.4 parts, a mixture of 2,2'-azobisisobutyronitrile 0.4 parts. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled, and the non-volatile component was measured by heating and drying at 180 ° C for 20 minutes, and methoxypropyl acetate was added in the previously synthesized resin solution so that the nonvolatile content became 30% by weight. The ester is prepared to prepare an acrylic resin solution.

[Physical properties of lanthanide black pigments]

Lanthanide black pigment 1’

"Lumogen Black FK4280" manufactured by BASF

Tethered black pigment 2'

Lanthanide black pigment C.I. Pigment Black 31 ("Paliogen Black S0084" manufactured by BASF Corporation),

Lanthanide black pigment 3'

Tantalum black pigment C. 1. Pigment black 32 ("Paliogen Black L0086" manufactured by BASF Corporation)

Lanthanide black pigment 4'

"Lumogen Black FK4281" manufactured by BASF, a black pigment

Lanthanide black pigment 5’

500 parts of a lanthanide black pigment CI Pigment Black 31 ("Paliogen Black S0084" by BASF Corporation), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.). The mixture was kneaded at 80 ° C for 5 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, I get a black pigment 5'.

Lanthanide black pigment 6’

500 parts of lanthanide black pigment ("Lumogen Black FK4281" manufactured by BASF Co., Ltd.), 2500 parts of sodium chloride and 250 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.) and mixed at 80 ° C. Refining for 5 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, I get a black pigment 6'.

Lanthanide black pigment 7’

500 parts of lanthanide black pigment ("Lumogen Black FK4281" manufactured by BASF Co., Ltd.), 2500 parts of sodium chloride and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel (manufactured by Inoue Co., Ltd.) and mixed at 40 ° C. Refining for 12 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, I get a black pigment 7'.

Lanthanide black pigment 8’

500 parts of a lanthanide black pigment CI Pigment Black 32 ("Paliogen Black L0086" by BASF Corporation), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.). The mixture was kneaded at 80 ° C for 12 hours. Next, the kneaded product was placed in 5 liters of warm water, and stirred while heating to 70 ° C for 1 hour to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One night, the lanthanide black pigment 8' of Table 1' was obtained.

[Structural formula of pigment derivative]

[Production of black pigment dispersion]

(black pigment dispersion 1')

After the mixture of the following composition was stirred and mixed uniformly, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("MINI MODEL M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then a filter of 5.0 μm was used. Filtration to produce a black pigment dispersion 1'.

Carbon black: 14.4 parts "#45" (Mitsubishi Chemical Co., Ltd.)

Pigment derivative 1': 0.6 parts

Resin type dispersant 1': 1.5 parts "BYK-110" (manufactured by BYK Chemical Japan Co., Ltd.)

(acid value is 53 mgKOH/g, non-volatile content is 52%)

Acrylic resin solution: 14.1 parts

Solvent: cyclohexanone: 69.4 parts

(black pigment dispersion 2' to 25')

Black pigment dispersions 2' to 25' were produced in the same manner as in the black pigment dispersion 1' except that the composition and the amount shown in Table 3' were changed.

The abbreviations and compounds in Table 3' are shown below.

‧pigment

R/B/Y pigment mixed color 1: black pigment mixed in a weight ratio of PR177/PB15:6/PY139=50/40/10

R/B/Y pigment mixed color 2: black pigment mixed in a weight ratio of PR179/PB15:6/PY185=50/40/10

‧Pigment derivatives

Derivatives 1' to 4': the pigment derivatives 1' to 4' shown in Table 2', respectively

Resin type dispersant

Resin type dispersant 1': Acid resin type dispersant "BYK-110" (manufactured by BYK Chemical Co., Ltd.) (acid value: 53 mgKOH/g, nonvolatile content: 52%)

Resin-type dispersant 2': an acidic resin type dispersant "BYK-111" (manufactured by BYK Chemical Co., Ltd.) (acid value: 129 mgKOH/g, nonvolatile content: 100%)

Resin type dispersant 3': Acid resin type dispersant "BYK-171" (manufactured by BYK Chemical Co., Ltd.) (acid value: 13 mgKOH/g, nonvolatile content: 40%)

Resin type dispersant 4: Basic resin type dispersant "BYK-6919" (manufactured by BYK Chemical Japan Co., Ltd.) (nonvolatile content is 60%)

Solvent: cyclohexanone

[Examples 1' to 22', comparisons 1' to 11']

(black resin composition 1' to 33')

The black pigment dispersion, the acrylic resin solution, and the solvent shown in Table 4' were stirred and mixed uniformly to prepare black resin compositions 1' to 33'.

