KR101859710B1 - Coloring composition for color filter and color filter - Google Patents

Abstract

One embodiment is a colored composition for a color filter containing a colorant, a resinous dispersant and a solvent, wherein the colorant has an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: 1 to 1: 3.5 Wherein the resinous dispersant is an AB block copolymer or a BAB block copolymer which is a B block having a hydrophilic A block and a functional group containing a nitrogen atom and the amine value is in the form of an effective solid content By weight of an acrylic block copolymer having an acid value of 10 mgKOH / g or more and 99 mgKOH / g or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring composition and a color filter for a color filter,

The present invention relates to a color filter for a color filter, a color filter having a filter segment and / or a black matrix, a black resin composition, a black matrix and a substrate for driving a thin film transistor (TFT) system color liquid crystal display .

A liquid crystal display device is a display device in which a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light passing through the first polarizing plate and controls the amount of light passing through the second polarizing plate , Twisted nematic (TN) type liquid crystals are used. Other typical liquid crystal display devices include an in-plane switching (IPS) system in which a pair of electrodes are provided on a substrate on one side and an electric field is applied in a direction parallel to the substrate, a nematic liquid crystal having negative dielectric anisotropy Vertical alignment (VA) system in which the liquid crystal molecules are vertically aligned, and Optical Reinbenefent Bend (OCB) system in which optical axes of the uniaxial retardation film are crossed with each other to perform optical compensation, and these systems are put to practical use .

In the liquid crystal display device, color display can be achieved by providing a color filter between two polarizing plates. Recently, since the liquid crystal display device is used in a TV monitor or a PC monitor, the demand for high contrast and high definition of color filters is increasing.

The color filter is formed by arranging filter segments in the form of fine stripes in two or more different colors on the surface of a transparent substrate such as glass in parallel or at an intersection or by arranging fine filter segments in a vertical and horizontal arrangement . The filter segments are fine, from several microns to several hundred microns, and are evenly arranged in a predetermined arrangement for each color.

In general, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and further an alignment film for orienting the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of such a transparent electrode and an orientation film, it is generally necessary to carry out the formation at a high temperature of 200 DEG C or higher, preferably 230 DEG C or higher. For this reason, at present, as a method of producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a coloring agent has become mainstream.

However, in general, a color filter in which a pigment is dispersed has a problem in that the degree of polarization controlled by the liquid crystal is disturbed by scattering of light by the pigment or the like. That is, since the transmitted light is attenuated when the light is to be blocked (OFF state) or when the light must be transmitted (ON state), the brightness of the light on the display in the ON state and the OFF state There is a problem that the ratio (contrast ratio) is low.

In order to realize high brightness and high contrast of a color filter, pigments contained in filter segments are often used by being refined. However, it is also possible to use a pigment (a mixture of a primary particle and a secondary particle aggregated by pigmentation treatment, which is referred to as a chrome having a particle diameter of 10 to 100 mu m produced by a chemical reaction, Even if the pigment is finely dispersed, the pigment in which the primary particles or the secondary particles are finely fined generally tends to flocculate, and when the fining proceeds too much, a large massive pigment solid is formed. In addition, it is very difficult to obtain a stable coloring composition even if the finely dispersed pigment is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are approached to stabilize as close as possible to the primary particles.

A coloring composition for a color filter formed by dispersing a pigment subjected to micronization treatment in a pigment carrier containing a resin or the like is problematic in that it is difficult to stably disperse the pigment in a high concentration and various problems It is known to cause.

For example, a pigment composition containing a pigment consisting of fine particles sometimes exhibits a high viscosity, which makes it difficult to obtain and transport the product from the dispersing device, and in the worst case, it causes gelation in the preservation, . Furthermore, the surface of the full-color coat of the pigment composition causes a defective state such as deterioration of gloss, leveling failure and the like. Further, when a mixture of different kinds of pigments is used, color unevenness or a marked decrease in tinting strength may appear in the full-color clothing due to color distinction due to agglomeration or development such as sedimentation.

Generally, a resinous dispersant is used in order to maintain a good dispersion state. The resinous dispersant has a structure in which a portion adsorbed to the pigment and a portion having a high affinity with a solvent that is a dispersion medium are combined, and the performance is determined by the balance of these two functional sites. As the resinous dispersant, various ones are used in accordance with the surface state of the pigment as a dispersion product.

The resinous dispersant is known to have excellent pigment dispersibility because of its structure having a block structure (Patent Document 1) or a comb structure (Patent Document 2). In either case, since the fineness of the pigment has recently progressed and the surface area has increased, a large amount of the pigment tends to be added to secure dispersion stability. There is a case in which the solubility in the developing solution is poor due to the increase in the amount of the dispersing agent, the solubility in the developing solution of the dispersing agent itself is poor and the developing can not be performed within a predetermined time, May easily remain. Furthermore, when the uncoloured resin composition remains in the non-fired portion on the substrate, the obtained color filter causes a decrease in transmittance and contrast. In addition, if the color filter remains in the pattern edge portion, Such as the occurrence of deterioration in sealing performance in the post-processing.

In the case of a comb structure, a portion of a comb having a functional group such as a carboxyl group or an acryloyl group in a polyamine compound having a primary or secondary amino group is grafted, and the remaining primary or secondary amine is adsorbed on the pigment surface Functional group, but primary or secondary amines are not preferable because of active hydrogen having high reactivity.

Regarding the color filter, not only high contrast but also high definition are required as described above. Generally, in order to obtain a high brightness, a high brightness is obtained by increasing the permeability of the dispersion by approaching the primary particles when the pigment is dispersed in the pigment carrier, and by making the spectral spectrum of the dispersion have a high transmittance.

In order to solve such a problem, attempts have been made to improve the structure and acid value of the acrylic block copolymer and improve the pigment dispersibility by adding a small amount thereof (see Patent Documents 3, 4 and 5).

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

The black matrix is required to have excellent light shielding property in order to make the image quality of the liquid crystal display excellent.

In order to cope with higher precision and higher brightness, there has been recently proposed a method of forming a black matrix on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, a method of forming a black matrix on a color filter substrate, BOA (Black Matrix on Array) method has been studied. In this BOA method, the bonding process as in the past for alignment with the device is not required, and the pixel aperture ratio (aperture ratio) can be greatly increased, which makes it possible to shorten the manufacturing process, Since the cost can be reduced, there are many advantages over the BM formed on the color filter substrate.

Since these BMs also require a high light shielding property, dispersion stability at a high pigment concentration is required, and a high resolution is also required to be imparted at the same time. Even in the case of a coloring composition for a black matrix, as in the case of a color resist, since the addition amount of the dispersing agent tends to increase in order to obtain dispersion stability, if the solubility in a developing solution is poor, the phenomenon can not occur within a predetermined time, There is a problem that the uncolored resin composition remains on the non-image portion after development of the water-repellent surface.

When 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, if the permittivity of the BM itself is high, display failure of the liquid crystal display is caused. In addition, since mask alignment performed at the time of BM formation is performed by using an infrared camera, a light transmittance in a near-infrared region of a certain level is also required. Therefore, carbon black, which has been mainly used as a BM material in the prior art, exhibits a high dielectric constant and is not only insufficient in insulation but also has a low light transmittance in the near infrared region, making it difficult to carry out alignment. It is difficult.

As a method for solving such a problem, there are a method of combining carbon black and at least one organic pigment (see Patent Document 6), a method of providing light shielding only by the combination of organic pigments without using carbon black (Patent Document 7 (Refer to Patent Documents 9 to 11), and the like. However, the method of using the black matrix as a light shielding property, the electric characteristic, and the mask alignment operation It is not possible to satisfy both of the sufficient light transmittance of the near infrared region for the light-receiving layer.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-31713 [Patent Document 2] JP-A-11-1515 [Patent Document 3] JP-A-2006-265528 [Patent Document 4] JP-A-2006-321979 [Patent Document 5] JP-A-2009-25813 [Patent Document 6] Japanese Patent Application Laid-Open No. 2005-215150 [Patent Document 7] JP-A-2009-069822 [Patent Document 8] JP-A-2009-282251 [Patent Document 9] JP-A-6-289602 [Patent Document 10] JP-A-4-190362 [Patent Document 11] JP-A-10-219167

In the first embodiment, a coloring composition for a color filter excellent in dispersibility, good flowability and stability, and excellent in developing property and a filter segment having a high contrast ratio using a coloring composition for the color filter or a black It is an object of the present invention to provide a high-quality color filter having a matrix.

In the second embodiment, a black resin composition excellent in fluidity and stability for producing a black matrix and a black matrix excellent in light transmittance, electrical characteristics and light transmittance in a near infrared region using the black resin composition, particularly thin film transistor (TFT) It is an object of the present invention to provide a black matrix for use in a substrate for driving a display device.

In the third embodiment, a black matrix used for a substrate for driving a black matrix, in particular, a thin film transistor (TFT) type color liquid crystal display device having excellent light shielding properties, electrical characteristics and near infrared region transmittance, It is an object of the present invention to provide a black resin composition excellent in fluidity and stability.

The inventors of the present invention have conducted intensive studies to solve the above problems and as a result have found that a colorant containing 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 an AB block copolymer or a BAB block copolymer composed of a B block having a functional group containing a nitrogen atom and an amine value of not less than 10 mgKOH / g and not more than 99 mgKOH / g in terms of effective solid content And that the above coalescence is used as a resinous dispersant to solve the above problems.

That is, the first embodiment is a colored composition for a color filter containing a colorant, a resinous dispersant and a solvent, wherein the colorant has an average primary particle diameter of 20 to 50 nm and an aspect ratio of pigment particles of 1: To 1: 3.5, wherein the resinous dispersant is an AB block copolymer or a BAB block copolymer comprising a B block having a hydrophilic A block and a functional group containing a nitrogen atom, And an acrylic block copolymer having an effective solid content of 10 mgKOH / g or more and 99 mgKOH / g or less.

Wherein the acrylic block copolymer contains in the A block having a hydrophilic property a B block having a functional group containing a nitrogen atom and containing 5 to 40 mol% of a repeating unit represented by the following general formula (I) as described below, May contain a repeating unit represented by the general formula (II).

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

[In the formula (II), R ₄ and R ₅ independently represent a cyclic or straight-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, and R ₃ Represents an alkylene group having at least 1 carbon atom, and R ₂ represents a hydrogen atom or a methyl group.

The acrylic block copolymer may further contain 50 to 90 moles of a constituent unit having a (meth) acrylic acid ester monomer other than the structural unit represented by the general formula (I) as a precursor in the A block having a hydrophilic property %.

The colorant may be a perylene-based black pigment.

The composition may further contain an acid derivative of an organic pigment or a pigment derivative which is a metal salt thereof.

The composition may further contain a photopolymerizable monomer and a photopolymerization initiator.

The first embodiment relates to a color filter comprising a substrate and a filter segment formed from the coloring composition for the color filter and / or a black matrix.

The second embodiment is a black resin composition comprising a light-blocking black pigment, a resin and a solvent, wherein the light-blocking black pigment has an average primary particle diameter of 50 nm or less and an aspect ratio of primary particles of 1: 1 to 1: Based black pigment and carbon black, wherein the content of the perylene black pigment is 78 to 95% by weight based on the total amount of the light-blocking black pigment (A), and the solid content concentration is 5 to 40% By weight based on the total weight of the black resin composition.

The average primary particle size of the perylene black pigment may be 20 to 45 nm.

The composition may further comprise a pigment dispersant.

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

The pigment dispersant may further comprise an acidic resin type dispersant.

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

The second embodiment relates to a black matrix formed from the black resin composition.

The black matrix may have a relative dielectric constant of 8.0 or less at a dry film thickness of 1.0 占 퐉.

The black matrix may have a light transmittance at a wavelength of 780 nm at a dry film thickness of 1.0 占 퐉 of 15% or more and less than 99%.

The black matrix may have an optical density of 2.50 or more at a dry film thickness of 1.0 占 퐉.

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

The third embodiment is a black resin composition comprising a light-blocking black pigment, a pigment dispersant, a resin and a solvent, wherein the light-blocking black pigment has an average primary particle diameter of 50 nm or less and an aspect ratio of pigment particles of 1: 1 to 1: 2, based on the total weight of the black resin composition.

The average primary particle diameter of the perylene black pigment may be 20 to 45 nm.

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

The matrix skeleton of the organic pigment may be either a dioxazine-based pigment or a diketopyrrolopyrrole-based pigment.

The pigment dispersant may further comprise a resinous dispersant.

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

The third embodiment relates to a black matrix formed from the black resin composition.

The black matrix may have a relative dielectric constant of 4.5 or less at a dry film thickness of 1.0 占 퐉.

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

The black matrix may have an optical density at a dry film thickness of 1.0 占 퐉 of 1.30 or more.

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

The coloring composition for a color filter according to the first embodiment is a stable coloring composition for a color filter which is excellent in flowability and developability and can be obtained by using the coloring composition for a color filter, A black matrix pattern with high optical density can be formed. Therefore, by using the coloring composition for this color filter, a high-quality color filter can be obtained.

The black matrix according to the second embodiment is excellent in light shielding property, so that it has excellent display contrast of a color liquid crystal display device and further has a low dielectric constant property. Therefore, the black matrix is referred to as alignment disorder of liquid crystal and conduction between electrodes formed on a TFT substrate The inconvenience caused by the electrical characteristics of the black matrix is less likely to occur and the light transmittance in the near infrared region is excellent so that the mask alignment operation is also possible and is also suitable for a substrate for driving a thin film transistor (TFT) system color liquid crystal display device .

According to the third embodiment, since the black matrix is excellent in light shielding property, the display contrast of the color liquid crystal display device is excellent, and furthermore, since the black matrix has a low dielectric constant property, alignment disorder of the liquid crystal and conduction between electrodes formed on the TFT substrate It is possible to perform a mask alignment operation and is also suitable for a substrate for driving a thin film transistor (TFT) system color liquid crystal display device because the transmittance of the near infrared region is excellent.

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

<Colorant>

The coloring agent includes a coloring agent for a filter segment and a coloring agent for a black matrix.

[Colorant for filter segment]

The pigment contained in the coloring agent for the filter segment is not particularly limited. However, considering the dispersibility of the pigment particles, the average primary particle diameter is preferably 20 nm or more. In consideration of the contrast ratio and brightness, the average primary particle diameter is preferably 50 nm or less. That is, as the average primary particle diameter becomes larger, light of the backlight is scattered and leakage light is generated when the polarizer is crossed, so that the contrast ratio is lowered. In addition, it affects the lowering of the brightness due to the lowering of the transmittance.

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

The shape of the pigment particle is not an acicular shape but preferably a spherical shape or an ellipsoidal shape. In the spherical shape, since the distance between the respective pigment primary particles becomes more uniform, light scattering becomes less likely to occur, and the contrast ratio and brightness become very high.

As the colorant, various color pigments such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used in the case of forming each color filter segment. Examples of the chemical structure include organic pigments such as azo pigments, phthalocyanine pigments, quinaclidone pigments, benzimidazolone pigments, isoindolinone pigments, dioxazine pigments, indanthrene pigments, and perylene pigments. In addition, various inorganic pigments and the like can be used.

