JPWO2015015962A1 - Pigment composition for color filter and color filter - Google Patents

Abstract

An object of the present invention is to provide a color filter organic pigment composition that is fine and has good dispersion stability and a color filter that contains them and has a high optical density. An organic pigment composition for a color filter comprising a perylene organic pigment and an organic dye derivative containing a sulfonic acid group has high dispersion stability even with fine particles, and has a light-shielding property comprising the organic pigment composition for a color filter. It was found that it is possible to obtain a high color filter.

Description

  The present invention is a color filter pigment composition for forming a color filter of a color liquid crystal display device, and a color filter, and is miniaturized together with a specific organic dye derivative to achieve both miniaturization and dispersion stability. The present invention relates to a pigment composition for a color filter that has a higher light-shielding property than a conventional one and a color filter using the same.

  In the field of liquid crystal display devices, a liquid crystal panel in which a color filter on array (COA) in which a color filter substrate and a TFT array substrate are integrated is attracting attention. The use of the COA eliminates the need for precise alignment performed when the above two substrates are used, and allows the red, blue, and green pixels of the color filter to be miniaturized to the limit. High definition panel can be achieved.

  Such a COA resin black matrix is required to have a large thickness because it requires a high light-shielding property. However, as the film thickness of the resin black matrix increases, the difference in crosslink density in the film thickness direction at the exposed part increases, making it difficult to achieve high sensitivity and obtain a well-shaped black pattern. Become. In addition, as a means of achieving high light shielding, attempts have been made to use a large amount of light shielding material, but when a conductive material such as carbon is used as the light shielding material, the relative permittivity of the black matrix increases and the volume resistance increases. There is a problem that the reliability of the display device is lowered due to the decrease.

  In order to eliminate such drawbacks, an attempt has recently been made to use a black organic pigment composition (organic black matrix) obtained by mixing a chromatic organic pigment so as to be black instead of carbon black as a light shielding material. It is active.

  In Patent Document 1, although there is a description of a light-shielding photosensitive resin composition containing a specific organic pigment for a resin black matrix that defines the maximum light transmittance in a specific wavelength range, it is compared with carbon black. The light shielding property was insufficient. In Patent Document 2, among organic pigments having light transmittance in the visible light region, a combination of a yellow pigment, a blue pigment, and a purple pigment, or a pseudo blackened mixed color organic material composed of a combination of a yellow pigment, a red pigment, and a blue pigment. Although there is a description of a colored resin composition for forming a light shielding curtain made of a pigment, the optical density (OD) is low and the light shielding property is not sufficient. Patent Document 3 proposes a black matrix pigment composition containing blue, yellow, and red organic pigments having a particle size equal to or less than a specific specific surface area. The light shielding property is not obtained. As described above, some inventions have been proposed by mixing pigments. However, it is difficult to obtain a color filter including a black matrix of a color filter that has high insulation, low dielectric constant, and high optical density. There was a problem.

JP 2009-69822 A JP-A-9-302265 JP 2012-32697 A

  The problem to be solved by the present invention is to provide an organic pigment composition for a color filter that is fine and has a high optical density, and a color filter containing them.

  As a result of intensive investigations in view of the above circumstances, the present inventors have found that an organic pigment composition for a color filter comprising a perylene organic pigment and an organic dye derivative containing a sulfonic acid group has high dispersion stability with fine particles. The inventors have found that it is possible to obtain a color filter having a high light shielding property comprising the organic pigment composition for a color filter, and have completed the present invention.

  The present invention relates to an organic pigment composition for a color filter, comprising 1 to 15 parts of an organic dye derivative containing a sulfonic acid group per 100 parts of a perylene organic pigment, and having a primary particle diameter of the pigment of 20 nm to 100 nm. Offer things.

  In the present invention, the perylene organic pigment may be C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 189, C.I. I. Pigment red 190, C.I. I. Pigment red 224, C.I. I. Pigment red 228, C.I. I. Pigment violet 29, C.I. I. Pigment black 31, C.I. I. The organic pigment composition for a color filter according to claim 1, wherein the organic pigment composition is selected from at least one of CI pigment black 32.

  The present invention also provides the organic pigment composition for a color filter according to claim 1, wherein the organic dye derivative is copper phthalocyanine sulfonic acid or a salt thereof.

