TWI429964B - Shading composition and color filter - Google Patents

Description

Shading composition and color filter

The present invention relates to a light-shielding composition and a color filter comprising the light-shielding composition.

[Background technique]

In the past, color filters have been widely used for the purpose of colorization of liquid crystal displays, etc. Generally, the pixels of the three primary colors of red, green, and blue are used in a mosaic configuration. In order to improve the display contrast between these pixels, it is usually set to have a light-shielding region, which is seen as a black grid, and is therefore called a black matrix.

The manufacturing method of the black matrix is roughly (A) a method of forming a metal thin film of chromium, nickel, aluminum or the like by vapor deposition or the like and etching the same, and (B) using dispersed carbon black, titanium black or the like. A method of producing a photosensitive resin composition of a coloring material having a high light-shielding property by photolithography. The method of (A) is relatively high in cost, and it is not easy to manufacture on a large substrate. Therefore, in recent years, the method of switching to (B) has been carried out. The method of (B) is widely used. However, in the state in which carbon black is used as the coloring material, there is a problem that it is difficult to maintain the insulating property required for the liquid crystal display of the IPS driving method or the STN driving method. Further, in the state in which titanium black is used as the coloring material, there is a problem that the dispersion of the titanium black which is difficult to carry out is difficult to be stabilized and the cost is high.

Therefore, review the application of organic pigments as high insulation and dispersion stability Color or good quality color material. For example, Patent Document 1 (Japanese Patent No. 2552391) or Patent Document 2 (Japanese Patent No. 3700398) discloses a mixed color organic pigment which is intended to be blackened by the use of a black organic pigment or a combination of a plurality of organic pigments. Use. However, in the state in which a general organic pigment is used as the coloring material, only insufficient light-shielding properties are obtained as the use of the black matrix. Therefore, in the invention described in these documents, in order to secure the light-shielding property, carbon black or Titanium black and other systems are essential. Therefore, the above problems cannot be solved.

On the other hand, a benzimidazolone dioxazine pigment is known as one of organic pigments. The benzimidazolone dioxazine pigment is characterized by a high degree of coloring power and a vivid hue. Patent Document 3 (JP-A-2005-49636) and Patent Document 4 (JP-A-2005-242123) In the patent document 5 (JP-A-2006-53329), it is disclosed that a benzimidazolone dioxazine pigment is used as a coloring material for a color filter. However, in the invention described in these documents, the benzimidazolone dioxazine pigment is used as a coloring material for improving the color characteristics (brightness, chroma, etc.) of the blue pixel, and therefore, the amount of the coloring material is The content is preferably in the solid component, and the content is less than 40% by weight, which is a desirable range; the purpose or embodiment is different from the present invention. Further, even in any of the inventions described in Patent Documents 1 to 5, there is no use of any light-shielding coloring material which is a benzimidazolone dioxazine pigment, even for benzene which is a coloring material of a black matrix. There is also no indication of the use of imidazolidin dioxazine pigments.

[Patent Document 1] Japanese Patent No. 2552391 [Patent Document 2] Japanese Patent Laid-Open No. Hei. No. 2005-49636 (Patent Document No. 5).

[Disclosure of the Invention]

The present invention has been made in view of the problems of the prior art, and an object thereof is to provide a light-shielding composition having high light-shielding property and excellent insulation or dispersion stability, and a color filter comprising the light-shielding composition. .

In order to solve the above problems, the present inventors have found that a specific organic pigment is suitable as a coloring material for a desired light-shielding composition, and contains a light-shielding composition of the organic pigment in a predetermined amount, and is suitable for a black matrix. The formation is completed to complete the present invention.

In other words, the present invention is a light-shielding composition which contains 40% by weight or more of a solid component and a benzimidazolone dioxazine pigment represented by the following formula (1) as an essential component. The light-shielding composition is characterized in that the optical density of the cured film of the cured light-shielding composition is 1 μm or more and 2.0 or more.

(However, R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent, and X represents a hydrogen atom or a halogen atom.)

Here, it is preferable that the coloring material contains 30% by weight or more of the benzimidazolone dioxazine pigment, and it is preferable that the coloring material contains at least one organic selected from yellow, orange, red or brown. The pigment is 1 to 70% by weight.

Further, the present invention is a light-shielding composition for a color filter, which comprises the light-shielding composition described above, and contains 5 to 50% by weight of a photosensitive resin and 1 to 10% by weight of a photopolymerization initiator in a solid component. It is possible to form an image by light lithography. Here, the volume resistivity of the cured film of the light-shielding composition for hardening the color filter is preferably 10 ¹⁴ Ω. More than cm.

Further, the present invention is a color filter comprising the above-described cured film of a light-shielding composition for a color filter.

Hereinafter, the present invention will be described in detail.