Specific examples of usable pigments are shown. The term &quot; C.I. &quot; in the following stands for the color X (C.I.).

As the red pigment, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48 , 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: : 3,57, 57: 1, 57: 2, 58: 4,60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, , 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, , 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 is preferable from the viewpoint of obtaining a high contrast ratio and high brightness, CI Pigment Red 177, 209, 224, 242 or 254.

Examples of the blue pigments include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 , 79, and the like.

Among them, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4 or 15: 6 is preferable from the viewpoint of obtaining a high contrast ratio and high brightness, It is in the Gentlemen 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 may be mentioned. Among them, CI Pigment Green 7, 36 or 58 is preferable from the viewpoint of obtaining a high contrast ratio and high brightness.

As the yellow pigment, for example, C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: : 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: , 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 these, from the viewpoint of obtaining a high contrast ratio and high brightness, it is preferable to use C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185, and more preferably C.I. Pigment Yellow 83, 138, 139, 150, or 180, respectively.

As the violet pigment, for example, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3,5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, it is preferable to use C.I. Pigment Violet 19 or 23, more preferably C.I. Pigment Violet 23.

As the orange pigment, for example, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, , 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, it is preferable to use C.I. Pigment Orange 38 or 71.

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

[Colorant for Black Matrix]

In the present specification, a coloring composition for a color filter containing a coloring agent for a black matrix is sometimes referred to as a &quot; black coloring composition &quot; or a &quot; black resin composition &quot;.

When a black matrix is formed, a black pigment as the coloring agent 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 nm to 50 nm, even more preferably 20 nm to 50 nm, in view of the light shielding property with respect to the upper limit and the pigment dispersibility with respect to the lower limit. And particularly preferably 20 to 45 nm. That is, as the average primary particle diameter becomes larger, the packing of the particles becomes sparse, and a gap is formed, and concealability is lowered. On the other hand, by suppressing the average primary particle size to 50 nm or less, packing of the particles becomes compact, and the light shielding property is enhanced.

The aspect ratio of the pigment particles is preferably 1: 1 to 1: 3.5, more preferably 1: 1 to 1: 2.0, even more preferably 1: 1 to 1: 1.5. Within the above range, the packing of the particles becomes dense, and concealability is improved due to the small gap.

The shape of the pigment particle is not an acicular shape but preferably a spherical shape or an ellipsoidal shape. Particularly, in the spherical phase, since the distance between the respective primary particles of the pigment becomes more uniform, the gap becomes less likely to occur, and concealability becomes very high.

Examples of usable black pigments include light-shielding black pigments such as perylene black pigments, carbon black, acetylene black, lamp black, black black, graphite, iron black, titanium black and the above-mentioned red, purple, , Green, and blue pigments. Among them, a pigment mixed color system such as a perylene black pigment, carbon black, red, purple, yellow, green, and blue pigment is preferable. More preferably, the perylene-based black pigment is used alone, or the combination of the perylene-based black pigment and carbon black is used in view of hiding and electrical characteristics.

When the perylene-based black pigment is used singly, the specific dielectric constant, dispersibility, and developability are particularly excellent.

When the perylene-based black pigment and the carbon black are used in combination, the content of the perylene-based black pigment in 100 wt% of the black pigment is preferably 78 to 95 wt%, and more preferably 80 to 95 wt%. Considering that sufficient light shielding property is obtained in the vicinity of 1.0 占 퐉, the proportion of the perylene black pigment is preferably 95% by weight or less. Considering that the transmittance at a wavelength of 1000 nm is increased so as to sufficiently recognize the infrared sensor of the alignment, and the orientation of the liquid crystal molecules is prevented from being disturbed by the drive voltage in the case of BM formation, % Or more.

The content of the black pigment is preferably 20 to 70% by weight, more preferably 30 to 70% by weight, based on 100% by weight of the total solid content of the coloring composition for a color filter, considering sufficient dispersion stability for the upper limit and sufficient light- By weight, more preferably from 30 to 60% by weight, still more preferably from 40 to 60% by weight.

The black matrix formed by using the black coloring composition composed of the perylene-based black pigment or the mixed color system is excellent in the display contrast of the color liquid crystal display device because of its excellent light shielding property and further has the low dielectric constant property, It is difficult to inconvenience due to the electric characteristics of the black matrix, such as confusion or conduction between the electrodes formed on the TFT substrate. On the other hand, since the transmissivity of the near infrared region is excellent, mask alignment can be performed, And is also suitable for a driving substrate of a color liquid crystal display device.

# 40, # 44, # 45, # 45L, # 47, # 50, # 30, # 32, # 33, # 40, PrIntex L, PrIntex P, PrIntex 30, PrIntex 35, PrIntex 40, PrIntex 45, PrIntex 55, PrIntex 60, PrIntex 300, PrIntex 350, SpecIal 55, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, Black 4, SpecIal Black 350, SpecIal Black 550, and the like. Of these, # 45 is preferable from the viewpoint of obtaining a high optical density (hereinafter sometimes referred to as OD). The carbon black may be used singly or as a mixture of two or more kinds.

When the colorant of the present invention has a pigment with an average primary particle diameter of 20 to 50 nm and an aspect ratio of 1: 1 to 1: 3.5, its content is preferably 30 to 100 By 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 thereof is usually at least 1% by weight More preferably not less than 5% by weight, and usually not more than 95% by weight, particularly preferably not more than 85% by weight. If it is 5% by weight or more, the film thickness with respect to the color density becomes large and does not become excessive, and there is no possibility that adverse influence is exerted on the gap control at the time of liquid crystal cell formation. On the other hand, if it is 95% by weight or less, sufficient dispersion stability can be obtained.

[Minification of Pigment]

The pigment used in the present invention may be finely ground by a salt milling treatment or the like. By using the finely divided pigment, a filter segment having a higher contrast ratio can be formed, and a black matrix having a high light shielding property can be formed.

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is mechanically kneaded while heating using a kneader such as a kneader, two roll mills, three roll mills, a ball mill, an attritor and a sand mill , And removing water-soluble inorganic salt and water-soluble organic solvent by washing with water. The water-soluble inorganic salt functions as a crushing aid, and at the time of salt milling, the pigment is crushed using the height of the hardness of the inorganic salt. By optimizing the conditions under which the pigment is subjected to the salt milling treatment, it is possible to obtain a pigment having a very fine primary particle size, narrow distribution width, and sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used. From the viewpoint of cost, however, sodium chloride (salt) is preferably used. The water-soluble inorganic salt is preferably used in an amount of from 50 to 2000 parts by weight, and most preferably from 300 to 1000 parts by weight, based on 100 parts by weight of the pigment, in both treatment efficiency and production efficiency.

The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves in water (miscible), and does not substantially dissolve the inorganic salt used. However, from the viewpoint of safety, a high boiling point solvent having a boiling point of 120 캜 or higher is preferable because the temperature rises during salt milling and the solvent becomes apt to evaporate. For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Monoethyl ether, and liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most 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 resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably a solid at room temperature, preferably water-insoluble, and more preferably partially soluble in the 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, and a surfactant. The dispersing agent is excellent in the dispersion of the pigment and prevents the pigment from re-aggregating after dispersion.

[Resinous dispersant]

An AB block copolymer or a BAB block copolymer composed of a B block having a hydrophilic group and a B group having a functional group containing a nitrogen atom as a resinous dispersant and having an amine value of not less than 10 mgKOH / And an acrylic block copolymer having a KOH / g or less.

The resinous dispersant has a coloring agent affinity site having a property of adsorbing to a colorant and a site compatible with the colorant carrier and adsorbs on the colorant to stabilize the dispersion of the colorant in the colorant carrier. Since the dispersing agent is randomly arranged in the pigment adsorber, it is easy to increase the viscosity by crosslinking.

On the other hand, since the block copolymer has a high density of pigment adsorbers, it is strongly adsorbed to the pigment and has no crosslinking. Therefore, the block copolymer can secure higher dispersion stability. When the amine value is 10 mgKOH / g or more and 99 mgKOH / g or less, solubility in a developing solution becomes favorable, development can be made in a predetermined time in the developing step, There is no case where the undissolved product remains.

The monomer which is a precursor of the A block having a hydrophilic property 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 capable of copolymerizing with a monomer constituting the B-block.

Examples of the A block include styrene-based monomers such as styrene and? -Methylstyrene; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate such as benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate and polypropylene glycol Monomers; (Meth) acrylic acid salt type monomers such as (meth) acrylic acid chloride; Vinyl acetate-based monomers; And glycidyl ether-based monomers such as allyl glycidyl ether, crotonic acid glycidyl ether, and the like.

Among them, examples of the A block include a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as a copolymerization component (that is, a polyalkylene glycol Rate-derived partial structure), and particularly preferably has a partial structure represented by the following general formula (I).

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

It is particularly preferable that the partial structure represented by the general formula (I) is contained in an amount of 5 to 40 mol% in the A block.

From the viewpoint of enhancing dispersion stability, it is preferable that the A block contains 50 to 90 mol% of a constitutional unit having a (meth) acrylic ester monomer other than the partial structure represented by the general formula (I) as a precursor , And more preferably 60 to 80 mol%. Among them, use is made of (meth) acrylic acid ester monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and octyl , Dispersibility and stability of the coloring composition are excellent.

By including the partial structure represented by the general formula (I) in the A block, the hydrophilicity is imparted and the solubility in the developer becomes good. On the other hand, by including a constitutional unit having a (meth) acrylic ester monomer other than the partial structure represented by the general formula (I) as a precursor, compatibility with the binder resin increases and dispersion stability improves.

As the B block having a functional group containing a nitrogen atom, it is preferable to have a primary to tertiary amino group as the functional group. The content of the primary to tertiary amino groups is preferably at least 10 mol%, more preferably at least 40 mol%, of the total nitrogen atom-containing functional groups.

The amino group is preferably -NR ₄ R ₅ , wherein R ₄ and R ₅ are each independently a cyclic or straight-chain alkyl group which may have a substituent, an aryl group which may have a substituent or aral And a preferable partial structure including this is represented by the following formula, for example.

[In the formula (II), R ₄ and R ₅ independently represent a cyclic or straight-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, and R ₃ R ₄ and R ₅ are preferably a methyl group, R ₃ is preferably a methylene group or an ethylene group, and R ₂ is preferably a methyl group, and R ₂ is a hydrogen atom or a methyl group. Do. A preferable example of such a partial structure is represented by the following expression.

Two or more kinds of partial structures containing the amino group may be contained in one B-block. In this case, the partial structure containing two or more kinds of amino groups may be contained in any form of random copolymerization or block copolymerization in the B-block. A partial structure not containing an amino group may be contained in a part of the B-block within a range that does not impair the effect of the present invention. Examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer . The content of the amino group-free partial structure in the B-block is preferably 0 to 60 mol%, more preferably 0 to 20 mol% Most preferably not included.

When a quaternary ammonium base is used as a B block having a functional group containing a nitrogen atom, there is a case where the quaternary ammonium base is thickened or gelated so that the polarity is strong and interacts with other resins so that adsorption to the colorant does not progress. Therefore, as the functional group containing a nitrogen atom, a primary, secondary or tertiary amine is preferable. Among them, tertiary amines are more preferable because they have both adsorption power and stability to a colorant.

That is, from the viewpoint of improving the dispersibility and solubility of the developer, the acrylic block copolymer contains 5 to 40 mol% of the repeating unit represented by the general formula (I) in the hydrophilic A block and contains nitrogen atom It is preferable to contain a repeating unit represented by the general formula (II) in a B block having a functional group capable of reacting with a hydroxyl group.

When the acrylic block copolymer contains an acid group such as carboxylic acid or phosphoric acid, the acid group interaction with the amine moiety or the like in the B block may cause a decrease in the dispersion stability, so that the acid value is preferably as low as possible, KOH / g is more preferable.

The content of the acrylic block copolymer is preferably 1 to 70 parts by weight, more preferably 10 to 60 parts by weight, based on 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. When the coloring composition is used and a pixel pattern of a color filter is formed by a photolithography method, it is preferably 70 parts by weight or less from the viewpoint of obtaining high alkali developability.

In addition, the coloring composition for a color filter of the present invention may contain, alone or in combination with the above resin type dispersing agent, other resin type dispersing agent.

Examples of the other resinous dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxane , Long-chain polyamino anhydrides, long chain polyamino acid myridates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides and salts thereof formed by reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group, Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, , A modified polyacrylate type, an ethylene oxide / propylene oxide addition compound, a phosphoric ester type, and the like can be used have.

As commercially available resinous dispersants usable in the present invention, DIsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 174, 180, 181, 182, 183, 184, 185, 190, 9076, 9077 or BYK-LPN 6919, 21324, 21407 or AntI- Terra-U, 203, 204 or BYK- 3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000 from Lubrizol Japan Ltd., P104S, 220S or LactImon, LactImon-WS or Bykumen , EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401 of EPC Chemicals, Inc., 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, PA111, PB711, PB821, PB822, and PB824 manufactured by Ajinomoto Fine Techno Co., Ltd., and the like, .

A pigment derivative, preferably a pigment skeleton of an organic pigment and a pigment derivative having an alkaline substituent are used as a pigment dispersant for a black pigment because electric characteristics are better. Further, by including a resinous dispersant, it is preferable because it improves new electrical properties and balances flowability and stability.

The resinous dispersant has a pigment affinity site having a property of adsorbing to the light-shielding black pigment and a site compatible with the black pigment carrier, and is adsorbed on the black pigment to stabilize the dispersion in the black pigment carrier .

The resinous dispersant, like the pigment derivative, imparts affinity to the black pigment and the pigment derivative, thereby making the molecular arrangement in the black resin composition more uniform, and further contributing to the improvement of electric characteristics in order to further reduce the convenience of electric charge It is preferable.

Particularly, it is preferable to use a pigment derivative having an acid substitution group and an acidic resin-type dispersant of a black pigment and an organic pigment, because it exhibits an excellent effect of both fluidity and electrical characteristics.

This is because the electric charge is neutralized by the interaction of the acidic resinous dispersant and the acidic basic substitution period of the pigment derivative having an alkaline substituent, and as a result, the convenience of local charge is suppressed, thereby improving the electric characteristics.

Among these, an acidic resinous dispersant is preferable for enhancing interaction with an alkaline derivative, and from the viewpoint of dispersion stability, the acid value of the resinous dispersant is preferably 129 mgKOH / g or less, and most preferably, 13 to 53 mg KOH / g.

[Pigment Derivative]

The coloring composition for a color filter of the present invention further preferably contains an acid derivative of an organic pigment or a pigment derivative which is a metal salt thereof. The acidic derivative of the organic pigment or its metal salt promotes the pigment adsorption of the pigment and the resinous dispersant more easily and improves the dispersibility of the pigment, so that the effect of preventing the re-aggregation of the pigment after dispersion is great. Therefore, in the case of using a colored composition in which a pigment is dispersed in a pigment carrier using an acid derivative of an organic pigment or a metal salt thereof, a color filter excellent in stability can be obtained. Further, when the resin is used simultaneously with the A-B block copolymer or the resin-type B-A-B block copolymer comprising a B block having a hydrophilic group and a B block having a functional group containing a nitrogen atom, dispersibility is further improved. It is considered that this is because the pigment adsorption of the dispersing agent is promoted by the interaction of the acidic substituent of the derivative disposed near the pigment and the acidic group of the alkaline substituent of the dispersant.