  Furthermore, the present invention provides a color filter comprising the organic pigment composition for a color filter described above.

  The black matrix composed of other organic pigment compositions such as blue and red used in combination with the organic pigment composition for a color filter of the present invention is excellent in dispersion stability and excellent in light-shielding properties with a high OD value. Play.

Details of the present invention will be described below.
The pigment composition for a color filter of the present invention can form fine particles by performing solvent salt milling of an organic pigment having a perylene structure and an organic dye derivative having a sulfonic acid group. Blue, yellow, red The organic pigment composition for black color filter is comprised by using together organic pigments, such as. The resulting black matrix containing the black organic pigment composition for a color filter has excellent dispersion stability and excellent light shielding properties with a high OD value.

  In the organic pigment composition for a color filter of the present invention, the organic pigment may be any as long as it has a perylene structure.

  Examples of the organic pigment having the above chemical structure include C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 189, C.I. I. Pigment red 190, C.I. I. Pigment red 224, C.I. I. Pigment red 228, C.I. I. Pigment violet 29, C.I. I. Pigment black 31, C.I. I. Pigment Black 32 can be raised. Each organic pigment can be used alone or in combination, and is selected from at least one of the above organic pigments.

  The primary particle diameter of the refined organic pigment is preferably 20 to 150 nm, and is preferably 20 to 100 nm in order to impart high light shielding properties. It has been found that when the primary particle size of the pigment exceeds 150 nm, the dispersion stability is deteriorated, and as a result, light scattering tends to occur.

  The primary particle diameter of the organic pigment in the present invention is that an organic pigment composition is dispersed in a solvent such as cyclohexanone, the dispersion is applied on a colloidal film, and an image of a scanning electron microscope (TEM) is taken. The size of 1000 particles of the obtained photographed image was measured, and the average value was taken as the primary particle diameter of the organic pigment.

  Such organic pigments finer than conventional ones can be broadly classified by a pulverization method such as dry pulverization or wet pulverization. However, as practiced in the present invention, Solvent salt milling, which is kneaded for a long time due to a high inorganic salt ratio, is suitable. This is a useful production method that can achieve both uniformity of particles and reduction in size. The ground mixture treated by solvent salt milling is subjected to washing, purification, and drying steps to become the organic pigment composition of the present invention.

  The solvent salt milling means kneading an organic pigment, a water-soluble inorganic salt, and a hydrophilic organic solvent. Specifically, an organic pigment, a water-soluble inorganic salt, and a hydrophilic organic solvent that does not dissolve the organic pigment are charged into a kneader, and kneading and grinding are performed therein. When the conversion of the crystal form is intended in the kneading, a crude pigment having a crystal form different from that after the kneading can be used as the raw material for the kneading.

  As the water-soluble inorganic salt, for example, inorganic salts such as sodium chloride, potassium chloride, sodium sulfate and the like are preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  Moreover, it is preferable to set it as 8-20 weight part with respect to 1 weight part of organic pigments, and, as for the usage-amount of the said inorganic salt, it is more preferable to set it as 10-15 weight part.

  As the water-soluble organic solvent, those capable of suppressing crystal growth can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2 -Propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene Recall monomethyl ether, dipropylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1-methoxy-2-but-propanol or the like can be used, ethylene glycol or diethylene glycol are preferred.

  Although the usage-amount of the said water-soluble organic solvent is not specifically limited, 0.01-5 weight part is preferable with respect to 1 weight part of organic pigments.

  The kneading temperature is preferably between 30 and 150 ° C. In the case of the organic pigment of the present invention, the above temperature is particularly preferably 80 to 100 ° C. in terms of fineness and crystallinity adjustment.

  As an apparatus used for this kneading, there is a kneader, a mix muller, Trimix (trade name) manufactured by Inoue Seisakusho, which is a planetary mixer described in JP-A-2007-100008, and JP-A-4-122778 The continuous twin-screw extruder described above, Miracle KCK manufactured by Asada Tekko Co., Ltd., which is a continuous single-screw kneader described in JP-A-2006-306996, and the like can be used.