The abbreviations and compounds in Table 4' are shown below.

Lanthanide pigment content (%): content of lanthanide pigment based on the total weight of the light-shielding black pigment (A) (%)

Solid component weight (%): solid content concentration in black resin composition Solvent: cyclohexanone

With respect to the obtained black resin composition, viscosity, optical density, film thickness, and light transmittance were measured by the following methods. The results are shown in Table 5.

[viscosity]

The viscosity of the black resin composition produced on the second day was measured at 25 ° C using a TVE-20L type viscometer (manufactured by Toki Sangyo Co., Ltd.) as an initial viscosity (η0: mPa ‧ s). Further, as the stability evaluation, the viscosity (η7: mPa‧s) after storage for 7 days at 40 ° C was measured in the same manner, and the rate of change was calculated according to the following formula.

Rate of change (%) = viscosity after 7 days of storage at 40 ° C (η7) / initial viscosity (η0) × 100

In addition, the rate of change with time is divided into three levels according to the following criteria.

○: The rate of change with time is less than 110%

△: The rate of change with time is 110% or more and less than 140%

×: The rate of change with time is 140% or more

[Optical density]

A black resin composition was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, and then a coating film having a dried film thickness of 1.0 μm was formed, and heated at 230 ° C for 20 minutes. The optical density (OD) of the black resin composition-coated substrate obtained above was measured by a Macbeth concentration meter (GRETAG D200-II), and the optical density (OD) at a film thickness of 1.0 μm was determined.

In addition, the OD is divided into three levels of evaluation according to the following criteria.

○: OD is 2.70 or more

△: OD is 2.50 or more and less than 2.70

×: OD is less than 2.50

[Light transmittance]

The black pigment dispersion was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, and then subjected to a baking step at 230 ° C for 20 minutes to prepare a coating film having a dry film thickness of 1.0 μm. The light transmittance of the obtained black pigment dispersion-coated substrate was measured with a spectrophotometer (HITACHI U.3900H), and the light transmittance was determined and classified into three levels according to the following criteria.

○: light transmittance (wavelength: 1000 nm) is 30% or more

△: light transmittance (wavelength of 1000 nm) is 15% or more and less than 30%

×: light transmittance (wavelength of 1000 nm) is less than 15%

In the light-shielding black pigment in the second embodiment, a black pigment dispersion containing a specific amount of an anthraquinone-based black pigment and carbon black is a dispersion excellent in fluidity and stability. In addition, by setting the content ratio of the lanthanoid black pigment in the light-shielding black pigment to 95% by weight or less, excellent light-shielding properties in which the optical density is also high are exhibited. In addition, the light transmittance at 780 nm also satisfies the required level of 15% or more in the mask alignment operation.

By using the pigment derivative as a pigment dispersant, the initial viscosity was lowered, the fluidity was improved, and stability with time was also observed (Examples 1' to 17', 19' to 25'). In addition, by using both the pigment derivative and the resin type dispersant, good stability with time is exhibited (Examples 1' to 5', 10' to 17', 20' to 25'), particularly using acidity In the case of the resin type dispersant, the fluidity is also better (Examples 1' to 5', 10', 11', 13' to 17', 20' to 25').

When the ratio of the lanthanoid black pigment in the light-shielding black pigment is small, the light transmittance in the near-infrared region is greatly deteriorated (Comparative Examples 1', 9' to 11'), and in many cases, the light-shielding property is poor (comparison) Example 2'). Further, when the lanthanoid black pigment does not satisfy any of the specific average particle diameter and the aspect ratio, the result is that the optical density becomes low, or the stability with time is deteriorated, or both occur simultaneously (Comparative Example 3' to 7').

Further, when the solid content concentration was 40% by weight, the viscosity was high and the fluidity suitable for coating was not obtained (Comparative Example 8').

When a combination of organic pigments was used as the coloring agent, the light transmittance in the near-infrared region and the stability with time were good, but the light-shielding property was poor (Comparative Examples 9', 10').