The light-shielding composition of the present invention contains 40% by weight or more of a coloring material containing, as an essential component, a benzimidazolone dioxazine pigment represented by the formula (1) in a solid component. Here, the term "coloring material" means pigments, dyes Wait. In addition, the solid content means a component other than the solvent in the light-shielding composition, and means a component which contributes to formation of a cured film of the light-shielding composition. The light-shielding composition of the present invention is required to contain 40% by weight or more of the coloring material in the solid content. However, in terms of improving the light-shielding property, it is preferably contained in an amount of 50% by weight or more, and more preferably 60% by weight or more. Further, the light-shielding composition of the present invention may contain a component other than the coloring material or the solvent, if necessary, and for example, a resin or a dispersing agent may be blended.

The light-shielding composition of the present invention is characterized in that the optical density of the cured film is 1 μm or more and 2.0 or more. The optical density is generally a value defined by the usual logarithm of the reciprocal of the transmittance. However, the measured value can be easily obtained by a commercially available optical densitometer ("D200-II" manufactured by GretagMacbeth Co., Ltd.). The light-shielding composition of the present invention must have an optical density of the cured film of 2.0 or more, preferably 2.2 or more, more preferably 2.5 or more in a film thickness of 1 μm. The optical density is an indicator of the light-shielding property, and it can be said that the higher the optical density per unit film thickness, the higher the light-shielding property. Further, by increasing the film thickness of the cured film, a higher optical density can be obtained, and in the light-shielding composition of the present invention, an optical density of 3.0 or more can be achieved while forming a film thickness of 1.5 μm, and 2.0 μm can be formed. In the state of the film thickness, an optical density of 4.0 or more is achieved.

Since the light-shielding composition of the present invention is used for evaluating the optical density, it is required to form a cured film having a film thickness of 1 μm. The most standard method for producing the cured film is a method in which a light-shielding composition is applied to a substrate or the like to perform ultraviolet irradiation at 100 mJ/cm ² and heat-hardening at 230 ° C for 20 minutes, and is cured by optical. When the cured film obtained as described above is measured by a concentration meter, the optical density of the object can be obtained. As a method of applying the light-shielding composition, a conventional method can be used, and for example, coating by a spin coater, a bar coater, a slit coater or the like can be mentioned. Here, in the state where the light-shielding composition contains a solvent, it is preferable to dry the light-shielding composition using a hot plate or a vacuum dryer after application. Next, the method of hardening may be a conventional method, and examples thereof include ultraviolet light irradiation using a xenon lamp, a halogen lamp, a tungsten lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and the like, and a heating plate. Heated by a hot air oven or the like. Further, the above-mentioned ultraviolet irradiation of 100 mJ/cm ² and the heating of 20 minutes at 230 ° C are the most standard hardening conditions, but in the actual use of the light-shielding composition, these conditions can be matched with the substrate used. The properties of the cured film of the property or the light-shielding composition are appropriately adjusted. For example, in the case of photohardening, ultraviolet irradiation of 10 to 1000 mJ/cm ² can be performed, and in the case of thermal curing, heating can be performed at 200 to 250 ° C for 20 to 60 minutes, and it is also possible to use both sides of the curing method. Moreover, it is also possible to perform only the one-side hardening method due to the state.

The benzimidazolone dioxazine pigment used in the present invention has a structure represented by the general formula (1), and exhibits absorption in a wavelength region of visible light which is characteristic of seven constricted structures. Here, when R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group which may have a substituent, it is not particularly limited, but is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms. Specific examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a vinyl group, and an allyl group. Specific examples of the substituent include a substituent. A halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group or the like is not limited thereto. Further, X represents a hydrogen atom or a halogen atom, but is preferably a halogen atom, particularly preferably a chlorine atom. These benzimidazolone dioxazine pigments may be used alone or in combination of two or more. In order to improve the light-shielding property, the benzimidazolone dioxazine pigment is preferably contained in the coloring material in an amount of 30% by weight or more, and more preferably 50% by weight or more.

Among the benzimidazolone dioxazine pigments having the above-mentioned configuration, as a particularly desirable series, R ¹ is a hydrogen atom, R ² is an ethyl group, and X is a chlorine atom. Blue80. As a Pigment. Examples of Blue80's commercial products are "Hostaperm Blue R5R VP2548", "Hostaperm Blue R5R 01 VP3317" and "Hostaperm Blue R5R-WD" by Clariant.