  The pigment composition for a color filter of the present invention may contain a free metal and a free metal ion source, but it is preferable that the amount is as small as possible. Such a free metal and free metal ion source can be washed with acids as described in JP-A-2008-308605. Examples of the acids used include hydrochloric acid and sulfuric acid, and the concentration of hydrochloric acid and sulfuric acid is preferably 0.5% to 4%. Moreover, the temperature at the time of washing | cleaning has preferable 50-90 degreeC. Moreover, you may wash | clean using water.

The organic dye derivative used in the present invention may have any chemical structure as long as the organic dye derivative has a sulfonic acid group or is a sulfonate. An organic pigment derivative having a sulfonic acid group or a sulfonate is often added in order to improve dispersibility in a binder and solvent system, and its effect is well known. The number of substituents of the sulfonic acid group is 1 to 4 per molecule, preferably 0 to 0. Since the perylene organic pigment used in the present invention has a purple hue, an organic dye derivative having the same color is preferable, but organic dye derivatives having different hues can be used. Specifically, there are an azo structure, a benzimidazolone structure, a quinacridone structure, a diketopyrrolopyrrole structure, a phthalocyanine structure, a dioxazine violet structure, etc. Among them, copper phthalocyanine sulfonic acid or a salt thereof is preferable. The metal that forms a salt with the sulfonic acid is a monovalent or divalent metal such as Ca, Na, K, Mg, Fe, Co, Ni, Cu, and Zn. Moreover, organic amine salts such as aliphatic amines (NHR ₂ , NH ₂ R, [NR ₄ ] ⁺ (R: an alkyl group having 1 to 20 carbon atoms)), and the like form salts other than metal salts.

  The organic dye derivative is contained in the range of 1 to 20 parts per 100 parts of the organic pigment. In consideration of hue and productivity, it is preferably contained in the range of 1 to 15 parts. The timing of adding the organic dye may be added in the step of refining the organic pigment carried out in the present invention, or may be added after washing and refining the organic pigment after the step of refining. However, in consideration of imparting a dispersibility effect by the organic dye derivative having a sulfonic acid group or a salt thereof, it is preferable to treat the organic pigment after being refined.

  As a method for treating the organic pigment derivative, there is a method in which the perylene organic pigment after miniaturization is dyed with solid or alkali and adsorbed on the surface of the organic pigment in an acidic state. In the case of a solid, it is added to a wet cake containing a refined organic pigment and a solvent such as water. Dyeing of organic pigment derivatives with alkali is usually carried out at a pH of 8 to 12, and then mixed with a finely divided organic pigment in a slurry, and then the system is acidified, usually adjusted to a pH of 3 to 5, on the surface of the organic pigment. An organic pigment derivative is precipitated. Moreover, when manufacturing the organic pigment composition for color filters of this invention, you may add various additives other than an organic pigment derivative. Specific examples include light or thermosetting resins, surfactants, dispersants, rosins, and the like.

  As an organic pigment used in combination with the organic pigment composition of the present invention, light shielding properties can be imparted by using a blue organic pigment, a yellow organic pigment, and a red organic pigment in combination. These color organic pigments include, for example, organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene based on the chemical structure. Can be mentioned. Hereinafter, specific examples of pigments that can be used in the present invention are indicated by pigment numbers.

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

  Examples of the yellow organic pigment include C.I. 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, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 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. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of the red organic pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and more preferably C.I. I. Pigment red 177, 209, 224, 254.

  In the present invention, only a blue organic pigment, a yellow organic pigment, and a red organic pigment can be used together, but if necessary, a green organic pigment, a purple organic pigment, an orange organic pigment, a brown organic pigment, You may adjust the color tone. As these other color organic pigments used in combination, it is preferable to use one having an average primary particle size of 20 to 100 nm.

  Examples of organic pigments other than blue, yellow and red suitable for use in combination include C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment orange 38, 71, C.I. I. And CI Pigment Violet 23.

  The organic pigment to be used and the combination thereof need only have the blackness required for the target black matrix. Making black by subtractively mixing the three primary colors of blue, yellow, and red belongs to the technical common sense of those skilled in the art, and the mixing ratio thereof is not particularly limited. However, for example, when the total of each color organic pigment of blue, yellow, and red is 100% in terms of mass, each color is centered on 33% by mass, and each color is increased or decreased by plus or minus 7%. The black color can be adjusted.