[Example 23']

(Photoresist material 1' (photosensitive black resin composition 1')) A mixture of the following composition was stirred and mixed uniformly, and then filtered with a filter of 1 μm to obtain a photoresist material 1' (photosensitive black resin composition 1) ').

Pigment dispersion 1': 12.00 parts

Pigment dispersion 3': 48.00 parts

Acrylic resin solution: 8.00 parts

Photopolymerization initiator 1': 0.04 parts "IRGACURE OXE-02" (manufactured by Ciba Japan Co., Ltd.)

Ethylene unsaturated compound: 2.00 parts "ARONIX M-402" (manufactured by Toagosei Co., Ltd.)

Surface conditioner: 1.00 part (a solution obtained by diluting "BYK-330" (manufactured by BYK Chemical Co., Ltd.) (produced by 50% by weight of non-volatile component) with 98 parts of propylene glycol monomethyl ether acetate)

Solvent: cyclohexanone: 30.60 parts

[Examples 24' to 29', Comparative Examples 12' to 20']

(Photoresist materials 2' to 16')

The photoresist materials 2' to 16' were produced in the same manner as the photoresist material 1' (photosensitive black resin composition 1') except for the composition and the amount of the composition shown in Table 6' (photosensitive black resin composition 2) 'to 16').

The abbreviations and compounds in Table 6' are shown below.

Photopolymerization initiator

Starting agent 1': "IRGACURE OXE-02" (manufactured by Ciba Japan)

Starting agent 2': a substance obtained by blending "IRGACURE 379EG" (manufactured by Ciba Japan Co., Ltd.) / "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.) at 90/10

Initiator 3: "IRGACURE 379EG" (manufactured by Ciba Japan Co., Ltd.) / "IRGACURE 907" (manufactured by Ciba Japan Co., Ltd.) / "DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) with 45/45/10 Substance

Ethylene unsaturated compound: "ARONIX M-402" (manufactured by Toagosei Co., Ltd.)

Surface conditioner: a solution obtained by diluting 2 parts of "BYK-330" (manufactured by BYK Chemical Co., Ltd.) (50% by weight of nonvolatile matter) with 98 parts of propylene glycol monomethyl ether acetate

Solvent: cyclohexanone

Regarding the obtained photoresist material, the optical density, the light transmittance, and the relative dielectric constant were measured by the following methods. The results are shown in Table 7'.

[Optical density]

The photoresist was coated on a 100 mm × 100 mm glass substrate by spin coating, and then vacuum dried. Thereafter, it was exposed to ultraviolet rays of 100 mJ/cm ² using an ultrahigh pressure mercury lamp. Next, the unexposed portion was spray-developed using an aqueous solution of sodium carbonate, and then washed with ion-exchanged water to remove the unexposed portion, and heated at 230 ° C for 20 minutes. Thus, a photoresist coated substrate having a film thickness of 1.0 μm was produced. The optical density (OD) of the substrate obtained above was measured by a Macbeth densitometer (GRETAG D200-II) to determine the optical density (OD) when the film thickness was 1.0 μm.

In addition, the OD is divided into three levels of evaluation according to the following criteria.

○: OD is 2.70 or more

△: OD is 2.50 or more and less than 2.70

×: OD is less than 2.50

[Light transmittance]

The photoresist was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, and then subjected to a baking step at 230 ° C for 20 minutes to prepare a coating film having a dry film thickness of 1.0 μm. The light transmittance of the obtained resist material-coated substrate was measured with a spectrophotometer (HITACHI U. 3900H), and the light transmittance was determined and classified into three levels according to the following criteria.

○: light transmittance (wavelength: 1000 nm) is 30% or more

△: light transmittance (wavelength of 1000 nm) is 15% or more and less than 30%

×: light transmittance (wavelength of 1000 nm) is less than 15%

[Relative permittivity]

The photosensitive black resin composition was applied at a constant number of revolutions on a 1.1 mm-thick glass substrate of 100 mm × 100 mm on which electrode aluminum was vapor-deposited using a spin coater so that the film thickness was 1.0 μm after the heating step described below. The thickness is obtained to thereby obtain a coated substrate. Subsequently, after drying under reduced pressure, ultraviolet light exposure was carried out using an ultrahigh pressure mercury lamp at a cumulative light amount of 100 mJ/cm ² and an illuminance of 25 mW/cm ² . After the coated substrate was heated at 230 ° C for 20 minutes and cooled, aluminum for the electrode of 3.464E to 4 m 2 was vapor-deposited on the obtained cured coating film, and a sample formed by sandwiching the cured coating film with an aluminum electrode was prepared. The relative dielectric constant of the obtained sample was measured using an impedance analyzer ("1260" impedance analyzer manufactured by Solartron Co., Ltd.) at an applied voltage of 100 mV. The relative dielectric constant was evaluated in three levels according to the following criteria.