Examples of the structure of the acid derivative of the organic pigment or the metal salt thereof include compounds represented by the following general formula (1).

P-Lx Formula (1)

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

Examples of the organic pigments constituting the organic pigment residue of P include diketopyrrolopyrrole pigments; Azo pigments such as azo, disazo and polyazo; Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine and non-metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and biorantrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Threne-based pigments; Quinophthalone pigments; Dioxazine pigments; Metal complex system pigments, and the like.

Among them, quinophthalone pigments, especially quinophthalone yellow pigments C.I. Pigment Yellow 138 is preferable because it is excellent in the composition, dispersion stability, heat resistance, light resistance, solvent resistance and the like of the coloring composition.

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

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, positive metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel .

Of these, alkaline earth metal ions such as calcium and barium, positive metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel are preferable. Among them, aluminum ions are particularly preferable because of their high heat resistance and dispersibility.

The acid derivative of the organic pigment or the metal salt thereof is particularly preferably a sulfonic acid derivative of quinophthalone or an aluminum salt thereof. The sulfonic acid derivative or its aluminum salt of quinophthalone is excellent in dispersion of the colorant and has a great effect of preventing re-aggregation of the colorant after dispersion. Therefore, the coloring composition obtained by dispersing the colorant in a colorant carrier such as a resin or an organic solvent by using a sulfonic acid derivative of quinophthalone or an aluminum salt thereof is excellent in stability.

For example, quinophthalone yellow pigments C.I. A sulfonic acid derivative of quinophthalone composed of Pigment Yellow 138 is represented by the following formula (2), and its aluminum salt is represented by the following formula (3).

Equation (2):

Equation (3):

The aluminum salt of the sulfonic acid derivative of quinophthalone is synthesized by a conventional method, but the following method is industrially advantageous. That is, the dye is added to the concentrated sulfuric acid or the fuming sulfuric acid, and the sulfonation is carried out by heating. Subsequently, this reaction solution is injected into a large amount of ice water, and the precipitated sulfonic acid derivative is washed with a filter press or the like.

Dispersing a water paste of the obtained sulfonic acid derivative in a large amount of water, adjusting the pH to weak alkalinity using an aqueous solution of sodium hydroxide, slowly adding an aqueous solution of aluminum sulfate to salt the sulfonic acid and forming an aluminum salt to be. Thereafter, the aluminum salt of the sulfonic acid derivative of the quinophthalone in powder form can be obtained through the steps of washing, washing, drying and pulverizing.

Examples of the pigment derivative which can be used in combination with the acid derivative of the organic pigment or the metal salt thereof are disclosed in Japanese Patent Application Laid-Open Nos. 63-305173, 57-15620, 59-40172, 63-17102, JP-A-5-9469, and the like.

Further, in the coloring composition for a color filter of the present invention, a compound represented by the following general formula (1 ') may be used as a pigment derivative. In particular, it is preferably used as a pigment derivative for a black coloring composition.

P'-L'n ????? (1 ')

[only,

P ': an organic pigment residue, an anthraquinone residue, an acridone residue or a triazine residue

L ': an alkaline substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent

n is an integer of 1 to 4.]

The organic pigments constituting the organic pigment residue of P 'include, for example, diketopyrrolopyrrole pigments; Azo pigments such as azo, disazo and polyazo; Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and non-metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and biorantrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Quinophthalone pigments; Threne-based pigments; Metal complex system pigments, and the like.

Among them, a pigment derivative in which the parent skeleton is an organic pigment is preferable, and a dioxazine-based pigment and a diketopyrrolopyrrole-based pigment can be more preferably used from the viewpoint of low dielectric tangent.

In the general formula (1 '), L' is preferably an alkaline derivative which is an alkaline substituent.

Among them, the parent skeleton of the organic pigment and the pigment derivative having an alkaline substituent contribute to improvement of electrical characteristics in order to impart affinity to the perylene black pigment, uniformize the molecular arrangement in the black resin composition, and reduce charge convenience .

Also, preferably L 'is a substituent selected from the group represented by the general formulas (2'), (3 ') and (4').

 General formula (2 '):

 General formula (3 '):

 The general formula (4 '):

In the formulas (2 ') to (4'), X represents -SO ₂ -, -CO-, -CH ₂ -, -CH ₂ NHCOCH ₂ -, -CH ₂ NHSO ₂ CH ₂ - ego,

Y is -NH-, -O- or a direct bond,

N is an integer of 1 to 10,

Y ¹ is -NH-, -NR ⁵⁸ -Z-NR ⁵⁹ - or a direct bond,

R ⁵⁸ and R ⁵⁹ are each 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,

Z is an alkylene group which may have a substituent or an allylene group which may have a substituent,

R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, or R ⁵⁰ and R ⁵¹ are integral with each other, A heterocyclic ring which may have a substituent, including a nitrogen atom, an oxygen atom or a sulfur atom,

R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent 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, An allylene group having 6 to 20 carbon atoms,

R ⁵⁶ 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,

R ⁵⁷ is a substituent represented by the general formula (2 ') or a substituent represented by the general formula (3'),

Q is a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (2 ') or a substituent represented by the general formula (3').

Examples of the amine component used for forming the substituent represented by the general formulas (2 ') - (4') include dimethylamine, diethylamine, methylethylamine, N, N- ethylisopropylamine, N , N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine , N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisooamylamine, N, N-dimethyloctylamine, N, N-dimethyloctylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-dimethylaniline, N, N-dimethylaminoethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoethylamine, N, Butyl N, N-diethylaminopropylamine, N, N-diethylaminobutylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentyl Amine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diethylaminoethylamine, N, N-dioleylaminoethylamine, N, N-diethylaminoethylamine, N, - distearyl aminobutylamine, piperidine, 2-piperolin, 3-piperolin, 4-piperolin, 2,4-lupetidine, 2,6-lupetidine, 3-hydroxypyrrolidine, N-aminoethylpiperazine, N-aminoethylpiperazine, N-methylpiperazine, N-methylpiperidine, Lysine, N-aminoethyl-4-pipercoline, N-amino Aminopropyl-4-piperacoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylpiperazine, N- N-methyl homopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

Pigment derivatives, anthraquinone derivatives and acridone derivatives having a basic substituent can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the formulas (5 ') to (8') into an organic dye, anthraquinone, or acridone, the compound represented by the formula The amine component forming the substituent, such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) Amino] -1,3,5-triazine 2-ylamino] aniline, and the like.

Equation (5 '): -SO ₂ Cl

Formula (6 '): -COCl

Expression _{(7 '): -CH 2 NHCOCH} 2 Cl

Formula (8 '): -CH ₂ Cl

Even when a part of the substituents of the formulas (5 ') - (8') is hydrolyzed and the chlorine is substituted by a hydroxyl group at the time of the reaction of the substituent of the formulas (5 ') to (8' good. In this case, the formula (5 ') and the formula (6') are respectively a sulfonic acid group and a carboxylic acid group, but either of them may be a free acid or a salt of a mono- to trivalent metal or the monoamine .

When the organic dye is an azo dye, the substituents represented by the general formulas (2 ') - (4') are introduced into the diazo component or the coupling component in advance, and then the coupling reaction is carried out, Derivatives may also be prepared.

The total amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and still more preferably 1 part by weight or more, in view of preventing a decrease in the contrast ratio and obtaining good electrical properties, relative to 100 parts by weight of the colorant. Most preferably at least 3 parts by weight. Further, 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, considering sufficient light resistance and good electrical characteristics in the black matrix.

The pigment derivatives may be used alone or in combination of two or more.

[Surfactants]

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate , Anionic surfactants such as monoethanolamine laurylsulfate, monoethanolamine laurylsulfate, ammonium laurylsulfate, stearic acid monoethanolamine, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; Alkyl betaine such as alkyldimethylaminoacetic acid betaine, and alkyl imidazoline. These surfactants may be used singly or in combination of two or more. However, the present invention is not limited thereto.

The amount of the resinous dispersant and the surfactant to be added is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the colorant, considering the good dispersibility.

<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 disperses a coloring agent, and a thermoplastic resin, a thermosetting resin, or the like can be used. It is preferable that the above-mentioned resin is a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the propagation region of 400 to 700 nm in the visible light region. When used in the form of an alkali developing photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond may be used.

In particular, the use of an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain improves the stability of the resist material, 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, polyvinyl acetate, polyurethane- (HDPE, LDPE), polybutadiene and polyimide resins, and the like can be given as examples of the resin composition of the present invention.

Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin and a phenol resin.

Examples of the vinyl-based alkali-soluble resin in which an ethylenically unsaturated monomer containing an acidic group is copolymerized include resins having an acidic group such as a carboxyl group and a sulfonic group.

Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an? -Olefin / (maleic anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer or an isobutylene / Maleic acid 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 highly suitably used because of its high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin into which an ethylenically unsaturated double bond is introduced by the method (i) or (ii) shown below.

[Method (i)]

Examples of the method (i) include a method in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to a side chain epoxy group of a copolymer obtainable by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, There is a method in which an addition reaction is carried out and, further, a polybasic acid anhydride is reacted with the resulting hydroxyl group 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, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4- (Meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the viewpoint of reactivity with an unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, alpha-position haloalkyl of alkenyl (meth) acrylic acid, alkoxyl, halogen, nitro, These may be used alone 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, and these may be used alone or in combination of two or more.

A tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used and the remaining anhydride group may be hydrolyzed if necessary, for example, by increasing the number of carboxyl groups . The use of tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond as the polybasic acid anhydride can further increase the ethylenically unsaturated double bond.

As a similar method of the method (i), an ethylenically unsaturated monomer having an epoxy group is addition-reacted to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing, for example, an ethylenically unsaturated monomer having a carboxyl group and at least one other monomer , An ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]

As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group can be used, and a copolymer of an unsaturated monobasic acid monomer having another carboxyl group and another monomer can be obtained by copolymerizing an ethylenically unsaturated monomer having an isocyanate group There is a method of reacting an isocyanate group.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (Meth) acrylates such as glycerol (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate. These may be used alone or in combination of two or more .

Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate, polyether mono (Poly) ester mono (meth) acrylate to which (poly) ε-caprolactone, and / or (poly) 12-hydroxystearic acid is added. From the viewpoint of coating water repellency, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [(meth) acryloyloxy] ethyl isocyanate. Or more.

In order to disperse the colorant preferably, 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. 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.

From the viewpoints of the dispersibility, stability, developability and heat resistance of the colorant, the acid value of the resin is preferably at least one selected from the group consisting of a colorant adsorbent and a carboxyl group serving as an alkali-soluble group at the time of development, a colorant carrier and an aliphatic group and an aromatic group Considering balance, the acid value is preferably 20 to 300 mg KOH / g. Considering the acid value, solubility in developing solution, and formation of fine patterns, 20 mgKOH / g or more is preferable. In consideration of the degree to which the fine pattern remains, it is preferably 300 mgKOH / g or less.

The resin is preferably used in an amount of not less than 30 parts by weight based on 100 parts by weight of the total weight of the colorant from the viewpoint of good film formability and resistance to chemicals and high colorant concentration and good color characteristics can be exhibited, It is preferably used in 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. The solvent is preferably such that the coloring agent is sufficiently dispersed in the resin and the colored composition of the present invention is applied on a transparent substrate such as a glass substrate so that the dry film thickness is preferably 0.1 to 10 탆 and more preferably 0.2 to 20 탆, In order to facilitate the formation of the &lt; / RTI &gt;

Examples of the solvent include 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, -Propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethyl Benzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n- butylbenzene, n-propylacetate, chlorobenzene, tert-butylbenzene,? -butyrolactone, isobutylalcohol, isophorone, isobutylalcohol, isobutylalcohol, isobutylalcohol, isobutylalcohol, Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Ethylene glycol monoethyl ether acetate, ethylene glycol mono tertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl 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, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether Diethylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Propyleneglycol monomethyl ether propionate, benzyl alcohol, methylisobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester To The.

These solvents may be used singly or as a mixture of two or more kinds in an optional ratio as required.

Among them, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate and the like, benzyl alcohol And ketones such as cyclohexanone are preferably used.

The solvent is preferably used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the coloring agent since the coloring composition can be adjusted to a proper viscosity and a desired filter layer of a desired film thickness can be formed.

The coloring composition for a color filter of the present invention can further be used as a color filter light-sensitive coloring composition (resist material) by adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable Monomer>

The coloring composition for a color filter of the present invention may contain a photopolymerizable monomer. The photopolymerizable monomer includes a monomer or an oligomer which is cured by ultraviolet rays or heat to produce a resin, and these may be used singly or in combination of two or more. The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on 100 parts by weight of the colorant, more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability, even more preferably 10 to 200 parts by weight Buddha. As the photopolymerizable monomer, a compound having one or more ethylenic unsaturated double bonds is preferable.

Examples of the photopolymerizable monomer include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (Meth) acrylate,? -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexane diol diglycidyl ether di ) Acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (metha) acrylate, dipentaerythritol penta (Meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid esters of methylol melamine, epoxy (meth) acrylates, urethane acrylates, and methacrylic esters (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Butadiene styrene resin, and the like, but are not limited thereto.

<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 to form a filter segment or a black matrix by a photolithography method, a photopolymerization initiator or the like can be added to form a solvent-developing type or an alkali development type photosensitive coloring composition.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane 1-one and 2- (dimethylamino) -2 - [(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenone-based compounds; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzyl dimethyl ketal; Benzoylbenzoic acid, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide or 3,3 ', 4,4'-tetra (t -Butylperoxycarbonyl) benzophenone; benzophenone-based compounds such as benzophenone; Thioxanthone compounds such as thioxanthone, 2-crothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone or 2,4- ; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s- triazine, 2- (p- methoxyphenyl) Tri (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6- Triazine-based compounds such as triazine or 2,4-trichloromethyl- (4'-methoxy styryl) -6-triazine; 2-oxo-2- (4 ', 5'-tetradecyloxy) (Methoxynaphthyl) ethylidene) hydroxylamine, ethanone, 1- [9-ethyl-6- Oxime); Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone; Borate compounds; Carbazole-based compounds; Imidazole-based compounds; Alternatively, a titanocene compound or the like is used.

These photopolymerization initiators may be used singly or as a mixture of two or more kinds in an optional ratio as required.

The content of the photopolymerization initiator is preferably 5 to 200 parts by weight based on 100 parts by weight of the colorant, more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability.

<Increase / decrease>

Furthermore, the coloring composition for a color filter of the present invention may contain a sensitizer.