  Thus, the organic pigment composition for color filter of the present invention, the pigment composition for black matrix containing the blue organic pigment and the red organic pigment can be easily prepared by mixing them in an arbitrary order.

  The coloring composition of the present invention contains each of the above-described organic pigment compositions, a resin dispersant, and an organic solvent. As a method for producing a colored composition, a colored composition in which each color organic pigment, organic solvent and dispersant are dispersed may be mixed separately, or all organic pigments may be dispersed with the organic solvent and dispersant at once. good.

  When these organic pigment compositions are dispersed in an organic solvent, a resin dispersant is used in combination for improving dispersibility and dispersion stability. This resin-based dispersant has a function of binding the organic pigment and the anchor site, and the compatible part extends into the dispersion medium to form a dispersion. An alkali used for the preparation of the photosensitive composition described later is used. The soluble resin and the photopolymerizable monomer are different types.

  Examples of the resin dispersant include those having a polymer chain, such as polyurethane resin, polyethyleneimine, polyoxyethylene glycol diester, acrylic resin, and polyester resin. Among these, polyester resin dispersants and / or acrylic resin dispersants are preferable in terms of dispersibility, heat resistance, and light resistance.

  Specific examples of various resin-based dispersants include trade names such as Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), EFKA (manufactured by Ciba), Disperbik (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE. (Manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. 1 type may be used for these dispersing agents, and 2 or more types can be used together by arbitrary combinations and a ratio.

  The resin dispersant is usually 30 to 60 parts, preferably 38 to 50 parts, per 100 parts by mass of the total amount of organic pigments of each color.

An organic solvent is used for the preparation of the coloring composition.
Examples of the organic solvent used here include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, and valsol. # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, n-amyl methyl ketone (2-heptanone) , Methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipente , Methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3 -Methoxypro On acid, 3-ethoxypropionic acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate , Diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-etc. Is mentioned.

  When preparing a photosensitive composition for forming a black matrix by a photolithographic method using a coloring composition, in order to make it low viscosity and excellent in coating property, workability, and ejection property, At least n-amyl methyl ketone (2-heptanone) is preferably used as the organic solvent contained in the coloring composition.

  In order to prepare a coloring composition, the organic solvent may be used individually by 1 type, and 2 or more types can be used together by arbitrary combinations and a ratio. However, in the colored composition of the present invention, the organic solvent is usually used in an amount of 300 to 800 parts, preferably 400 to 600 parts, per 100 parts in terms of the total mass of the organic pigments of each color.

  In preparing the colored composition, for example, various pigment derivatives can be used in combination as required. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group directly on the pigment skeleton or an alkyl group and an aryl group. And those bonded via a heterocyclic group or the like.

  The coloring composition can be prepared by stirring and mixing the organic pigment composition of each color, the resin dispersant, and the organic solvent. If necessary, it can be prepared by shaking for a required time in the presence of various grinding media such as beads and rods and dispersing the media by filtration or the like.

  The coloring composition can be used for forming the black matrix portion by a conventionally known method.

  A typical production method of a color filter is a photolithography method, and a black matrix is prepared by applying a photosensitive composition described later prepared from the coloring composition of the present invention onto a transparent substrate for a color filter and heating. After drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photo-curable compound at the location corresponding to the black matrix portion, and then developing the unexposed portion with a developer. The non-pixel portion is removed and the pixel portion is fixed to the transparent substrate. By this method, a black matrix portion made of a cured colored film of the photosensitive composition is formed on the transparent substrate. Each of the RGB pixel portions can also be prepared in the same manner as described above from a photosensitive composition prepared from each color organic pigment having a larger specific surface area.

  Examples of a method for applying a photosensitive composition described later on a transparent substrate such as glass include a spin coating method, a roll coating method, a slit coating method, and an inkjet method.

  Although the drying conditions of the coating film of the photosensitive composition apply | coated to the transparent substrate differ also with the kind of each component, a compounding ratio, etc., they are 50-150 degreeC and are about 1 to 15 minutes normally. This heat treatment is generally referred to as “pre-baking”. Moreover, as light used for photocuring of the photosensitive composition, it is preferable to use ultraviolet rays or visible light in the wavelength range of 200 to 500 nm. Various light sources that emit light in this wavelength range can be used.