○: The relative dielectric constant is 8.0 or less

△: The relative dielectric constant exceeds 8.0 and is 9.0 or less.

×: Relative dielectric constant exceeds 9.0

As shown in Table 7', when the fluorene-based black pigment is contained in an amount of from 78 to 95% by weight as a light-shielding black pigment, the optical density is 2.5 or more, and the light transmittance at 780 nm is also 15% or more. The electric constant is also 9.0 or less, and all satisfy the required characteristics of the BM provided in the TFT color display device of the BOA method.

When the ratio of the lanthanoid black pigment in the light-shielding black pigment is small, the relative dielectric constant and the light transmittance in the near-infrared region are greatly deteriorated (Comparative Example 12'), and in many cases, the light-shielding property is not satisfied ( Comparative Example 13').

Further, when the lanthanoid black pigment did not satisfy any of the specific average particle diameters and aspect ratios, the light-shielding property and the electrical property were both poor (Comparative Examples 14' to 18'). When a combination of organic pigments was used as the colorant (Comparative Examples 19' and 20'), the light transmittance and the relative dielectric constant in the near-infrared region were good, but the light-shielding property was poor.

As described above, the comparative examples could not all satisfy the light blocking property, the light transmittance, and the relative dielectric constant.

<Production of Color Liquid Crystal Display Device>

The color liquid crystal display device can be produced by a conventionally known method, for example, the method shown in JP-A-2000-162643.

It is produced by using a driving substrate of a thin film transistor (TFT) type color liquid crystal display device having a black matrix formed of the black resin composition according to the second embodiment.

First, a TFT and a transparent ITO electrode layer were patterned on the surface of the (first) glass substrate, and RGB color filters were formed thereon. An ITO film as a pixel electrode was formed on the color filter, and after etching into a predetermined pattern, a black matrix was formed between RGB pixels to fabricate an array substrate.

On the other hand, the ITO electrode layer was patterned on the surface of the other (second) glass substrate, and a polyimide polyimide alignment layer was formed thereon to fabricate a counter substrate.

The array substrate and the counter substrate prepared as described above are opposed to each other, and the electrode layers are opposed to each other, and the distance between the two substrates is kept constant while the spacers are used, and the liquid crystal composition is injected into the opening portion to seal the periphery with the sealant. . After the liquid crystal composition is injected from the opening, the opening is sealed. The liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to fabricate a color display device.

As a result, the color display device including the driving substrate of the thin film transistor (TFT) type color liquid crystal display device including the black matrix formed of the black resin composition of the present invention is excellent in light blocking property, and thus the color liquid crystal display device is excellent. The display contrast is excellent, and due to the low dielectric constant characteristics, the adverse effect on the electrical characteristics such as alignment disorder of the liquid crystal is small, and since the light transmittance in the near-infrared region is excellent, the mask alignment operation can be performed. .

Next, the third embodiment will be described with reference to examples and comparative examples.

[Modulation of Acrylic Resin]

800.0 parts of cyclohexanone was placed in a reaction vessel, nitrogen gas was injected into the vessel and heated to 100 ° C, and 60.0 parts of methacrylic acid, 65.0 parts of butyl methacrylate, and methyl methacrylate 65.0 were added dropwise at the same temperature for 1 hour. a mixture of 60.0 parts of styrene and 10.0 parts of azobisisobutyronitrile, and further reacted at 100 ° C for 3 hours, and then added a solution obtained by dissolving 2.0 parts of azobisisobutyronitrile in 50.0 parts of cyclohexanone, and further at 100 The reaction was continued for 1 hour at ° C to synthesize a resin solution. After cooling to room temperature, about 2.0 g of the resin solution was sampled, and the non-volatile component was measured by heating and drying at 180 ° C for 20 minutes, and cyclohexanone was added in the previously synthesized resin solution so that the nonvolatile content became 20% by weight. The acrylic resin solution was prepared. Further, the weight average molecular weight of the acrylic resin solution was 40,000.