Examples of the sensitizer include unsaturated ketones represented by carcon derivatives, dibenzalacetone and the like, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Polymethine dyes such as a chitosan derivative, a chitosan derivative, a thioxantene derivative, a xanthone derivative, a thioxanthone derivative, a coumarin derivative, a ketocoumarin derivative, a cyanine derivative, a melocyanine derivative, There can be mentioned an azine derivative, a thiazine derivative, an oxazine derivative, an indoline derivative, an azene derivative, an azulene derivative, a squalinium derivative, a porphyrin derivative, a tetraphenylporphyrine derivative, a triarylmethane derivative, a tetrabenzoporphyrin derivative, A pyrazine derivative, a phthalocyanine derivative, a tetraazaporphyrazine derivative, a tetraquinoxariaporphirazine derivative, A thiopyrimidine derivative, a tetrapyrine derivative, an anuran derivative, a spiropyran derivative, a spirooxazine derivative, a thiospyropyran derivative, a metal isocyanate complex, an organolithium complex or an organometallic complex. Anthracene derivatives, hiraketone derivatives,? -Acyloxy esters, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'- , 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4'-diethylaminobenzophenone.

These sensitizers may be used singly or as a mixture of two or more kinds in an optional ratio as required.

More specifically, it is also known as "functional coloring matter chemistry" (1981, Shim City), "Chikuso Handbook" (1986, Kodansha), Makoto Ogawara, Quot; and &quot; Additional Functional Materials &quot; (1986, SiMi), but are not limited thereto. In addition, it is also possible to add a sensitizer which exhibits absorption of light from the ultraviolet ray to the near infrared region.

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

<Leveling agent>

In the coloring composition for a color filter of the present invention, it is preferable to add a leveling agent in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure on the main chain include FZ-2122 manufactured by Toray Dowconin Co., Ltd., and BYK-333 manufactured by Big Chemie. Specific examples of the dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Vickerskymy. It may also be used in combination with a dimethylsiloxane having a polyether structure in the main chain and a dimethylsiloxane having a polyester structure in the main chain. The content of the leveling agent is usually 0.003 to 0.5% by weight based on 100% by weight of the total weight of the coloring composition.

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophobic group in the molecule, and has a characteristic that when the hydrophilic group is soluble in water and added to a coloring composition, its surface tension lowering ability is low , And that the wettability to the glass plate is good regardless of the lowering of the surface tension lowering ability, and that the chargeability can be suppressed sufficiently at an addition amount at which defects of the coating film due to foaming do not appear. As the leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The form of bonding of the polyalkylene oxide unit with the dimethylpolysiloxane may be a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, an end-casting bonded to the terminal of the dimethylpolysiloxane, alternating with the dimethylpolysiloxane Or a linear block copolymer type in which a linear block copolymer is combined. FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2191, and FZ-2122 are commercially available from Toorra Dowcon K.K., 2203, and FZ-2207, but are not limited thereto.

It is also possible to add anionic, cationic, nonionic or amphoteric surfactants to the leveling agent. The surfactants may be used in combination of two or more. Examples of the anionic surfactant added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, alkyldiphenyl ether disulfonic acid Sodium lauryl sulfate, monoethanolamine laurylsulfate, triethanolamine laurylsulfate, ammonium laurylsulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester And the like.

Examples of the chaotropic surfactant which is added to the leveling agent as an auxiliary include alkyl quaternary ammonium salts and such ethylene oxide adducts. Examples of the nonionic surfactant which is supplementarily added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, Polyethylene glycol monolaurate and the like; Alkyl betaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

<Amine compound>

The coloring composition for a color filter of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2- 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl paratoluidine, and the like.

<Curing agent, hardening accelerator>

The coloring composition for a color filter of the present invention may contain a curing agent, a curing accelerator and the like as necessary in order to assist curing of the thermosetting resin. As the curing agent, a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not limited thereto, and any curing agent that can react with a thermosetting resin May be used. Among them, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably used.

Examples of the curing accelerator include amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, Amines, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride), block isocyanate compounds (e.g., dimethylamine) 2-cyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, (For example, triphenylphosphine), a guanamine compound (e.g., triphenylphosphine, etc.) (For example, melamine, guanamine, acetoguanamine, benzoguanamine and the like), S-triazine derivatives (for example, 2,4-diamino 6-methacryloyloxy 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4- 6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct) and the like can be used. These may be used alone, or two or more kinds may be used in combination.

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).

&Lt; Other additive components >

The coloring composition for a color filter of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Further, in order to improve the adhesion with the transparent substrate, an adhesion improving agent such as a silane coupling agent may be contained.

Examples of the storage stabilizer include organic acids such as quaternary ammonium chloride, lactic acid and oxalic acid such as benzyltrimethyl chloride and diethylhydroxyamine, and methyl ether thereof, t-butyl pyrocatechol, tetraethylphosphine, tetraphenylphosphine Organophosphine such as a pin, phosphite, and the like. 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 improver include vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as? -Methacryloxypropyltrimethoxysilane ,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (3,4-epoxycyclohexyl) methyltrimethoxysilane, Epoxy silanes such as silane,? - (3,4-epoxycyclohexyl) methyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane and? -Glycidoxypropyltriethoxysilane, N-β Aminoethyl)? -Aminopropyltrimethoxysilane, N-? (Aminoethyl)? -Aminopropyltriethoxysilane, N-? (Aminoethyl)? -Aminopropylmethyldiethoxysilane,? -Aminopropyltri Aminopropyltrimethoxysilane, N-phenyl- gamma -aminopropyltrimethoxysilane, N-phenyl-gamma- Aminopropyltriethoxysilane and the like, and silane coupling agents such as thiocylans such as? -Mercaptopropyltrimethoxysilane and? -Mercaptopropyltriethoxysilane.

The adhesion-improving agent may be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total weight of the colorant.

&Lt; Production method of colored composition >

The coloring composition for a color filter of the present invention can be produced by finely dispersing the respective components together using various dispersion means such as three roll mills, two roll mills, sand mill, kneader or attritor ).

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or an alkali-developing type coloring composition. The solvent-developing type or alkali-developing type coloring composition can be adjusted by mixing the pigment dispersion, the photopolymerizable monomer and / or the photopolymerization initiator and, if necessary, a solvent, other pigment dispersant and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

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 in consideration of viscosity, film thickness, fluidity and coating property. The coloring composition for a color filter is preferably colored with a coarse particle of 5 占 퐉 or larger, preferably coarse particle of 1 占 퐉 or larger, more preferably coarse particle of 0.5 占 퐉 or larger, It is preferable to carry out the removal. As described above, the coloring composition for a color filter preferably does not contain coarse particles. More preferably 0.3 mu m or less.

When the colored composition for a color filter according to the first embodiment is used, it is preferable to use 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 as a colorant; An AB block copolymer or a BAB block copolymer comprising a B block having a hydrophilic group A and a functional group containing a nitrogen atom as a resinous dispersant and having an amine value of not less than 10 mgKOH / An acrylic block copolymer having a KOH / g or less; solvent; And other components may be mixed as required.

Particularly, when the coloring composition for a color filter of the present invention is made of a black resin composition as a black coloring composition (second embodiment), the light-blocking black pigment has an average primary particle diameter of 50 nm or less, A perylene black pigment and carbon black having an aspect ratio of particles of 1: 1 to 1: 2; Suzy; solvent; The content of the perylene black pigment is 78 to 95% by weight based on the total amount of the light-shielding black pigment (A), and the solid content of the black resin composition is 5 to 40% by weight %. &Lt; / RTI &gt;

Furthermore, when the coloring composition for color fills of the present invention is a black resin composition as a black coloring composition (third embodiment): When the light-blocking black pigment has an average primary particle size of 50 nm or less and the aspect ratio of the pigment particles is A 1: 1 to 1: 2 perylene black pigment; Pigment dispersants; Suzy; solvent; And other components may be mixed as required.

<Color Filter>

Next, a color filter according to the present invention will be described.

The color filter of the present invention has a filter segment and / or a black matrix formed from the coloring composition for a color filter of the present invention on a substrate and can be provided with, for example, a black matrix and filter segments of red, green, have.

The formation of the filter segments and / or the black matrix by photolithography is carried out in the following manner. That is, the colored resin composition prepared as the solvent-developing type or alkali-developing type coloring resin composition (resist material) is applied on a transparent substrate by a spray coating method, a spin coat method, a slit coat method, If necessary, the dried film is subjected to active energy ray exposure through a mask having a predetermined pattern provided in contact with or in contact with the film. Thereafter, a filter segment and / or a black matrix having a desired pattern can be formed by dipping in a solvent or an alkaline developing solution, spraying a developing solution by spraying or the like, and removing the uncured portions. Further, in order to accelerate the polymerization of the photosensitive black resin composition, heating may be carried out if necessary. According to the photolithography method, a filter segment and / or a black matrix having higher precision than the printing method can be formed.

As the substrate of the color filter, a glass plate such as soda lime glass, a low alkali borosilicate glass, or an alkali-free aluminoborosilicate glass having a high transmittance to visible light, a resin such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate Plate is used. 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 for liquid crystal driving after paneling.

On the occasion of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and organic alkalis such as dimethylbenzylamine and triethanolamine may be used. A defoaming agent or a surfactant may be added to the developer.

As the developing treatment method, a shower developing method, a spray developing method, a dipping (developing) developing method, a paddle (liquid) developing method, or the like can be applied.

In order to increase the ultraviolet exposure sensitivity, the coloring composition for a color filter is coated and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen After the film is formed, active energy ray exposure may be performed.

As the active energy ray, an electron beam, ultraviolet ray, visible light of 400 to 500 nm can be used. As the source of the electron beam irradiated from the side of the composition application side, a thermionic emission gun, field emission gun and the like can be used. For example, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halides, gallium lamps, xenon lamps, carbon arc lamps and the like can be used for ultraviolet rays and visible light sources (light sources) of 400 to 500 nm. Specifically, since it is a point light source and the brightness is stable, an ultra-high pressure mercury lamp or xenon mercury lamp is often used. The dose of the active energy irradiated from the side of the composition application surface can be suitably set in the range of 5 to 1000 mJ, but it is preferably in the range of 20 to 300 mJ which is easy to manage in the process.

If the black matrix is formed in advance before the filter segments are formed on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, a multilayer film of chromium, chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, but the present invention is not limited thereto.

Further, a thin film transistor (TFT) may be formed on the transparent substrate or the reflective substrate in advance, and then a filter segment may be formed. By forming the filter segments and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased to improve the brightness.

Here, a method of forming a colored layer on a TFT substrate will be described. First, a light-shielding layer is formed on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed, so as to divide a portion for forming a pixel if necessary, After the coloring composition in which the pigment is dispersed is applied, prebaking is performed to evaporate the solvent to form a coating film.

Subsequently, this coating film is exposed through a photomask and then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film. Thereafter, post-baking is performed to form a pixel array in which pixel patterns are arranged in a predetermined arrangement do. The photomask used at that time is provided with a pattern for forming a through-hole in the form of a through hole or a character in the form of a letter other than the pattern for forming the pixel.

As the TFT substrate used for forming the colored layer, the same substrate as that of the above-mentioned color filter can be used. Such a substrate is subjected to a chemical treatment using a silane coupling agent or the like, a plasma treatment, ion plating, sputtering, It may be subjected to a suitable pretreatment such as vapor deposition.

In order to apply the coloring composition to the substrate, it is possible to use the same method as the above-mentioned substrate of the color filter.

The coating film thickness of the filter segment is preferably 0.1 to 10 탆, more preferably 0.5 to 6.0 탆, as a film thickness after drying.

The coating thickness of the black matrix is preferably in the range of 0.2 to 10.0 mu m, more preferably 0.2 to 5.0 mu m, as a film thickness after drying. And more preferably in the range of 0.5 to 2.5 占 퐉 which facilitates balancing of coatability and light shielding property.

From the viewpoint of the insulating property, the relative dielectric constant of the black matrix near the dried film thickness of 1.0 mu m is preferably 8.0 or less, more preferably 4.5 or less.

Furthermore, in order to carry out alignment using infrared rays, it is preferable that the light transmittance at a wavelength of 780 nm is 15% or more and less than 99% in a black matrix having a dry film thickness of 1.0 탆. The transmittance at a wavelength of 1000 nm is preferably 60% or more and less than 99%.

From the viewpoint of high order light, the optical density is preferably 1.30 or more, and more preferably 2.50 or more in a black matrix having a dry film thickness of 1.0 占 퐉. The optical density is preferably as high as possible, but the cured coating film is difficult to obtain in the case where the active energy ray is ultraviolet rays or visible light.

When the coating film is dried, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

On the color filter, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film and the like are formed as necessary.

In the color filter, a liquid crystal is injected from an injection port provided in a sealing portion against a counter substrate by using a sealing agent, and then an injection port is sealed, and a polarizing film or a retardation film is adhered to the outside of the substrate as required .

Such a liquid crystal display panel is widely used in various fields such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical re- OCB) can be used for a liquid crystal display mode in which coloring is performed.

&Lt; Substrate for driving a thin film transistor (TFT) system color liquid crystal display device &

A substrate for driving a thin film transistor (TFT) type color liquid crystal display device is a substrate for a thin film transistor (TFT) which is formed by a coating method such as spin coating, slit coating, roll coating, Forming a filter segment, and then forming a black matrix.

In addition, a black matrix may be formed on the substrate of the thin film transistor (TFT), and a color filter segment may be formed thereon.

[Example]

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are "parts by weight" and "% by weight", respectively. The polymerization average molecular weight (Mw) of the resin, the acid value of the resin or the resinous dispersant and the amine value of the resinous dispersant, the specific surface area of the pigment, the average primary particle diameter and the aspect ratio of the pigment, the contrast ratio of the coating film, Is as follows.

&Lt; Polymerization average molecular weight (Mw) of resin >

The polymerization average molecular weight (Mw) of the acrylic resin was measured by GPC (HLC-8120 GPC, manufactured by Toray Industries, Inc.) equipped with an RI detector using a TSK gel column (manufactured by Toray Industries, Weight average molecular weight (Mw) in terms of conversion.

&Lt; Acid value of resin or resinous dispersant >

The acid value was determined by a potentiometric titration method using a 0.1N potassium hydroxide-ethanol solution. Acid value indicates the acid value of the solid content.

&Lt; Amine value of resinous dispersant >

The amine concentration was determined by a potentiometric titration method using 0.1N hydrochloric acid aqueous solution, and then converted to the equivalent amount of potassium hydroxide. The amine value represents the amine value of the solid.

<Specific Surface Area of Pigment>

The specific surface area of the pigment was measured by an apparatus for measuring the amount of adsorbed water vapor ("BELSORP18" manufactured by Bell Laboratories, Japan) according to the BET method of nitrogen adsorption.

<Average primary particle size and aspect ratio of pigment>

The average primary particle diameter of the pigment and the aspect ratio of the pigment particle were measured by a method of directly measuring the size of primary particles from an electron microscope photograph. Specifically, the short axis length and the major axis diameter of the primary particles of each pigment were measured, and the average was determined as the particle diameter of the pigment particles. Then, the volume (weight) of each of the 100 or more pigment particles was determined in a manner similar to that of the cube of the obtained particle size, and the volume average particle diameter was determined as the average primary particle diameter. As described above, the aspect ratios when the minor axis and the major axis of the primary particles of each pigment were measured were taken as the ratio of the average values of the minor axis and the major axis. The transmission electron microscope (TEM) was used.