  Examples of the developing method include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photosensitive composition, the transparent substrate on which the black matrix or the pixel portion of the necessary color is formed is washed with water and dried. The color filter thus obtained is subjected to heat treatment (post-baking) at 100 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the colored coating film, and at the same time, The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.

  The photosensitive composition for forming the black matrix part of the color filter has the coloring composition of the present invention, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator as essential components, and these are mixed. Can be prepared.

  When the colored resin film forming the black matrix portion is required toughness that can withstand baking performed in the actual production of the color filter, only the photopolymerizable monomer is used in preparing the photosensitive composition. In addition, it is essential to use this alkali-soluble resin together. When an alkali-soluble resin is used in combination, it is preferable to use an organic solvent that dissolves it.

  As the method for producing the photosensitive composition, the colored composition of the present invention is prepared in advance, and then an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator are added to the photosensitive composition. The method of making a product is common.

Examples of the alkali-soluble resin used for the preparation of the photosensitive composition include a resin containing a carboxyl group or a hydroxyl group exhibiting acidity, for example, a novolac type phenol resin, a (meth) acrylic acid alkyl ester- (meth) acrylic acid copolymer, Examples include styrene- (meth) acrylic acid copolymers and styrene-maleic acid copolymers. In addition, in this invention, description with (meth) acryl is a general term which combined acrylic and methacryl.
Especially, in order to raise the heat resistance of a cured film more, it is preferable to use alkali-soluble resin containing each polymerization unit of an imide structure, styrene, and (meth) acrylic acid.

  This alkali-soluble resin does not have the function of binding the organic pigment and the anchor part and having the compatible part extend into the dispersion medium to constitute the dispersion, but on the other hand, it is in contact with the alkali. This is used exclusively for the purpose of removing unexposed portions of the photosensitive composition, taking advantage of the characteristics of dissolution.

  Examples of the photopolymerizable monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis [( (Meth) acryloxyethoxy] bisphenol A, bifunctional monomers such as 3-methylpentanediol di (meth) acrylate, trimethylol propaton tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxy Ethyl) isocyanurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, etc. Relatively high molecular weight of small polyfunctional monomer, polyester acrylate, polyurethane acrylate, a large multi-functional monomer having a relatively molecular weight such as polyether acrylate. Similarly to the above, the description of (meth) acrylate is a general term that combines acrylate and methacrylate.

  Especially, in order to improve the heat resistance of a cured film more, it is preferable to use tetrafunctional-hexafunctional (meth) acrylate.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid, ethanone, 1- [9-ethyl-6- [2-methyl-4- ( 2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
However, since the photosensitive composition of the present invention is black, it is preferable to use a photopolymerization initiator having excellent curability.

  By selecting an alkali-soluble resin that does not affect the light transmittance and a photopolymerizable monomer, the cured film of the photosensitive composition has a maximum light transmittance in a wavelength range of 400 to 800 nm suitable for a black matrix. 1% or less, and the light transmittance in the near infrared region with a wavelength of 800 to 1100 nm can be 80%.

  The light transmittance of the black matrix is a spectrophotometer for a 3 μm thick black matrix (cured film) formed on a transparent substrate such as a glass substrate, with the substrate on which the resin black matrix is not formed as a control. It refers to the measured light transmittance.

  The maximum light transmittance means the largest value among the light transmittances in a specific wavelength region (range). More specifically, the maximum value of the light transmittance curve in a specific wavelength region. For example, “the maximum light transmittance in the wavelength range of 400 nm to 800 nm is 1% or less” means that the maximum value of the light transmittance curve in the wavelength range of 400 nm to 800 nm is 1% or less. It means that there is no region where the transmittance exceeds 1%.

On the other hand, “wavelength 800 nm to 1100 nm” means a so-called near infrared region. “A black matrix having a light transmittance of 80% or more in the near infrared region having a wavelength of 800 nm to 1100 nm is a black matrix having a low light absorption and a high light transmittance in the near infrared long region.
The larger the light transmittance in the near infrared region, the more easily the black matrix emits heat generated in the TFT element that is a heat source. For this reason, in the TFT element, an increase in on-current and off-current is small, and thermal runaway is difficult to occur.