[苝 black pigment]

The same lanthanide black pigment as the lanthanide black pigments 1' to 8' shown in Table 1' was prepared.

[Structural formula of pigment derivative]

The same pigment derivatives as those of the pigment derivatives 1' to 4' shown in Table 2' were prepared.

[Example 1"]

After the mixture of the following composition was stirred and mixed uniformly, zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("MINI MODEL M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then a filter of 5.0 μm was used. Filtration was carried out to prepare a black resin composition (black pigment dispersion 1").

Lanthanide black pigment 1': 6.5 parts

Pigment derivative 1': 0.7 parts

Resin type dispersant 1': 1.4 parts "BYK-110" manufactured by BYK Chemical Japan Co., Ltd. (acid value: 53 mgKOH/g)

Acrylic resin solution: 33.6 parts

Solvent: cyclohexanone: 57.8 parts

[Example 2" to 13", Comparative Example 1", 2", 4" to 9"]

Black pigment dispersions 2" to 13", 15" to 122" were produced in the same manner as in Example 1" (black pigment dispersion 1") except that the composition and the amount shown in Table 3 were changed.

The abbreviations and compounds in Table 3" are the same as those described in Table 3'.

[Comparative Example 3"]

The mixture was stirred and mixed uniformly, and then zirconia beads having a diameter of 0.5 mm were used, and dispersed by an Eiger mill ("MINI MODEL M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then filtered through a 5.0 μm filter. Thus, a black pigment dispersion 14" was produced.

Carbon black (Mitsubishi Chemical Co., Ltd. #45): 6.5 parts

Pigment derivative 1': 0.7 parts

Acrylic resin solution: 33.6 parts

Resin type dispersant 1': 1.4 parts "BYK-110" manufactured by BYK Chemical Japan Co., Ltd. (acid value: 53 mgKOH/g)

Solvent: cyclohexanone: 57.8 parts

[Viscosity Evaluation and Rate of Change of Black Pigment Dispersion]

In the viscosity of the black pigment dispersion, the viscosity at a rotation number of 20 rpm was measured using an E-type viscometer (TVE-20L type viscometer (manufactured by Toki Sangyo Co., Ltd.) at 25 ° C on the day of preparation of the pigment dispersion (initial) Viscosity).

Then, for the black pigment dispersion which was left at 40 ° C for 7 days from the day of preparation of the black pigment dispersion, the sample temperature was returned to 25 ° C, and the viscosity with time was measured according to the above viscosity measurement method. The equation is used to find the rate of change over time.

Rate of change with time (%) = (viscosity with time) / (initial viscosity) × 100

In addition, the rate of change with time was evaluated in three levels according to the following criteria.

The results are shown in Table 4".

○: The rate of change with time is less than 110%

△: The rate of change with time is 110% or more and less than 140%

×: The rate of change with time is 140% or more

[Optical density]

The black pigment dispersion was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, dried under vacuum, and heated at 230 ° C for 20 minutes. Thus, a black pigment dispersion-coated substrate having a film thickness of 1.0 μm was produced. The optical density (OD) of the substrate was measured with a Macbeth densitometer (GRETAG D200-II) to determine the optical density (OD) when the film thickness was 1.0 μm.

The results are shown in Table 4".

[penetration rate]

The black pigment dispersion was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, and then subjected to a baking step at 230 ° C for 20 minutes to prepare a coating film having a dry film thickness of 1.0 μm. The transmittance of the obtained black pigment dispersion-coated substrate was measured with a spectrophotometer (HITACHI U-3900H), and the transmittance was determined and classified into three levels according to the following criteria.

The results are shown in Table 4".

○: The transmittance (wavelength: 1000 nm) is 80% or more

△: the transmittance (wavelength of 1000 nm) is 60% or more and less than 80%

×: The transmittance (wavelength of 1000 nm) is less than 60%

Table 4"

The light-shielding black pigment which is a feature of the present invention has a fluidity of a black pigment dispersion composed of an oxime-based black pigment having an average primary particle diameter of 50 nm or less and a specific aspect ratio of pigment particles, a pigment dispersant, a resin, and a solvent. It is excellent in stability, high in OD value, exhibits good light-shielding property, and excellent in transmittance (Examples 1" to 13").