&Lt; Contrast ratio of coating film &

Light emitted from a backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a dried coating film of a colored composition applied on a glass substrate, and reaches a polarizing plate. When two polarizing plates are parallel, light passes through the polarizing plate, but when the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the dried coating film of the coloring composition, scattering due to the pigment particles occurs, and if a difference occurs in a part of the polarizing plane, the amount of light transmitted through the polarizing plate When the polarizing plate is orthogonal, a part of the light is transmitted through the polarizing plate. The transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plate was parallel and the brightness when the polarizing plate was orthogonal was calculated.

(Contrast ratio) = (luminance in parallel) / (luminance in orthogonal)

A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the sum of the luminance and a polarizer ("NPF-G1220DUN" manufactured by Nitto Denki Corporation) was used as the polarizer. In addition, in order to block unnecessary light, a black mask having a hole of about 1 cm was placed in the measurement area.

&Lt; Film Thickness of Coating Film &

The film thickness of the coating film was measured using a surface shape measuring device (Dektak 6M, manufactured by Al Bass Co., Ltd.).

First, the first embodiment will be described with reference to examples and comparative examples.

&Lt; Process for producing resinous dispersant >

(Resinous dispersant solution A)

To a four-aperture separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 86.7 parts of butyl acrylate, 11.8 parts of Bremma PME-200 (methoxypolyethylene glycol-methacrylate) 2.8 parts of tetraene and 1.9 parts of ethyl bromo iso-lactate, and the mixture was heated to 40 占 폚 under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled to confirm that the polymerization yield was 95% or more and the weight average molecular weight (Mw) was 6860 from the solid content of the polymerization, and 1.4 parts of dimethylaminoethyl methacrylate and 20.0 parts of methyl ethyl ketone And further polymerization was carried out. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling at room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone and 60 parts of a cation exchange resin &quot; Daiion PK228LH (manufactured by Mitsubishi Chemical Corporation) &quot; was added thereto. The mixture was stirred at room temperature for 1 hour, and further diluted with "Kyowaud 500SN ) Was added and stirred for 30 minutes. By removing the cation exchange resin and the adsorbent by filtration, the debris of the polymerization catalyst was removed. Further, the resinous dispersant solution was concentrated and substituted with ethylene glycol monomethyl ether acetate to obtain a resinous dispersant solution A (dispersant A) having a solid content of 50% by weight (amine value: 5 mgKOH / g, acid value: 0 mgKOH / g ).

(Resinous dispersant solution B)

80 parts of butyl methyl acrylate, 85.5 parts of butyl acrylate, 11.7 parts of Bremma PME-200 (methoxypolyethylene glycol-methacrylate) 2.8 parts of tetraene and 1.9 parts of ethyl bromo iso-lactate, and the mixture was heated to 40 占 폚 under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled to confirm that the polymerization yield was 95% or more and the weight average molecular weight (Mw) was 6860 from the solid content of polymerization, and 2.9 parts of dimethylaminoethyl methacrylate and 20.0 parts of methyl ethyl ketone And further polymerization was carried out. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling at room temperature. 100 parts of the obtained resin solution was diluted in 100 parts of methyl ethyl ketone and 60 parts of a cation exchange resin &quot; Dai Aon PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.) was added and stirred for 1 hour at room temperature. Manufactured by Kagaku Kogyo Co., Ltd.) was added and stirred for 30 minutes. By removing the cation exchange resin and the adsorbent by filtration, the debris of the polymerization catalyst was removed. Further, the resinous dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resinous dispersant solution B (dispersant B) having a solid content of 50% by weight (amine value: 10 mgKOH / g, acid value: 0 mgKOH / g ).

(Resinous dispersant solution C)

To a four-opening separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 71.0 parts of butyl acrylate, 9.0 parts of Bremma PME-200 (methoxypolyethylene glycol-methacrylate) 2.8 parts of tetraene and 1.9 parts of ethyl bromo iso-lactate, and the mixture was heated to 40 占 폚 under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After 3 hours of polymerization, the polymerization solution was sampled to confirm that the polymerization yield was 95% or more and the weight average molecular weight (Mw) was 6860 from the solid content of the polymerization, and 20.0 parts of dimethylaminoethyl methacrylate and 20.0 parts of methyl ethyl ketone And further polymerization was carried out. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling at room temperature. 100 parts of the obtained resin solution was diluted in 100 parts of methyl ethyl ketone and 60 parts of a cation exchange resin &quot; Dai Aon PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.) was added and stirred for 1 hour at room temperature. Manufactured by Kagaku Kogyo Co., Ltd.) was added and stirred for 30 minutes. By removing the cation exchange resin and the adsorbent by filtration, the debris of the polymerization catalyst was removed. Further, the resinous dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resinous dispersant solution C (dispersant C) having a solid content of 50 wt% (amine value: 70 mgKOH / g, acid value: 0 mgKOH / g ).

(Resinous dispersant solution D)

To a four-opening separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 64.1 parts of butyl acrylate, 8.7 parts of Brenma PME-200 (methoxy polyethylene glycol-methacrylate) 2.8 parts of tetraene and 1.9 parts of ethyl bromo iso-lactate, and the mixture was heated to 40 占 폚 under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled to confirm that the polymerization yield was 95% or more and the weight average molecular weight (Mw) was 6860 from the solid content of polymerization, and 27.1 parts of dimethylaminoethyl methacrylate and 20.0 parts of methyl ethyl ketone And further polymerization was carried out. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling at room temperature. 100 parts of the obtained resin solution was diluted in 100 parts of methyl ethyl ketone and 60 parts of a cation exchange resin &quot; Dai Aon PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.) was added and stirred for 1 hour at room temperature. Manufactured by Kagaku Kogyo Co., Ltd.) was added and stirred for 30 minutes. By removing the cation exchange resin and the adsorbent by filtration, the debris of the polymerization catalyst was removed. Further, the resinous dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resinous dispersant solution D (dispersant D) having a solid content of 50 wt% (amine value: 95 mgKOH / g, acid value: 0 mgKOH / g ).

(Resinous dispersant solution E)

To a four-opening separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 57.8 parts of butyl acrylate, 7.9 parts of Bremma PME-200 (methoxypolyethylene glycol-methacrylate) 2.8 parts of tetraene and 1.9 parts of ethyl bromo iso-lactate, and the mixture was heated to 40 占 폚 under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After polymerization for 3 hours, the polymerization solution was sampled to confirm that the polymerization yield was 95% or more and the weight average molecular weight (Mw) was 6860 from the solid content of polymerization, and 34.3 parts of dimethylaminoethyl methacrylate and 20.0 parts of methyl ethyl ketone And further polymerization was carried out. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling at room temperature. 100 parts of the obtained resin solution was diluted in 100 parts of methyl ethyl ketone and 60 parts of a cation exchange resin &quot; Dai Aon PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.) was added and stirred for 1 hour at room temperature. Manufactured by Kagaku Kogyo Co., Ltd.) was added and stirred for 30 minutes. By removing the cation exchange resin and the adsorbent by filtration, the debris of the polymerization catalyst was removed. Further, the resinous dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resinous dispersant solution E (dispersant E) having a solid content of 50% by weight (amine value: 120 mgKOH / g, acid value: 0 mgKOH / g ).

(Resinous dispersant solution F)

To a four-opening separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 80 parts of methyl ethyl ketone, 70.4 parts of butyl acrylate, 9.6 parts of Bremma PME-200 (methoxypolyethylene glycol-methacrylate) 2.8 parts of tetraene, 1.9 parts of ethyl bromo iso-lactate and 20.0 parts of dimethylaminoethyl methacrylate were charged and the temperature was raised to 40 占 폚 under a nitrogen stream. 1.1 parts of cuprous chloride was added, and the temperature was raised to 75 캜 to initiate polymerization. After 3 hours of polymerization, the polymerization solution was sampled to confirm that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling at room temperature. 100 parts of the obtained resin solution was diluted in 100 parts of methyl ethyl ketone and 60 parts of a cation exchange resin &quot; Dai Aon PK228LH (manufactured by Mitsubishi Chemical Co., Ltd.) was added and stirred for 1 hour at room temperature. Manufactured by Kagaku Kogyo Co., Ltd.) was added and stirred for 30 minutes. By removing the cation exchange resin and the adsorbent by filtration, the debris of the polymerization catalyst was removed. Further, the resinous dispersant solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resinous dispersant solution F (dispersant F) having a solid content of 50% by weight (amine value: 70 mgKOH / g, acid value: 0 mgKOH / g ).

Table 1 summarizes the resin structure of each resinous dispersant and the amine value in terms of effective solid content.

&Lt; Production method of pigment derivative >

(Pigment derivative 1 (metal salt of quinophthalone skeletal sulfonic acid))

30 parts of quinophthalone-based yellow pigment (CI Pigment Yellow 138) was dissolved in 300 parts of 98% sulfuric acid and stirred at 70 캜 for 8 hours to carry out the sulfonation reaction. The end point of the reaction was determined by measuring the spectral spectrum of the sulfuric acid solution so that no change in the spectrum was observed. Subsequently, this reaction solution was poured into 3000 parts of iced water, and the precipitated sulfonated pigment derivative was filtered, washed with water, and dried to obtain C.I. A quinophthalone skeleton sulfonic acid having a structure represented by the formula (4) which is a sulfonated derivative of Pigment Yellow 138 was obtained. The yield after drying was 334 parts, and the yield was 99%

Equation (4)

The paste of quinophthalone skeletal sulfonic acid was redispersed (pH 2.5) in 10000 parts of water. Then, the solution was adjusted to pH 11 with an aqueous solution of sodium hydroxide and dissolved to give a red solution. To this solution, 278 parts of an aqueous solution of aluminum sulfate (liquid sulfuric acid band) was slowly added. The precipitates appeared sequentially from the dropping point, and the pH dropped with the addition, and at the end of the addition, pH was 3.6. The bleed could not be seen. The slurry containing this precipitate was washed with water, washed with C.I. A pigment derivative 1 which is a metal salt of a quinophthalone skeleton sulfonic acid having the structure represented by the formula (5) which is an aluminum salt of a sulfonated derivative of Pigment Yellow 138 was obtained. The yield after drying was 334 parts, and the yield was 99%.

Equation (5)

&Lt; Production method of micronized pigment >

(Green pigment PG-1)

, 500 parts of a phthalocyanine-based 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 poured into a stainless steel first gallon kneader (manufactured by INOUE CO. And kneaded at 80 DEG C for 8 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, A dry, 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 Manufacturing Co., Ltd.), 1500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by INOUE KK) Lt; 0 &gt; C for 2 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a green pigment PG-2.

(Green pigment PG-3)

500 parts of phthalocyanine-based 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 poured into a stainless steel first gallon kneader (manufactured by INOUE KK) Lt; 0 &gt; C for 12 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, Followed by drying to obtain a 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 Manufacturing Co., Ltd.), 1500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by INOUE KK) Lt; 0 &gt; C for 2 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a 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 Manufacturing Co., Ltd.), 1500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by INOUE KK) Lt; 0 &gt; C for 4 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a green pigment PG-5.

(Yellow pigment PY-1)

, 200 parts of a nickel complex yellow pigment CI Pigment Yellow 150 ("E-4 GN" available from Rank Sess), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a 1 gallon stainless steel kneader (manufactured by INOUE KK) For 8 hours. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while being heated to 80 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 DEG C for one day and one night To obtain a yellow pigment PY-1.

(Yellow pigment PY-2)

, 200 parts of quinophthalone yellow pigment CI Pigment Yellow 138 ("K0961HD" manufactured by BASF Co.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a 1 gallon stainless steel kneader (manufactured by INOUE KK) Kneaded. Subsequently, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while being heated to 80 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 DEG C for one day and one night To obtain a yellow pigment PY-2.

(Yellow pigment PY-3)

200 parts of isoindoline yellow pigment CI Pigment Yellow 185 ("PalIotolYellowL1155" manufactured by BASF), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a 1 gallon stainless steel kneader (manufactured by INOUE KK), kneaded at 80 ° C. for 8 hours Respectively. Then, this kneaded product was charged into 8000 parts of hot water and stirred for 2 hours while being heated to 80 to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C, Yellow pigment PY-3 was obtained.

(Black pigment PBLK-2)

Perylene-based black pigment C.I. , 500 parts of Pigment Black 32 (&quot; PalIogenBlackL0086 &quot; manufactured by BASF), 2500 parts of sodium chloride, and 100 parts of diethylene glycol:

Was kneaded in a stainless steel first gallon kneader (manufactured by Inoue Kogyo Co., Ltd.) at 80 DEG C for 12 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a black pigment PBLK-2.

(Black pigment PBLK-3)

500 parts, 2500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by Inoue Kogyo Co., Ltd.), and kneaded at 40 占 폚 for 12 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a black pigment PBLK-3.

(Black pigment PBLK-4)

500 parts of sodium perchlorate, and 250 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by Inoue Kogyo Co., Ltd.) at 80 ° C and 5 parts of 5% by mass of CI Pigment Black 31 ("PalIogen Black S0084" Time. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a black pigment PBLK-4.

(Black pigment PBLK-5)

500 parts of sodium perchlorate, and 250 parts of diethylene glycol were poured into a 1-gallon stainless steel gallon kneader (manufactured by Inoue Kogyo Co., Ltd.), and kneaded at 80 ° C for 5 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a black pigment PBLK-5.

Table 2 shows the average primary particle size and aspect ratio of the pigment.

PY-4: Nickel complex system yellow pigment C.I. Pigment Yellow 150 (&quot; E-4 GN &quot;

PY-5: quinophthalone yellow pigment C.I. Pigment Yellow 138 ("K0961HD" manufactured by BASF)

PY-6: isoindophene yellow pigment C.I. Pigment Yellow 185 ("PalIotolYellowL1155" manufactured by BASF)

PBLK-1: Perylene black pigment "Lumogen Black FK 4280" manufactured by BASF

PBLK-6: Carbon black pigment "# 45" manufactured by Mitsubishi Chemical Corporation

PBLK-7: Carbon black pigment "MA220" manufactured by Mitsubishi Chemical Corporation

&Lt; Process for producing acrylic resin solution >

(Preparation of acrylic resin solution 1)

In a separable four-necked flask, 70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by TOA Corporation) And 0.4 part of 2'-azobisisobutyronitrile was added dropwise over 2 hours. 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 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl ether acetate was added to the resin solution so that the non-volatile content became 20 wt% Acrylic resin solution 1 was obtained.