  Further, if the volume resistivity is 1 × 10 13 Ω · cm or more and the dielectric constant is 5 or less, short circuit of the TFT element (switching element made of a thin film transistor) due to leakage current can be reduced, and switching of the TFT element can be performed. It is transmitted accurately and disturbance of driving of the liquid crystal can be reduced.

  Volume resistivity is a measure of the insulating properties of a substance and is the electrical resistance per unit volume. The volume resistivity is described in, for example, the Institute of Electrical Engineers of Japan “The Institute of Electrical Engineers of Japan, Electrical and Electronic Materials-From Basics to Test Methods” (Ohm Co., Ltd., 2006, pages 223 to 230). It can be measured by a technique.

  The dielectric constant means a so-called relative dielectric constant, which is a ratio between a dielectric constant of a substance and a dielectric constant of a vacuum. The dielectric constant is, for example, a method described in the Institute of Electrical Engineers of Japan, “The University of Electrical Engineers, Electrical and Electronic Materials-From Basics to Test Methods” (Ohm Co., Ltd., 2006, pp. 233 to 243). Can be measured.

  In the photosensitive composition of the present invention having such characteristics, the total of the alkali-soluble resin and the photopolymerizable monomer is 3 to 20 parts per 100 parts of the colored composition of the present invention, and 0.05 per part of the photopolymerizable monomer. Photosensitivity for forming a black matrix part by adding ~ 3 parts photopolymerization initiator and, if necessary, the organic solvent used for the preparation of the above-described coloring composition, and stirring and dispersing so as to be uniform. Can be obtained.

  In order to form a black matrix by a photolithography method, in order to make the photosensitive composition of the present invention low in viscosity and excellent in coatability and workability, at least the nonvolatile content is 5 to 20% in terms of mass. It is preferable to prepare such that

  As the developer, a known and commonly used alkaline aqueous solution can be used. In particular, since the photosensitive composition contains an alkali-soluble resin, washing with an aqueous alkaline solution is effective for forming the black matrix portion. The excellent heat resistance of the photosensitive composition of the present invention is exhibited in a method for producing a color filter in which baking is performed after such alkali washing.

  Among the pigment dispersion methods, the method for producing the black matrix portion by photolithography was described in detail, but the black matrix portion prepared using the photosensitive composition of the present invention is not limited to other electrodeposition methods, transfer methods, A color filter may be produced by forming the electrode by a method such as a micelle electrolysis method or a PVED (Photovoltaic Electrodeposition) method.

  The color filter uses a red organic pigment, a green organic pigment, a blue organic pigment, and a photosensitive composition of each color obtained by using the coloring composition of the present invention, and encapsulates a liquid crystal material between a pair of parallel transparent electrodes. In addition, the transparent electrode is divided into discontinuous fine sections, and red (R), green (G), and blue (B) are divided into the fine sections divided in a lattice form by the black matrix on the transparent electrode. It can be obtained by providing a color filter coloring pixel portion selected from any one color alternately in a pattern, or by forming a color filter coloring pixel portion on a substrate and then providing a transparent electrode.

  The black matrix portion obtained from the photosensitive composition of the present invention contains the above-mentioned blue, yellow, and red organic pigments so as to be black. At first glance, the photosensitive compositions of the respective colors are mixed. It seems as if a black matrix similar to that obtained when the black photosensitive composition is prepared as described above, but in the present invention, at the time of preparing the coloring composition, which is the previous stage of making the photosensitive composition, As a result of mixing the organic pigments of the respective colors in advance, more uniform mixing is achieved, and a black matrix having better characteristics is obtained.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples and comparative examples, “part” and “%” are both based on mass.

[Example 1]

<Salt milling process of pigment>
<Salt milling process of pigment>
Irgazin Violet 129 (CI Pigment Violet 29 manufactured by Ciba Specialty) 100 parts, 1000 parts of sodium chloride, and 200 parts of diethylene glycol were charged into a stainless steel 1 L kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 7 hours. Next, this mixture was poured into 2 liters of warm water, stirred for 30 minutes to form a slurry, filtered and washed with water until the specific conductivity was 150 μS / cm or less, and sodium chloride and the solvent were removed to remove wet cake (W− 1) was obtained.