In addition, by using both the pigment derivative and the resin type dispersant, good stability with time is exhibited (Examples 1" to 4", 9" to 13"), in particular, when an acidic resin type dispersant is used. It is even better (Examples 1 to 4", 9", 10", 12", 13").

[Example 14"]

(Photoresist material 1")

Then, the mixture of the following composition was stirred and mixed uniformly, and then filtered using a 1 μm filter to obtain a photosensitive black resin composition (photoresist 1).

Black pigment dispersion 1": 48.0 parts

Acrylic resin solution: 17.2 parts

Photopolymerization initiator: 0.4 parts ("IRGACURE OXE-02" manufactured by Ciba Japan)

Ethylene unsaturated compound: 2.9 parts ("ARONIX M-402" manufactured by Toagosei Co., Ltd.)

Surface conditioner: 1.0 part (a solution obtained by diluting 2 parts of "BYK-330" (50% by weight of non-volatile component) manufactured by BYK Chemical Co., Ltd. with 98 parts of propylene glycol monomethyl ether acetate)

Solvent: cyclohexanone: 30.5 parts

[Examples 15" to 26", Comparative Examples 10" to 18"]

[Photoresist material 2" to 22"]

The photoresist materials 2" to 22" were produced in the same manner as in Example 14" (photo resist material 1) except that the black pigment dispersion shown in Table 5" was changed.

[Optical density]

After applying a photoresist material on a 100 mm × 100 mm glass substrate by a spin coating method, vacuum drying was performed, and then ultraviolet rays of 100 mJ/cm ² were exposed using an ultrahigh pressure mercury lamp. Next, the unexposed portion was spray-developed using an aqueous solution of sodium carbonate, and then washed with ion-exchanged water to remove the unexposed portion, and heated at 230 ° C for 20 minutes to prepare a resist material-coated substrate having a film thickness of 1.0 μm. The optical density (OD) of the substrate thus obtained was measured by a Macbeth densitometer (GRETAG D200-II) to determine the optical density (OD) when the film thickness was 1.0 μm.

The results are shown in Table 5".

[penetration rate]

The photoresist was applied onto a 100 mm × 100 mm glass substrate by a spin coating method, and then subjected to a baking step at 230 ° C for 20 minutes to prepare a coating film having a dry film thickness of 1.0 μm. The transmittance of the obtained resist material-coated substrate was measured with a spectrophotometer (HITACHI U. 3900H), and the transmittance was determined and classified into three levels according to the following criteria.

The results are shown in Table 5".

○: The transmittance (wavelength: 1000 nm) is 80% or more

△: the transmittance (wavelength of 1000 nm) is 60% or more and less than 80%

×: The transmittance (wavelength of 1000 nm) is less than 60%

[relative dielectric constant, tan δ (dielectric loss tangent)]

The photosensitive black resin composition was applied to a 1.1 mm-thick glass substrate of 100 mm × 100 mm on which electrode aluminum was vapor-deposited by a spin coater at a constant number of revolutions so that the film thickness after the following heating step was 1.0 μm. The thickness is obtained to thereby obtain a coated substrate. Subsequently, after drying under reduced pressure, ultraviolet light exposure was carried out using an ultrahigh pressure mercury lamp at a cumulative light amount of 100 mJ/cm ² and an illuminance of 25 mW/cm ² .

After the coated substrate was heated at 230 ° C for 20 minutes and cooled, aluminum for electrodes of 3.464E to 4 m ² was vapor-deposited on the obtained cured coating film, and a sample obtained by sandwiching the cured coating film with an aluminum electrode was prepared. The relative dielectric constant and tan δ of the obtained sample were measured using an impedance analyzer ("1260 type" impedance analyzer manufactured by Solartron Co., Ltd.) at an applied voltage of 100 mV. The relative dielectric constant was evaluated in three levels according to the following criteria.

○: Relative dielectric constant is less than 3.5

△: The relative dielectric constant is 3.5 or more and 4.5 or less.

×: Relative dielectric constant exceeds 4.5

Tan δ was evaluated in three levels according to the following criteria.

○: tan δ is less than 0.1

△: tan δ is 0.1 or more and less than 0.2

×: tan δ is 0.2 or more

The results are shown in Table 5".