(Preparation of acrylic resin solution 2)

370 parts of cyclohexanone was poured into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer. The temperature of the flask was raised to 80 占 폚 and the inside of the flask was purged with nitrogen. 18 parts of cumyl phenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2,2'-azobisisobutyl And 2.0 parts of ronitryl was added dropwise over 2 hours. After dropwise addition, the mixture was further reacted at 100 DEG C for 3 hours, and then 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 DEG C for 1 hour. Subsequently, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the vessel, and the reaction was continued at 120 DEG C for 6 hours to obtain a solid content 0.5, the reaction was terminated to obtain a solution of the acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the hydroxyl groups formed) and 0.5 part of triethylamine were added and reacted at 120 ° C for 3.5 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 19000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Cyclohexanone was added to the resin solution so that the nonvolatile content became 20 wt% To obtain an acrylic resin solution 2 as a curable resin.

[Example 1]

(Pigment dispersion (D-1))

The mixture was stirred and homogeneously mixed, and then dispersed for 3 hours by means of zirconia beads having a diameter of 0.5 mm ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) And filtered through a 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]

The pigment dispersions (D-2 to D-30) were 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 blending amounts shown in Tables 3 and 4.

&Lt; Evaluation of pigment dispersion >

The viscosity characteristics and the contrast ratio (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 characteristic)

The viscosity of the pigment dispersion was measured by using an E-type viscometer ("ELD-type viscometer" manufactured by Synchro Industry Co., Ltd.) at 25 캜. Separately, 25 g of the pigment dispersion was allowed to stand in a sealed state in a glass container at 40 占 폚 for 7 days, and then the viscosity was measured in the same manner as described above to obtain a viscosity with time. In addition, the evaluation was made in three stages based on the following criteria.

○: Viscosity less than 20 mPa · s

?: Viscosity of not less than 20 mPa 占 퐏, less than 40 mPa 占 퐏

×: Viscosity of 40 mPa · s or more

(Contrast ratio (CR))

The resulting pigment dispersions (D-1 to D-17) were spin coated at a rotation number of 3 to prepare a coated substrate having a dried film thickness of about 1 mu m. After coating, the film was dried at 80 DEG C for 30 minutes in a hot air oven, and then the film thickness and the contrast ratio were measured. From the data of the three points, the contrast ratio (CR) at a film thickness of 1 mu m was determined by a first correlation method. In addition, the evaluation was made in three stages based on the following criteria.

○: CR8000 or higher

?: Less than CR8000, more than 6000

×: less than CR6000

(Optical density (OD))

The resulting pigment dispersion (D-18 to 30) was coated on a 100 mm x 100 mm glass substrate by a spin coat method, and then a coating film having a dry film thickness of 1.0 탆 was prepared and heated at 230 캜 for 20 minutes. The optical density (OD) of the thus obtained pigment dispersion coated substrate was measured with a Macbeth densitometer (GRETAGD200-II) to determine the optical density (OD) at a film thickness of 1.0 mu m.

The OD was evaluated in three stages based on the following criteria.

○: OD 1.5 or higher

DELTA: OD of 1.3 or more, less than 1.5

×: less than OD 1.3

An AB block having an average primary particle diameter of 20 to 50 nm and a coloring agent containing a pigment having an aspect ratio of pigment particles of 1: 1 to 1: 3.5, a B block having a functional group containing a hydrophilic A block and a hydrophilic solvent, Wherein the coloring composition for a color filter of the present invention comprising an acrylic block copolymer and a resinous dispersant having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solids, All were low in viscosity and stable, and good CR results were obtained (Examples 1 to 8).

Among them, the pigment dispersion (D-3) of Example 3, in which the metal salt of quinophthalone skeleton sulfonic acid was further added to the pigment dispersion (D-1) of Example 1, CR and viscosity are even better.

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

The pigment dispersion (D-13) of Comparative Example 5 and the pigment dispersion (D-12) of Comparative Example 4 having an amine value of less than 10 mgKOH / g and a 99 mgKOH / g or higher of the resinous dispersant had a high viscosity, In particular, the pigment dispersion (D-13) of Comparative Example 5 having less than 10 mgKOH / g had a low CR, and the pigment dispersion (D-14) of Comparative Example 6 using a random dispersant exhibited a high viscosity .

An AB block having an average primary particle diameter of 20 to 50 nm and a coloring agent containing a pigment having an aspect ratio of pigment particles of 1: 1 to 1: 3.5, a B block having a functional group containing a hydrophilic A block and a hydrophilic solvent, Wherein the coloring composition for a color filter of the present invention comprising an acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solids, together with a resinous dispersant, , All of which were low in viscosity and stable, and had good OD (Examples 9 to 14).

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

On the other hand, the pigment dispersion (D-24) of Comparative Example 10 containing pigment particles having an average primary particle diameter of 15 nm greatly increased in viscosity. The OD of the pigment dispersion (D-25) of Comparative Example 11 containing pigment particles having an average primary particle diameter of 100 nm is greatly poor. Furthermore, the OD of the pigment dispersion (D-26) of Comparative Example 12 in which the pigment particles having an aspect ratio of 1: 4.0 is included is significantly poor.

The pigment dispersion (D-28) of Comparative Example 14 having an amine value of the resinous dispersant of less than 10 mgKOH / g and the pigment dispersion (D-27) of Comparative Example 13 having a viscosity of 99 mgKOH / g or more had a viscosity . In particular, the pigment dispersion (D-28) of Comparative Example 14 having an OD of less than 10 mgKOH / g has a low OD, and the pigment dispersion (D-29) of Comparative Example 15 using a random dispersant has a high viscosity .

[Example 15]

(Photosensitive coloring composition (R-1))

The following mixture was stirred and mixed so as to be homogeneous, and then filtered through a filter of 1.0 탆 to obtain a photosensitive coloring composition (R-1).

(Pigment dispersion) (total 50 parts)

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

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

Photopolymerization initiator ("Irgacure 907" manufactured by Chiba Japan): 1.2 parts

(EAB-F manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Silane coupling agent (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

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

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

The photosensitive coloring compositions (R-2 to R-32) were obtained in the same manner as in the photosensitive coloring composition (R-1) except that the pigment dispersions were changed to the kinds and blending amounts of the pigment dispersions shown in Tables 7 and 8. In the photosensitive coloring composition, the pigment dispersions 1 and 2 are used in combination, but the total amount as a pigment dispersion is 50 parts in all the photosensitive coloring compositions.

&Lt; Evaluation of Photosensitive Coloring Composition >

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

(Viscosity characteristic)

The viscosity of the photosensitive coloring composition was measured by using an E-type viscometer ("ELD-type viscometer" manufactured by Synchro Industry Co., Ltd.) at 25 캜. Separately, 25 g of the pigment dispersion was allowed to stand in a sealed container in a glass container at 40 占 폚 for 7 days, and then the viscosity was measured in the same manner as described above to obtain a viscosity with time.

○: Viscosity less than 4.0 mPa · s

?: Viscosity 4.0 mPa 占 퐏 or more, less than 7.0 mPa 占 퐏

×: Viscosity of 7.0 mPa · s or more

(Contrast ratio (CR))

The resulting photosensitive coloring compositions (R-1 to R-18) were spin-coated to prepare three coated substrates so as to have a dry thickness of about 2 占 퐉 by changing the number of revolutions. After coating, the film was dried at 80 DEG C for 30 minutes in a hot air oven, and then the film thickness and the contrast ratio were measured. From the data of the three points, the contrast ratio (CR) at a film thickness of 1 mu m was determined by a first correlation method. In addition, the evaluation was made in three stages based on the following criteria.

○: CR8000 or higher

?: Less than CR8000, more than 6000

×: less than CR6000

(Optical density (OD))

The obtained photosensitive coloring compositions (R-19 to 32) were coated on a 100 mm x 100 mm glass substrate by a spin coat method, and then a coated film having a dry film thickness of 1.0 탆 was prepared and heated at 230 캜 for 20 minutes. The optical density (OD) of the thus obtained pigment dispersion coated substrate was measured by a Macbeth densitometer (GRETAGD200-II) to determine the optical density (OD) at a film thickness of 1.0 mu m.

The OD was evaluated in three stages based on the following criteria.

○: OD 1.5 or higher

DELTA: OD of 1.3 or more, less than 1.5

×: less than OD 1.3

(Developing speed)

The photosensitive coloring composition was coated on a 10 cm x 10 cm glass substrate by a spin coat method and then heated in a clean oven at 70 캜 for 15 minutes to remove the solvent to obtain a coating film having a thickness of about 2 탆. Subsequently, the substrate was exposed to 60 mJ / cm ² through a mask pattern with high-pressure mercury or the like, sprayed at a pressure of 0.25 MPa using 0.04 wt% potassium hydroxide aqueous solution (developing liquid temperature 26 캜) The time until the substrate surface was exposed (development dissolution time) was measured by dissolving the coating film. The development dissolution time for each photosensitive coloring composition was measured and evaluated in three stages based on the following criteria.

○: Less than 20 seconds

?: 20 seconds or more, less than 30

×: more than 30 seconds

An AB block having an average primary particle diameter of 20 to 50 nm and a coloring agent containing a pigment having an aspect ratio of pigment particles of 1: 1 to 1: 3.5, a B block having a functional group containing a hydrophilic A block and a hydrophilic solvent, And a coloring composition for a color filter of the present invention comprising an acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solids, together with a resinous dispersant (Examples 15 to 19 and 23 to 24), all of which were low in viscosity, stable, high in CR, and fast in development speed.

Among them, the photosensitive coloring composition (R-3) of Example 17, in which the metal salt of quinophthalone skeleton sulfonic acid was added to the photosensitive coloring composition (R-1) of Example 15, This was a more preferable result.

On the other hand, the photosensitive coloring composition (R-11) of Comparative Example 17 in which the pigment particles had an average primary particle diameter of 15 nm and 150 nm had a high initial viscosity and markedly increased with time. On the other hand, in the photosensitive coloring composition (R-12) of Comparative Example 18 in which the pigment particles have an average primary particle diameter of 95 nm and 150 nm, the CR is largely inferior. Further, the photosensitive coloring composition (R-13) of Comparative Example 19, in which the aspect ratios of the pigment particles are 1: 4.5 and 1: 4.3, is greatly poor in CR.

As described above, all of the comparative examples could not satisfy CR, viscosity, and development speed.

An AB block made of 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, a B block having a functional group containing a hydrophilic A block and a hydrophilic solvent, Copolymer or a BAB block copolymer and an acrylic block copolymer having an amine value of 10 mgKOH / g or more and 99 mgKOH / g or less in terms of effective solids, together with a resinous dispersant, is used as the coloring composition for a color filter of the present invention, All of them had a low viscosity, a high stability, a high OD, and a high developing speed, which were good (Examples 25 to 31).

Among them, the photosensitive coloring composition (R-21) of Example 27, in which the metal salt of the quinophthalone skeleton sulfonic acid is added to the photosensitive coloring composition (R-19) of Example 25, Results.

On the contrary, the photosensitive coloring composition (R-26) of Comparative Example 25 having an average primary particle diameter of the pigment particles of 15 nm was significantly thickened. The OD of the photosensitive coloring composition (R-27) of Comparative Example 26 in which the average primary particle diameter of the pigment particles is 100 nm is significantly poor. Furthermore, the OD of the photosensitive coloring composition (R-28) of Comparative Example 27 in which the aspect ratio of the pigment particles is 1: 4.0 is greatly poor.

The photosensitive coloring composition (R-30) of Comparative Example 29 having an amine value of the resinous dispersant of less than 10 mg KOH / g or the photosensitive coloring composition (R-29) of Comparative Example 28 having a viscosity of not less than 99 mgKOH / . Further, the photosensitive coloring composition (R-29) of Comparative Example 28 was a result of a slow development rate due to a high amine value. The photosensitive coloring composition (R-31) of Comparative Example 30 using a random dispersant exhibited high viscosity.

&Lt; Production of color filter &

5.0 parts of the total amount of the green pigment and the yellow pigment in the photosensitive coloring composition (R-1), 5.0 parts of the carbon black pigment (PBLK-7) in the black photosensitive coloring composition 1, and 5.0 parts of CI Pigment Red CI Pigment Blue 15: 3 was added to 5.0 parts of CI Pigment Green 58 / CI Pigment Yellow 150 = 3.0 parts / 2.0 parts in the case of the green photosensitive coloring composition 1, Except that the photosensitive coloring composition 1, the red photosensitive coloring composition 1, the green photosensitive coloring composition 1, and the blue photosensitive coloring composition 1 were prepared in the same manner as the photosensitive coloring composition (R-1) .

[Preparation of color filter 1]

A Daikotaro black photosensitive coloring composition 1 was coated to a thickness of about 1.0 mu m on a glass substrate of 100 mm x 100 mm, and the solvent was removed and dried in an oven at 70 DEG C for 20 minutes. Subsequently, stripe pattern exposure was performed by ultraviolet light using an exposure apparatus. The exposure dose was 100 mJ / cm ² . Further, the unexposed portions were removed by a developing solution containing a sodium carbonate aqueous solution, and then cleaned with ion-exchanged water. The substrate was heated at 230 占 폚 for 20 minutes to form a black matrix having a line width of about 10 占 퐉.

Subsequently, a red photosensitive coloring composition 1 was coated to a thickness of about 2 탆 on a glass substrate on which a black matrix was formed, and the solvent was removed and dried in an oven at 70 캜 for 20 minutes. Subsequently, stripe pattern exposure was performed by ultraviolet light using an exposure apparatus. The exposure dose was 100 mJ / cm ² . Further, the unexposed portion was removed by spraying with a developing solution comprising an aqueous solution of sodium carbonate, cleaned with ion-exchanged water, and the substrate was heated at 230 占 폚 for 30 minutes to form a red filter segment having a line width of about 50 占 퐉. Then, in the same operation, a blue filter segment was formed using a photosensitive coloring composition (R-1) and a blue photosensitive coloring composition 1 in the vicinity of the red filter segment, and three color filters The color filter 1 having the filter segments of FIG.

[Production of color filter 2]

A dicotaro photosensitive coloring composition (R-24) was coated to a thickness of about 1.0 mu m on a 100 mm x 100 mm TFT substrate, and the solvent was removed and dried in an oven at 70 DEG C for 20 minutes. Subsequently, stripe pattern exposure was performed by ultraviolet light using an exposure apparatus. The exposure dose was 100 mJ / cm ² . Further, the unexposed portions were removed by spraying with a developing solution comprising an aqueous sodium carbonate solution, and then cleaned with ion-exchanged water. The substrate was heated at 230 占 폚 for 20 minutes to form a black matrix having a line width of about 10 占 퐉.

Subsequently, a red photosensitive coloring composition 1 was applied to a thickness of about 2 탆 on a glass substrate having a black matrix formed thereon, and the solvent was removed and dried in an oven at 70 캜 for 20 minutes. Subsequently, stripe pattern exposure was performed by ultraviolet light using an exposure apparatus. The exposure dose was 100 mJ / cm ² . Further, the unexposed portion was removed by spraying with a developing solution comprising an aqueous solution of sodium carbonate and then cleaned with ion-exchanged water. The substrate was heated at 230 占 폚 for 30 minutes to form a red filter segment having a line width of about 50 占 퐉. Then, in the same operation, a blue filter segment was formed by using the green photosensitive coloring composition 1 and then the blue photosensitive coloring composition 1 in the vicinity of the red filter segment, and three color filter segments To obtain a color filter 2.