<Process for treating organic pigment derivative with sulfonic acid to pigment>
Wet cake (W-1) (solid content 30%) was taken into a beaker so that the pigment content would be 100 parts, and 3500 parts of water was added to sufficiently reslurry. Subsequently, an aqueous sodium hydroxide solution containing 5 parts of a copper phthalocyanine sulfonic acid derivative was added to the pigment slurry, and after stirring for 1 hour, hydrochloric acid was added to bring the pH of the slurry back to 7, which was precipitated on the pigment surface. It was. After being kept for 1 hour, it was filtered, washed with warm water, dried and pulverized to obtain a pigment composition (P-1).

<Process for producing colored composition>
Pigment composition (P-1) 5.1 parts, FASTOGEN BLUE EP-CF (DIC Pigment Blue 15: 6, manufactured by DIC Corporation) 5.59, Symbol Fast Yellow 4119 (CI Pigment, manufactured by DIC Corporation) Yellow 139) 4.31 parts, PB-821 (polyester resin-based dispersant manufactured by Ajinomoto Fine Techno Co., Ltd.) 4.5 parts as a resin dispersant, 0.2 to 0 in a mixture of propylene glycol monomethyl acetate 73.75 g .3 mmφ zirconia beads were added and dispersed for 2 hours with a paint conditioner to obtain a colored composition (A-1).

<Production process of photosensitive resin composition>
100 parts of coloring composition (A-1), methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / benzyl methacrylate copolymer (copolymerization mass ratio) as alkali-soluble resin (B) = 25/10/30/20/15, Mw = 12,000, Mn = 6,500) 5 parts, as photopolymerizable monomer (C), 10 parts of dipentaerythritol hexaacrylate, as photopolymerization initiator (D) Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) as an organic solvent (E) as an organic solvent (E) 25 parts by weight, propylene glycol monomethyl ether acetate 25 parts by weight, 3-methoxybutyl acetate A photosensitive resin composition (X-1) was prepared by mixing 75 parts by weight and 50 parts by weight of cyclohexanone.

<Black matrix production process>
A 10 cm square glass substrate (Nippon Electric Glass color filter glass plate “OA-10”) is immersed in a 1% diluted solution of Shinetsu Chemical's silane coupling agent “KBM-603” for 3 minutes and washed with water for 10 seconds. After draining with an air gun, it was dried in an oven at 110 ° C. for 5 minutes. On this glass substrate, the photosensitive resin composition (X-1) prepared above was applied using a spin coater. After vacuum drying for 1 minute, it was heated and dried at 90 ° C. for 90 seconds on a hot plate to obtain a coating film having a dry film thickness of about 3.5 μm. Thereafter, from the coating film side, two types of exposure are performed: one that exposes an image through a fine line pattern mask with a width of 15 μm (pattern 1) and one that exposes the entire surface without passing through a mask (pattern 2). It was. The exposure conditions were 50 mJ / cm 2 (i-line standard) using a 3 kW high-pressure mercury lamp. Next, using a developer composed of an aqueous solution containing 0.05% potassium hydroxide and 0.08% nonionic surfactant (“A-60” manufactured by Kao), a shower having a water pressure of 0.15 MPa at 23 ° C. After development, development was stopped with pure water and washed with water spray to obtain a black matrix (B-1). The shower development time was adjusted between 10 and 120 seconds, and was 1.5 times the time during which the unexposed coating film was dissolved and removed.
[Example 2]

In the sulfonic acid derivative treatment step of Example 1, a colored composition (A-2) was produced under the same conditions as in Example 1 except that 5 parts of the copper phthalocyanine sulfonic acid derivative was changed to 12 parts. A black matrix (B-2) was prepared in the same manner as in Example 1 except that the colored composition (A-1) was replaced with the colored composition (A-2).
[Example 3]

In the salt milling process of Example 1, Irgazin Violet 129 was changed to Indo Fast Brilliant Scallet R-6335 (DIC Pigment Red 123 manufactured by DIC Corporation) under the same conditions as in Example 1 ( A-3) was produced. A black matrix (B-3) was prepared in the same manner as in Example 1 except that the colored composition (A-1) was replaced with the colored composition (A-3).
[Example 4]