As shown in Table 5", a lanthanide black pigment, a pigment dispersant, a resin, and a solvent having crystal particles having an average primary particle diameter of 50 nm or less and an aspect ratio of 1:1 to 1:2 were used as the light-shielding black pigment. As a result of the photoresist material according to the third embodiment, the optical density is high, the light-shielding property is excellent, the dielectric constant is low, and the transmittance in the near-infrared region is also excellent (Examples 14 to 26"). When the bismuth-based pigment does not satisfy any of the specific average particle diameters and aspect ratios, the results are as follows: not only the optical density is low, the light-shielding property is poor, and the electrical properties are also poor (Comparative Examples 13" to 17").

Among them, a photoresist material using a pigment skeleton having a matrix of an organic pigment and a pigment derivative of a basic substituent as a pigment dispersant exhibits more excellent electrical properties (Example 24"), and the parent skeleton of the organic pigment is two. The tan δ of the photoresist material of the diketopyrrolopyrrole also becomes more excellent (Example 19", 21" to 23").

In addition, the tan δ of the photoresist material using the pigment derivative and the acidic resin type dispersant having an acid value of 100 to 200 mg KOH/g is more excellent, the initial viscosity can be suppressed to a low level, and the stability is also good ( Example 22").

Further, Comparative Examples 10" and 11" (photoresist materials 12" and 13") in which a black resin composition was formed by mixing organic pigments as a light-shielding black pigment, the relative dielectric constant and the transmittance were practical. Horizontal, but the optical density was low, and Comparative Example 12" (Photoresist Material 14) using carbon black showed excellent optical density but very poor transmittance in the relative dielectric constant and the near-infrared region.

Further, in the case of Comparative Examples 13" to 17" (photoresist materials 15" to 19") in which the lanthanoid black pigment did not satisfy any of the specific average particle diameter and aspect ratio, the result was that not only the optical density was low, Poor opacity and poor electrical properties.

As described above, none of the comparative examples satisfies all of the relative dielectric constant, the transmittance, and the light blocking property.

<Production of Color Liquid Crystal Display Device>

The color liquid crystal display device can be produced by a conventionally known method, for example, the method shown in JP-A-2000-162643.

It is produced by using a driving substrate of a thin film transistor (TFT) type color liquid crystal display device having a black matrix formed of the black resin composition according to the third embodiment.

First, a TFT and a transparent ITO electrode layer were patterned on the surface of the (first) glass substrate, and RGB color filters were formed thereon. An ITO film as a pixel electrode was formed on the color filter, and after etching into a predetermined pattern, a black matrix was formed between RGB pixels to fabricate an array substrate.

On the other hand, a transparent ITO electrode layer was patterned on the surface of the other (second) glass substrate, and a polyimide polyimide alignment layer was formed thereon to fabricate a counter substrate.

The array substrate and the counter substrate prepared as described above are disposed to face each other, and the electrode layers are opposed to each other, and the distance between the two substrates is kept constant while using the spacer beads, and the liquid crystal composition injection opening is sealed with a sealant. around. After the liquid crystal composition is injected from the opening, the opening is sealed. The liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to fabricate a color display device.

As a result, the color display device including the driving substrate of the thin film transistor (TFT) color display device including the black matrix formed of the black resin composition of the present invention is excellent in light blocking property, and thus the display contrast of the color display device is high. It is excellent, and because of its low dielectric constant characteristics, it has little adverse effect on the electrical characteristics of the alignment disorder of the liquid crystal, and since the transmittance in the near-infrared region is excellent, the mask alignment operation can be performed.

Claims (29)