Since the color filters 1 and 2 each include at least one of the filter segments and the black matrix formed from the color composition for a color filter of the present invention, it is possible to circularize in a short time without leaving any residue in the developing process, Since the ratio is high and the color reproduction area is wide, the liquid crystal display device using the color filter can display a bright color having stretchability.

In the color filter 2 of the present invention, although the BM is formed on the TFT, there is no image sticking because of its excellent electric characteristics. In addition, since the manufacturing process can be simplified, the liquid crystal display device using the color filter can reproduce a clear color with a high response speed and low cost.

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

First, preparation of an acrylic resin solution used in Examples and Comparative Examples, physical properties of a perylene black pigment, a structural formula of a pigment derivative, and production of a black pigment dispersion will be described.

[Preparation of acrylic resin solution]

In a separable four-necked flask, 70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer, and the temperature of the reactor was raised to 80 ° C. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by TOA Corporation) And 0.4 part of 2'-azobisisobutyronitrile was added dropwise over 2 hours. 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 heated and dried at 180 DEG C for 20 minutes to measure the non-volatile content. To the resin solution thus synthesized, methoxypropyl acetate was added so that the non-volatile content became 30% Solution.

[Physical Properties of Perylene-Based Black Pigment]

The perylene black pigment 1 '

Perylene black pigment "Lumogen Black FK4280" manufactured by BASF

The perylene black pigment 2 '

Perylene-based black pigment C.I. Pigment Black 31 ("Paliogen Black S0084" manufactured by BASF)

The perylene black pigment 3 '

Perylene-based black pigment C.I. Pigment Black 32 ("Paliogen Black L0086" manufactured by BASF)

Periferous black pigment 4 '

Perylene black pigment "Lumogen Black FK4281" manufactured by BASF

The perylene black pigment 5 '

Perylene-based black pigment C.I. 500 parts of Pigment Black 31 ("Paliogen Black S0084" manufactured by BASF), 2500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a 1 gallon stainless steel kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 5 hours. Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a perylene black pigment 5 '.

The perylene black pigment 6 '

500 parts, 2500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by Inoue Kogyo Co., Ltd.) of a perylene black pigment ("Lumogen Black FK4281" manufactured by BASF) and kneaded at 80 ° C for 5 hours . Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a perylene black pigment 6 '.

The perylene black pigment 7 '

500 parts, 2500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by INOUE MFG. CO., LTD.) Of a perylene black pigment ("Lumogen Black FK4281" manufactured by BASF) . Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a perylene black pigment 7 '.

The perylene black pigment 8 '

500 parts of a perylene black pigment CIPigment Black 32 ("Paliogen Black L0086" manufactured by BASF), 2500 parts of sodium chloride and 250 parts of diethylene glycol were poured into a 1 gallon stainless steel kneader (manufactured by INOUE KK) and kneaded at 80 ° C for 12 hours . Next, this kneaded product was charged into 5 liters of hot water and stirred for 1 hour while being heated to 70 DEG C to form a slurry, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, And dried to obtain a perylene black pigment 8 'shown in Table 11.

[Structural Formula of Pigment Derivative]

[Production of black pigment dispersion]

(Black pigment dispersion 1 ')

The mixture of the following composition was uniformly stirred and then dispersed for 5 hours by means of zirconia beads having a diameter of 0.5 mm by means of an Agger mill (Mini Model M-250 MKII, manufactured by Eiger Japan) To obtain a black pigment dispersion 1 '.

Carbon black: 14.4 parts &quot;# 45 &quot; (manufactured by Mitsubishi Chemical Corporation)

Pigment derivative 1 ': 0.6 part

Resin type dispersant 1 ': 1.5 parts

&Quot; BYK-110 &quot; (manufactured by VICK Chemie Japan)

(Acid value 53 mgKOH / g, nonvolatile content 52%) Acrylic resin solution: 14.1 parts

Solvent: Cyclohexanone: 69.4 parts

(Black pigment dispersions 2 'to 25')

Black pigment dispersions 2 'to 25' were prepared in the same manner as in the black pigment dispersion 1 'except that the composition and blending amount shown in Table 13 were used.

The abbreviations and compounds in Table 13 are shown below.

· Pigment

R / B / Y pigment mixture 1: PR177 / PB15: 6 / PY139 = 50/40/10

R / B / Y Pigment mixed color 2: Mixed in weight ratio of PR179 / PB15: 6 / PY185 = 50/40 /

· Pigment derivatives

Derivatives 1 'to 4': The pigment derivatives 1 'to 4'

· Resin type dispersant

Resin type dispersant 1 ': Acid resin type dispersant BYK-110

(Acid value 53 mg KOH / g, nonvolatile content 52%) (trade name, manufactured by Bigk Chemie Japan)

Resin type dispersant 2 ': Acid resin type dispersant BYK-111

(Manufactured by Vick Chemical Co., Ltd.) (acid value: 129 mgKOH / g, nonvolatile content: 100%)

Resin Type Dispersant 3 ': Acid Resin Type Dispersant "BYK-171"

(Acid value 13 mgKOH / g, nonvolatile content 40%) manufactured by Vick Chemical Co.,

Resin type dispersant 4: Alkali resin type dispersant "BYK-6919"

(Bigk Chemie Japan) (nonvolatile content 60%)

Solvent: Cyclohexanone

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

(Black resin composition 1 'to 33')

The black pigment dispersions, acrylic resin solution and solvent shown in Table 14 were stirred and mixed so as to be uniform so that black resin compositions 1 'to 33' were prepared.

The abbreviations and compounds in Table 14 are shown below.

Perylene content (%): Content (%) of perylene pigment based on the total amount of light-shielding black pigment (A)

Solid content (%): Solid content concentration in black resin composition

Solvent: Cyclohexanone

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

[Viscosity]

The viscosity of the black resin composition on the day after the preparation was measured at 25 캜 using a TVE-20 L type viscometer (manufactured by Synchro Industry Co., Ltd.) to obtain an initial viscosity (? 0: mPa 占 퐏). In addition, as a stability evaluation, the viscosity (? 7: mPa 占 퐏) after preservation at 40 占 폚 for 7 days was measured in the same manner, and the rate of change was calculated by the following formula.

Change rate (%) = viscosity after storage at 40 占 폚 for 7 days (? 7) / initial viscosity (? 0) 占 100

In addition, the change rate over time was evaluated in three stages based on the following criteria.

○: Less than 110% change over time

?: Over time change rate 110% or more, less than 140%

×: Over 140% change over time

[Optical density]

A black resin composition was coated on a 100 mm x 100 mm glass substrate by a spin coating method, and then a coated film having a dried film thickness of 1.0 탆 was prepared and heated at 230 캜 for 20 minutes. The optical density (OD) of the black resin composition coated substrate thus obtained was measured by a Macbeth densitometer (GRETAGD200-II) to determine the optical density (OD) at a film thickness of 1.0 mu m.

The OD was evaluated in three stages based on the following criteria.

○: OD 2.70 or higher

?: OD 2.50 or more and less than 2.70

×: less than OD 2.50

[Light transmittance]

The black pigment dispersion was coated on a 100 mm x 100 mm glass substrate by a spin coating method and then subjected to a baking process at 230 캜 for 20 minutes to prepare a coating film having a dry film thickness of 1.0 탆. The light transmittance of the obtained black pigment dispersion coated substrate was measured by a spectrophotometer (HITACHIU-3900H), and the light transmittance was determined and evaluated in three stages based on the following criteria.

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

?: Light transmittance (wavelength 1000 nm) 15% or more and less than 30%

X: light transmittance (wavelength 1000 nm) less than 15%

As the light-shielding black pigment according to the second embodiment, the perylene black pigment and the black pigment dispersion containing a specified amount of carbon black were all excellent in fluidity and stability. When the content of the perylene black pigment in the light-shielding black pigment is 95 wt% or less, the optical density is also high and good light-shielding properties are exhibited. Furthermore, the light transmittance at 780 nm satisfied 15% or more, which is a level required for the mask alignment operation.

By using the pigment derivative as the pigment dispersant, the initial viscosity was lowered and the flowability was improved, and the stability with time was also improved (Examples 1 'to 17', 19 'to 25'). Further, when the pigment derivative and the resinous dispersant are used together, they exhibit good stability over time (Examples 1 'to 5', 10 'to 17' and 20 'to 25'), (Examples 1 'to 5', 10 ', 11', 13 'to 17', 20 'to 25').

When the proportion of the perylene 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 (Comparative Example 2 '). Further, when the perylene black pigment did not satisfy any one of the specific average particle diameter and the aspect ratio, the optical density was lowered or the stability with time deteriorated, or both (Comparative Examples 3 'to 4) 7 ').

Further, when the solid content concentration was 40% by weight, the viscosity became high and the liquidity did not have a proper coating property for the coating (Comparative Example 8 ').

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

[Example 23 ']

(Resist material 1 '(photosensitive black resin composition 1'))

The mixture having the following composition was stirred and mixed so as to be homogeneous, and then filtered with a 1 탆 filter to obtain a resist 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 ': 0.40 part

"Irugakia OXE-02" (made by Chiba Japan)

Ethylenic unsaturated compound: 2.00 parts

&Quot; ARONIX M-402 &quot;

Surface conditioner: 1.00 part

(A solution obtained by diluting 2 parts of "BYK-330" (trade name, manufactured by BICK Chemie Japan) (nonvolatile content 50% by weight) with 98 parts of propylene glycol monomethyl ether acetate)

Solvent: Cyclohexanone: 30.60 parts

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

(Resist materials 2 'to 16')

Resist materials 2 'to 16' (photosensitive black resin compositions 2 'to 16') were produced in the same manner as the resist material 1 '(photosensitive black resin composition 1') except that the composition and blending amount shown in Table 16 were used .

The abbreviations and compounds in Table 16 are shown below.

· Photopolymerization initiator

Initiator 1 ': "Irgacure OXE-02" (manufactured by Chiba Japan)

Initiator 2 ': "Irgacure 379 EG" (manufactured by Chiba Japan) / "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.) in a ratio of 90/10

Initiator 3: "Irgacure 379 EG" (manufactured by Chiba Japan) / "Irgacure 907" (manufactured by Chiba Japan) / "DETX-S" (manufactured by Nippon Kayaku Co., Ltd.)

Ethylenic unsaturated compound: "Aronix M-402" (manufactured by Donga Synthetic Chemical Co., Ltd.)

Surface-adjusting agent: A solution prepared by diluting 2 parts of "BYK-330" (trade name, manufactured by BICK Chemie Japan) (nonvolatile matter 50% by weight) with 98 parts of propylene glycol monomethyl ether acetate

Solvent: Cyclohexanone

Optical density, light transmittance and relative dielectric constant of the obtained resist material were measured by the following methods. The results are shown in Table 17.

[Optical density]

A resist material was coated on a glass substrate of 100 mm x 100 mm by a spin coating method and vacuum-dried. Thereafter, ultraviolet rays were exposed to 100 mJ / cm ² using an ultra-high pressure mercury lamp. Subsequently, the unexposed portion was spray-developed using an aqueous solution of sodium carbonate and then cleaned with ion-exchanged water to remove the unexposed portion and heated at 230 占 폚 for 20 minutes to prepare a resist-coated substrate having a thickness of 1.0 占 퐉. The optical density (OD) of the substrate thus obtained was measured by a Macbeth densitometer (GRETAGD200-II) to determine the optical density (OD) at a film thickness of 1.0 mu m.

The OD was evaluated in three stages based on the following criteria.

○: OD 2.70 or higher

?: OD 2.50 or more and less than 2.70

×: less than OD 2.50

[Light transmittance]

A resist material was coated on a 100 mm x 100 mm glass substrate by a spin coating method and then subjected to a baking process at 230 캜 for 20 minutes to prepare a coating film having a dry film thickness of 1.0 탆. The light transmittance of the resist-coated substrate thus obtained was measured by a spectrophotometer (HITACHIU-3900H), and the light transmittance was determined and evaluated in three stages based on the following criteria.

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

?: Light transmittance (wavelength 1000 nm) 15% or more and less than 30%

X: light transmittance (wavelength 1000 nm) less than 15%

[Specific dielectric constant]

The photosensitive black resin composition was coated on a glass substrate having a thickness of 1.1 mm, which was 100 mm x 100 mm and aluminum deposited for electrodes, using a spin coating machine at a rotational speed of 1.0 m thick after the following heating step, To obtain a coated substrate. Subsequently, after the drying under reduced pressure, an ultra-high pressure mercury lamp was used to perform ultraviolet exposure at an integrated light quantity of 100 mJ / cm ² and an illumination of 25 mW / cm ² . After the coated substrate was heated at 230 캜 for 20 minutes and cooled, aluminum for electrode having an area of 3.464E-4 m ² was deposited on the obtained cured coating film, and a sample having a cured coating film sandwiched by aluminum electrodes was produced. The relative dielectric constant of the obtained sample was measured at an applied voltage of 100 mV using an impedance analyzer ("1260 type" Impedance Analyzer manufactured by Solartron). The relative permittivity was evaluated in three stages according to the following criteria.

?: Specific dielectric constant of 8.0 or less

DELTA: Pass ratio 8.0 8.0 or less

×: Specific dielectric constant exceeding 9.0

As shown in Table 17, when 78 to 95% by weight of the perylene black pigment was contained as the light-blocking black pigment, the optical density was 2.5 or more and the light transmittance at 780 nm was 15% or more, 9.0 or less, and satisfies all the required characteristics of the BM provided in the BOA type TFT color display device.

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

In addition, when the perylene black pigment did not satisfy any one of the specific average particle diameter and the aspect ratio, the light shielding property and electric characteristics were bad (Comparative Examples 14 'to 18'). In the case of using a combination of organic pigments as colorants (Comparative Examples 19 ', 20'), the light transmittance and the relative dielectric constant in the near infrared region were good, but the light shielding property was bad.

As described above, in all of the comparative examples, it is impossible to satisfy all of the light shielding property, the light transmittance and the relative permittivity.

<Fabrication of color liquid crystal display device>

The color liquid crystal display can be manufactured by a conventionally known method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2000-162643.

(TFT) type color liquid crystal display device having a black matrix formed from 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 serving as a pixel electrode was formed on the color filter, etched in a predetermined pattern, and then a black matrix was formed between RGB pixels to produce 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 alignment layer was formed thereon to prepare a counter substrate.

The array substrate and the counter substrate prepared as described above were arranged so as to face each other with the electrode layers facing each other. The space between the substrates was kept constant by using spacer beads, and the periphery was sealed with a sealing agent Lt; / RTI &gt; After the liquid crystal composition was injected into the opening, the opening was sealed. A liquid crystal display device thus manufactured was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

As a result, all of the color display devices having the driving substrate of the thin film transistor (TFT) type color liquid crystal display device including the black matrix formed using the black resin composition of the present invention are excellent in light shielding property, The display contrast of the display device is excellent, and furthermore, since the display device has a low dielectric constant property, it has a small adverse effect on electric characteristics called the alignment disorder of the liquid crystal and has excellent light transmittance in the near infrared region.