A colored composition (A-4) under the same conditions as in Example 1 except that Irgazin Violet 129 was changed to Irgazin Red 179 (CI Pigment Red 179 manufactured by Ciba Specialty) in the salt milling process of Example 1. Was made. A black matrix (B-4) was prepared in the same manner as in Example 1 except that the colored composition (A-1) was replaced with the colored composition (A-4).
[Example 5]

In the salt milling process of Example 1, Irgazin Violet 129 was changed to Indo Fast Brillant Scallet R-6500 (DIC Pigment Red 190 manufactured by DIC Corporation) under the same conditions as in Example 1 ( A-5) was obtained. A black matrix (B-5) was prepared in the same manner as in Example 1 except that the colored composition (A-1) was replaced with the colored composition (A-5).
[Example 6]

A colored composition (A-6) under the same conditions as in Example 1 except that Irgazin Violet 129 was changed to Irgazin Red BPT (CI Pigment Red 224 manufactured by Ciba Specialty) in the salt milling process of Example 1. Got. A black matrix (B-6) was prepared in the same manner as in Example 1 except that the colored composition (A-1) was replaced with the colored composition (A-6).

(Comparative Example 1)
Except that the pigment composition (P-1) was used as it was with Irgazin Violet 129 in the coloring composition preparation step without the salt milling step of the pigment of Example 1 and the sulfonic acid organic dye derivative treatment on the pigment. A colored composition (A-7) was obtained under the same conditions as in Example 1. A black matrix (B-7) was prepared in the same manner as in Example 1 except that the colored composition (A-1) was replaced with the colored composition (A-7).

(Comparative Example 2)
In the sulfonic acid derivative treatment step of Example 1, a colored composition (A-8) was obtained under the same conditions as in Example 1 except that 5 parts of the copper phthalocyanine sulfonic acid derivative was changed to 0 parts. A black matrix (B-8) was prepared in the same manner as in Example 1 except that the colored composition (A-1) was replaced with the colored composition (A-8).

The OD values of the black matrices prepared in Examples and Comparative Examples are shown in Table 1 with the OD value of Example 1 converted to 100. Moreover, the primary particle diameter of the obtained orange pigment composition was also described.
From the above, it has been clarified that the pigment composition of the present invention has a small primary particle diameter, and that the black matrix containing the pigment composition has an improved OD value compared to the conventional one.

The organic dye derivative used in the present invention may have any chemical structure as long as the organic dye derivative has a sulfonic acid group or is a sulfonate. An organic pigment derivative having a sulfonic acid group or a sulfonate is often added in order to improve dispersibility in a binder and solvent system, and its effect is well known. The number of substituents of the sulfonic acid group is 1 to 4 per molecule . Since the perylene organic pigment used in the present invention has a purple hue, an organic dye derivative having the same color is preferable, but organic dye derivatives having different hues can be used. Specifically, there are an azo structure, a benzimidazolone structure, a quinacridone structure, a diketopyrrolopyrrole structure, a phthalocyanine structure, a dioxazine violet structure, etc. Among them, copper phthalocyanine sulfonic acid or a salt thereof is preferable. The metal that forms a salt with the sulfonic acid is a monovalent or divalent metal such as Ca, Na, K, Mg, Fe, Co, Ni, Cu, and Zn. Moreover, organic amine salts such as aliphatic amines (NHR ₂ , NH ₂ R, [NR ₄ ] ⁺ (R: an alkyl group having 1 to 20 carbon atoms)), and the like form salts other than metal salts.

Claims (4)

An organic pigment composition for a color filter, comprising 1 to 15 parts of an organic dye derivative containing a sulfonic acid group per 100 parts of a perylene organic pigment, and having a primary particle diameter of the pigment of 20 nm to 100 nm. The perylene organic pigment is C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 189, C.I. I. Pigment red 190, C.I. I. Pigment red 224, C.I. I. Pigment red 228, C.I. I. Pigment violet 29, C.I. I. Pigment black 31, C.I. I. The organic pigment composition for a color filter according to claim 1, wherein the organic pigment composition is selected from at least one of pigment black 32. The organic pigment composition for a color filter according to claim 1, wherein the organic dye derivative is copper phthalocyanine sulfonic acid or a salt thereof. A color filter comprising the organic pigment composition for a color filter according to claim 1.