A coloring composition for a color filter, characterized by a coloring composition for a color filter containing a coloring agent, a resin type dispersing agent, and a solvent, wherein the coloring agent contains an average primary particle diameter of 20 to 50 nm and a length and width of the pigment particles. a pigment having a ratio of 1:1 to 1:3.5, the above-mentioned resin type dispersant containing an acrylic block copolymer which is composed of a solvophilic A block and a functional group having a nitrogen atom The AB block copolymer or the BAB block copolymer composed of the B block, and the amine value is 10 mgKOH/g or more and 99 mgKOH/g or less in terms of effective solid content. The coloring composition for a color filter according to the first aspect of the invention, wherein the acrylic block copolymer contains 5 to 40 mol% of the following formula in the A-block having solvophilicity ( The repeating unit represented by I) contains a repeating unit represented by the following formula (II) in a B block having a functional group containing a nitrogen atom, [In the formula (I), n represents an integer of 1 to 5, and R ₁ represents a hydrogen atom or a methyl group], [In the general formula (II), R ₄ and R ₅ each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent, R ₃ It represents an alkylene group having 1 or more carbon atoms, and R ₂ represents a hydrogen atom or a methyl group]. The coloring composition for color filters according to claim 2, wherein the acrylic block copolymer further contains a formula of 50 to 90 mol% in the A block having solvophilicity ( A component other than the constituent unit represented by I) is a (meth)acrylate monomer as a precursor. The colored composition for a color filter according to claim 1, wherein the coloring agent is a perylene black pigment. The colored composition for a color filter according to claim 1, wherein the acid derivative of the organic pigment or a metal derivative thereof is further contained. The coloring composition for a color filter according to claim 1, wherein the photopolymerizable monomer and the photopolymerization initiator are further contained. A color filter comprising a color filter segment and/or a black matrix formed of the coloring composition for a color filter according to any one of claims 1 to 6 on the substrate. A black resin composition comprising a light-blocking black pigment, a resin, and a solvent, wherein the light-shielding black pigment has an average primary particle diameter of 50 nm or less and an aspect ratio of the pigment primary particles of 1:1 to 1:2. The lanthanide black pigment and the carbon black are contained, and the content of the lanthanoid black pigment is 78 to 95% by weight based on the total amount of the light-shielding black pigment, and the solid content concentration is 5% by weight or more and less than 40% by weight. %. The black resin composition according to claim 8, wherein the lanthanide black pigment has an average primary particle diameter of 20 to 45 nm. The black resin composition according to claim 8, wherein the pigment dispersant is further contained. The black resin composition according to claim 10, wherein the pigment dispersant comprises a pigment derivative having a matrix skeleton of an organic pigment and a basic substituent. The black resin composition according to claim 10, wherein the pigment dispersant further comprises an acidic resin type dispersant. The black resin composition according to claim 8, wherein the ethylenically unsaturated compound and the photopolymerization initiator are further contained. A black matrix formed by the black resin composition described in claim 8 of the patent application. The black matrix according to claim 14, wherein the relative dielectric constant when the dry film thickness is 1.0 μm is 8.0 or less. The black matrix according to claim 14, wherein the light transmittance at a wavelength of 780 nm when the film thickness is 1.0 μm is 15% or more and less than 99%. The black matrix according to claim 14, wherein the optical density when the dry film thickness is 1.0 μm is 2.50 or more. A substrate for driving a thin film transistor type color liquid crystal display device, comprising the black matrix according to any one of claims 14 to 17. A black resin composition comprising a light-blocking black pigment, a pigment dispersant, a resin, and a solvent, wherein the light-shielding black pigment has an average primary particle diameter of 50 nm or less and an aspect ratio of the pigment particles of 1:1 to 1 : 2 is a black pigment. The black resin composition according to claim 19, wherein the lanthanide black pigment has an average primary particle diameter of 20 to 45 nm. The black resin composition according to claim 19, wherein the pigment dispersant is a pigment derivative having a matrix skeleton of an organic pigment and a basic substituent. The black resin composition according to claim 21, wherein the parent skeleton of the organic pigment is two (dioxazine) is any one of a pigment or a diketo pyrrolopyrrole pigment. The black resin composition according to claim 21, wherein the pigment dispersant further comprises a resin type dispersant. The black resin composition according to claim 19, which further comprises an ethylenically unsaturated compound and a photopolymerization initiator. A black matrix formed by the black resin composition described in claim 19 of the patent application. The black matrix according to claim 25, wherein the relative dielectric constant when the dry film thickness is 1.0 μm is 4.5 or less. The black matrix according to claim 25, wherein a transmittance of a wavelength of 1000 nm when the film thickness is 1.0 μm is 60% or more and less than 99%. The black matrix according to claim 25, wherein the optical density when the dry film thickness is 1.0 μm is 1.30 or more. A substrate for driving a thin film transistor (TFT) type color liquid crystal display device, comprising the black matrix according to any one of claims 25 to 28.