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

[Preparation of acrylic resin solution]

The reaction vessel was charged with 800.0 parts of cyclohexanone, and the mixture was heated to 100 占 폚 while introducing nitrogen gas into the vessel. 60.0 parts of methacrylic acid, 65.0 parts of butyl methacrylate, 65.0 parts of methyl methacrylate, 60.0 parts of styrene, And 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour, and the mixture was further reacted at 100 DEG C for 3 hours. Then, 2.0 parts of azobisisobutyronitrile was dissolved in 50.0 parts of cyclohexanone, and the mixture was further stirred at 100 DEG C And the reaction was continued for 1 hour to synthesize a resin solution. After cooling to room temperature, about 2.0 g of the resin solution was sampled and heated and dried at 180 DEG C for 20 minutes to measure non-volatile components. Cyclohexanone was added to the resin solution so that the nonvolatile content was 20% Was prepared. At this time, the weight average molecular weight of the acrylic resin was 40,000.

[Perylene black pigment]

Perylene black pigments such as the perylene black pigments 1 'to 8' shown in Table 11 were prepared.

[Structural Formula of Pigment Derivative]

Pigment derivatives such as the pigment derivatives 1 'to 4' shown in Table 12 were prepared.

[Example 1 &quot; ']

The mixture of the following composition was uniformly stirred and then dispersed for 5 hours by means of zirconia beads having a diameter of 0.5 mm by means of an Agger mill (Mini Model M-250 MKII, manufactured by Eiger Japan) To obtain a black resin composition (black pigment dispersion 1 &quot;).

Perylene black pigment 1 ': 6.5 parts

Pigment derivative 1 ': 0.7 part

Resin type dispersant 1 ': 1.4 parts

&Quot; BYK-110 &quot; manufactured by Bigk Chemie Japan (acid value 53 mgKOH / g)

Acrylic resin solution: 33.6 parts

solvent; Cyclohexanone: 57.8 parts

[Examples 2 '' to 13 '', Comparative Examples 1 '', 2 '' and 4 '' to 9 '']

The black pigment dispersions 2 '' to 13 '' and 15 '' to 22 '' were prepared in the same manner as in Example 1 '' (black pigment dispersion 1 '') except that the composition and mixing amount shown in Table 18 were used. .

The abbreviations and compounds in Table 18 are the same as those described for Table 13.

[Comparative Example 3 &quot; ']

The mixture was stirred and homogeneously mixed, and then dispersed for 5 hours by means of zirconia beads having a diameter of 0.5 mm ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) And filtered through a filter to prepare a black pigment dispersion 14 &quot;.

Carbon black (manufactured by Mitsubishi Chemical Corporation, # 45): 6.5 parts

Pigment derivative 1 ': 0.7 part

Acrylic resin solution: 33.6 parts

Resin type dispersant 1 ': 1.4 parts

&Quot; BYK-110 &quot; manufactured by Bigk Chemie Japan (acid value 53 mgKOH / g)

solvent; Cyclohexanone: 57.8 parts

[Evaluation of viscosity of black pigment dispersion and rate of change with time]

The viscosity of the black pigment dispersion was measured at 25 ° C on the day of preparation of the pigment dispersion by using an E-type viscometer (TVE-20 L type viscometer (manufactured by Sekisui Kagaku Co., Ltd.)) at a revolution of 20 rpm .

Then, the black pigment dispersion which had been counted from the day of preparation of the black pigment dispersion and left to stand at 40 캜 for 7 days was returned to the sample temperature at 25 캜, and the viscosity at the elapsed time was measured according to the above viscosity measurement method. And the change rate over time was obtained.

Change over time (%) = (time viscosity) / (initial viscosity) x 100

In addition, the change rate over time was evaluated in three stages based on the following criteria.

Table 19 shows the results.

○: Less than 110% change over time

?: Over time change rate 110% or more, less than 140%

×: Over 140% change over time

[Optical density]

The black pigment dispersion was coated on a glass substrate of 100 mm x 100 mm by spin coating, vacuum dried, and then heated at 230 캜 for 20 minutes. Thus, a black pigment dispersion coated substrate having a thickness of 1.0 m was prepared, and the optical density (OD) of this substrate was measured by a Macbeth densitometer (GRETAGD200-II) to determine the optical density OD) was obtained.

Table 19 shows the results.

[Transmittance]

The black pigment dispersion was coated on a 100 mm x 100 mm glass substrate by a spin coating method and then subjected to a firing step at 230 캜 for 20 minutes to prepare a coating film having a dried film thickness of 1.0 탆. The transmittance of the coated black pigment dispersion coated substrate was measured with a spectrophotometer (HITACHIU-3900H), and the transmittance was determined. The transmittance was evaluated in three stages according to the following criteria.

Table 19 shows the results.

?: Transmittance (wavelength 1000 nm) 80% or more

?: Transmittance (wavelength 1000 nm) 60% or more and less than 80%

X: transmittance (wavelength 1000 nm) less than 60%

As the light-shielding black pigment, which is a feature of the present invention, a black pigment dispersion having a perylene-based black pigment, pigment dispersant, resin and solvent having an average primary particle diameter of 50 nm or less and an aspect ratio of pigment particles of a specific value, All have good fluidity and stability, and further have high OD value, exhibit good light shielding property, and excellent transmittance (Examples 1 '' to 13 '').

In addition, when the pigment derivative and the resin type dispersing agent are used together, they exhibit a favorable aging stability (Examples 1 '' to 4 '', 9 '' to 13 ''), especially when an acidic resin type dispersant is used (Examples 1 "to 4", 9 ", 10", 12 ", 13").

[Example 14 &quot; ']

(Resist material 1 &quot;)

Subsequently, the mixture having the following composition was stirred and mixed so as to be homogeneous, and then filtered through a 1 탆 filter to obtain a photosensitive black resin composition (resist material 1 ").

Black pigment dispersion 1 &quot; ': 48.0 parts

Acrylic resin solution: 17.2 parts

Photopolymerization initiator: 0.4 parts (Irgacure OXE-02 made by Chiba Japan)

Ethylenically unsaturated ethylenically unsaturated compound: 2.9 parts (Aronix M-402 manufactured by East Asia Synthetic Chemical Industry Co., Ltd.)

1.0 part of a surface conditioner (a solution prepared by diluting 2 parts of BYK-330 (50% by weight of nonvolatile matter) by 98 parts of propylene glycol monomethyl ether acetate manufactured by BICK Chemie Japan)

solvent; Cyclohexanone: 30.5 parts

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

(Resist materials 2 &quot; to 22 &quot;),

Resist materials 2 "to 22" were prepared in the same manner as in Example 14 "(resist material 1") except for changing to the black pigment dispersion shown in Table 20.

[Optical density]

A resist material was coated on a glass substrate of 100 mm x 100 mm by a spin coating method and vacuum-dried. Thereafter, ultraviolet rays were exposed to 100 mJ / cm ² using an ultra-high pressure mercury lamp. Subsequently, the unexposed portion was spray-developed using an aqueous solution of sodium carbonate, cleaned with ion-exchanged water to remove unexposed portions, and heated at 230 占 폚 for 20 minutes to prepare a resist-coated substrate having a thickness of 1.0 占 퐉. The optical density (OD) of the substrate thus obtained was measured by a Macbeth densitometer (GRETAGD200-II) to determine the optical density (OD) at a film thickness of 1.0 mu m.

Table 20 shows the results.

[Transmittance]

A resist material was coated on a 100 mm x 100 mm glass substrate by a spin coating method and then subjected to a baking process at 230 캜 for 20 minutes to prepare a coating film having a dry film thickness of 1.0 탆. The transmittance of the resist-coated substrate thus obtained was measured by a spectrophotometer (HITACHIU-3900H), and the transmittance was determined. The transmittance was evaluated in three stages according to the following criteria.

The results are shown in Table 5.

?: Transmittance (wavelength 1000 nm) 80% or more

?: Transmittance (wavelength 1000 nm) 60% or more and less than 80%

X: transmittance (wavelength 1000 nm) less than 60%

[Specific dielectric constant, tan? (Dielectric tangent)]

The photosensitive black resin composition was coated on a glass substrate of 1.1 mm in thickness and 100 mm in length and 100 mm in thickness for an electrode for electrodes by a spin coating machine at a rotational speed of 1.0 mu m in thickness after the following heating step, To obtain a coated substrate. Subsequently, after the drying under reduced pressure, an ultra-high pressure mercury lamp was used to perform ultraviolet exposure at an integrated light quantity of 100 mJ / cm ² and an illumination of 25 mW / cm ² . After the coated substrate was heated at 230 캜 for 20 minutes and then cooled, aluminum for electrode having an area of 3.464 E-4 m ² was deposited on the obtained cured coating film to prepare a sample having a cured coating film sandwiched by an aluminum electrode. The relative dielectric constant and tan? Of the obtained sample were measured at an applied voltage of 100 mV using an impedance analyzer ("1260 type" impedance analyzer manufactured by Solutron). The relative dielectric constant was evaluated in three stages according to the following criteria.

○: Specific dielectric constant less than 3.5

DELTA: Specific dielectric constant 3.5 or more 4.5 or less

X: Specific dielectric constant exceeding 4.5

The tan δ was evaluated in three stages according to the following criteria.

?: Less than tan? 0.1

?: Tan? 0.1 to less than 0.2

X: tan? 0.2 or more

Table 20 shows the results.

As shown in Table 20, the light-shielding black pigment used was a perylene black pigment having crystal grains having an average primary particle diameter of 50 nm or less and an aspect ratio of 1: 1 to 1: 2, and a third pigment using a pigment dispersant, The resist material according to the embodiment exhibited high optical density, excellent light shielding property, low dielectric constant, and excellent transmittance in the near infrared region (Examples 14 '' to 26 ''). On the other hand, when the perylene pigment did not satisfy any one of the specific average particle diameter and aspect ratio, the optical density was low, the light shielding property was bad, and the electrical properties were also bad (Comparative Example 13 ' '~ 17' ').

Among them, a resist material using a pigment derivative having a parent skeleton of an organic pigment and a basic substituent as a pigment dispersant shows superior results in terms of electrical properties (Example 24 ''), and the organic skeleton of the organic pigment is a dioxazine or diketopyrrole The roll-in resist material also had better tan δ (Examples 19 ", 21" to 23 ").

Further, the resist material using the pigment derivative together with the acidic resin type dispersant having an acid value of 100 to 200 mgKOH / g together with better tan δ, lower initial viscosity, and good stability (Example 22 ").

In Comparative Examples 10 '' and 11 '' (resist materials 12 '' and 13 '') formed of a black resin composition by mixing organic pigments as light-blocking black pigments, the relative dielectric constant and transmittance are at a practical level, The comparative example 12 '' (resist material 14 '') having a low concentration and carbon black exhibited excellent optical density but had a very poor transmittance in the relative dielectric constant and near infrared region. In Comparative Examples 13 '' to 17 '' (resist materials 15 '' to 19 '') in which the perylene pigment did not satisfy any one of the specific average particle diameter and aspect ratio, the optical density was low, Not only is this bad, but also the electrical properties are bad.

Thus, all of the comparative examples could not satisfy the relative dielectric constant, the transmittance, and the light shielding property.

<Fabrication of color liquid crystal display device>

The color liquid crystal display can be manufactured by a conventionally known method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2000-162643.

(TFT) type color liquid crystal display device having a black matrix formed from 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 serving as a pixel electrode was formed on the color filter, etched in a predetermined pattern, and then a black matrix was formed between RGB pixels to produce an array substrate.

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

The array substrate and the counter substrate prepared as described above were disposed so as to face each other with the electrode layers facing each other. The spacers were aligned with the spacer beads while maintaining the gap therebetween, Lt; / RTI &gt; After the liquid crystal composition was injected through the opening, the opening was sealed. A liquid crystal display device thus manufactured was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

As a result, all of the color display devices having the driving substrate of the thin film transistor (TFT) type color liquid crystal display device including the black matrix formed using the black resin composition of the present invention are excellent in light shielding property, The display contrast of the display device is excellent, and furthermore, the low dielectric constant characteristic has a small adverse effect on the electric characteristic called the alignment disorder of the liquid crystal and the excellent transmissivity in the near infrared region is also possible, thereby achieving the mask alignment operation.

Claims (29)

A black resin composition comprising a light-blocking black pigment, a pigment dispersant, a resin, and a solvent,
Wherein the light-blocking black pigment comprises a perylene black pigment and carbon black having an average primary particle diameter of 50 nm or less and an aspect ratio of pigment primary particles of 1: 1 to 1: 2,
Wherein the content of the perylene-based black pigment is 78 to 95% by weight based on the total amount of the light-shielding black pigment, and the solid content is less than 5% by weight and less than 40%
Wherein the pigment dispersant is a pigment dispersant comprising a pigment derivative having an organic substituent group and an acidic resin type dispersant,
Characterized by
Black resin composition.
The method according to claim 1,
Wherein the average primary particle diameter of the perylene black pigment is 20 to 45 nm.
The method according to claim 1,
Wherein the black resin composition further comprises an ethylenically unsaturated compound and a photopolymerization initiator.
A black matrix formed from the black resin composition according to any one of claims 1 to 3.
5. The method of claim 4,
And a relative dielectric constant at a dry film thickness of 1.0 m is 8.0 or less.
5. The method of claim 4,
And a light transmittance at a wavelength of 780 nm at a dry film thickness of 1.0 占 퐉 is 15% or more and less than 99%.
5. The method of claim 4,
Wherein the optical density at a dry film thickness of 1.0 占 퐉 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 claim 4.
A black resin composition comprising a light-blocking black pigment, a pigment dispersant, a resin, and a solvent,
Wherein the light-blocking black pigment is a perylene black pigment having an average primary particle diameter of 50 nm or less and an aspect ratio of pigment particles of 1: 1 to 1: 2, and a solid concentration of 5% by weight or more and less than 40%
Wherein the pigment dispersant is a pigment dispersant comprising a pigment derivative having an organic substituent group and an acidic resin type dispersant,
Characterized by
Black resin composition.
10. The method of claim 9,
Wherein the average primary particle diameter of the perylene black pigment is 20 to 45 nm.
10. The method of claim 9,
Wherein the matrix skeleton of the organic pigment is one of a dioxazine-based pigment and a diketopyrrolopyrrole-based pigment.
10. The method of claim 9,
Wherein the black resin composition further comprises an ethylenically unsaturated compound and a photopolymerization initiator.
A black matrix formed from the black resin composition according to any one of claims 9 to 12.
14. The method of claim 13,
And a relative dielectric constant at a dry film thickness of 1.0 m is 4.5 or less.
14. The method of claim 13,
And a transmittance of a wavelength of 1000 nm at a dry film thickness of 1.0 占 퐉 is 60% or more and less than 99%.
14. The method of claim 13,
Wherein the optical density at a dry film thickness of 1.0 占 퐉 is 1.30 or more.
A substrate for driving a thin film transistor type color liquid crystal display device, which comprises the black matrix according to claim 13. delete delete delete delete delete delete delete delete delete delete delete delete