In the light-shielding composition of the present invention, a coloring material other than the benzimidazolone dioxazine pigment (hereinafter referred to as "other coloring material") may be blended. As other coloring materials, conventional pigments, dyes, and the like can be used, but azo-based pigments, condensed azo-based pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, and isoindoles are preferred. Ketone pigments, isoindane pigments, carbazole dioxazine pigments, Shihlin pigments, perylene pigments, perinone pigments, quinacridone pigments, dioxopyrrolopyrrole pigments, thioindigo pigments, etc. The insulating organic pigment represented by the present invention is particularly advantageous in that the coloring material contains at least one organic pigment selected from yellow, orange, red or brown in a range of 70% by weight or less, more preferably in the range of 70% by weight or less. The color material contains at least one organic pigment in a range of 50% by weight or less. As a series of organic pigments of yellow, orange, red and brown, for example, Pigment. Yellow 1, Pigment. Yellow 3, Pigment. Yellow 12, Pigment. Yellow 13, Pigment. Yellow 14, Pigment. Yellow 16, Pigment. Yellow 17, Pigment. Yellow 55, Pigment. Yellow 73, Pigment. Yellow 74, Pigment. Yellow 81, Pigment. Yellow 83, Pigment. Yellow 93, Pigment. Yellow 95, Pigment. Yellow 97, Pigment. Yellow 109, Pigment. Yellow 110, Pigment. Yellow 111, Pigment. Yellow 117, Pigment. Yellow 120, Pigment. Yellow 126, Pigment. Yellow 127, Pigment. Yellow 128, Pigment. Yellow 129, Pigment. Yellow 130, Pigment. Yellow 136, Pigment. Yellow 138, Pigment. Yellow 139, Pigment. Yellow 150, Pigment. Yellow 151, Pigment. Yellow 153, Pigment. Yellow 154, Pigment. Yellow 155, Pigment. Yellow 173, Pigment. Yellow 174, Pigment. Yellow 175, Pigment. Yellow 176, Pigment. Yellow 180, Pigment. Yellow 181, Pigment. Yellow 183, Pigment. Yellow 185, Pigment. Yellow 191, Pigment. Yellow 194, Pigment. Yellow 199, Pigment. Yellow 213, Pigment. Yellow 214, Pigment. Orange 5, Pigment. Orange 13, Pigment. Orange 16, Pigment. Orange 34, Pigment. Orange 36, Pigment. Orange 38, Pigment. Orange 43, Pigment. Orange 61, Pigment. Orange 62, Pigment. Orange 64, Pigment. Orange 67, Pigment. Orange 68, Pigment. Orange 71, Pigment. Orange 72, Pigment. Orange 73, Pigment. Orange 74, Pigment. Orange 81, Pigment. Red 2, Pigment. Red 3, Pigment. Red 4, Pigment. Red 5, Pigment. Red 9, Pigment. Red 12, Pigment. Red 14, Pigment. Red 22, Pigment. Red 23, Pigment. Red 31, Pigment. Red 38, Pigment. Red 112, Pigment. Red 122, Pigment. Red 144, Pigment. Red 146, Pigment. Red 147, Pigment. Red 149, Pigment. Red 166, Pigment. Red 168, Pigment. Red 170, Pigment. Red 175, Pigment. Red 176, Pigment. Red 177, Pigment. Red 178, Pigment. Red 179, Pigment. Red 184, Pigment. Red 185, Pigment. Red 187, Pigment. Red 188, Pigment. Red 202, Pigment. Red 207, Pigment. Red 208, Pigment. Red 209, Pigment. Red 210, Pigment. Red 213, Pigment. Red 214, Pigment. Red 220, Pigment. Red 221, Pigment. Red 242, Pigment. Red 247, Pigment. Red 253, Pigment. Red 254, Pigment. Red 255, Pigment. Red 256, Pigment. Red 257, Pigment. Red 262, Pigment. Red 264, Pigment. Red 266, Pigment. Red 272, Pigment. Red 279, Pigment. Brown 23, Pigment. Brown 25, Pigment. Brown 41, etc., however, is not limited to these. In addition, in the state of training other coloring materials Next, the lower limit for substantially achieving the purpose is 1% by weight in the coloring material.

In the light-shielding composition of the present invention, the reason why the benzimidazolone dioxazine pigment is selected as an essential component of the coloring material is obtained by the high coloring power caused by the absorption of the wavelength region in the visible light according to the characteristics. The light-shielding property as an organic pigment. Further, by using at least one organic pigment selected from yellow, orange, red or brown in combination as the other coloring material, the distribution of the wavelength absorption region can be optimized and the light shielding property can be further improved. In addition, in the state where the coloring material does not use the benzimidazolone dioxazine pigment and the organic pigment other than this is used to constitute the light-shielding composition, the light-shielding property is generally insufficient, and the optical density of the cured film having a film thickness of 1 μm is not reached. 2.0.

In the light-shielding composition of the present invention, in order to further improve the light-shielding property, carbon black or titanium black may be blended as another coloring material. However, in the state containing carbon black, it is not easy to mix the amount to maintain the insulating property, and in the state containing titanium black, the maintenance of the dispersion stability is a problem.

The light-shielding composition of the present invention is characterized in that the optical density of the cured film is 1 μm or more and 2.0 or more; however, in order to stably achieve this, it is selected by using yellow, orange, red or brown color. In the state of at least one organic pigment as the other coloring material, the amount of the coloring material in the solid component P (% by weight) and the amount of the benzimidazolone dioxazine pigment in the coloring material Q (% by weight) It is preferable to set the formulas of (2) to (4) which satisfy the following three formulas.

Q≧30 (2) P+Q≧90 (3) 5P-2Q≧100 (4)

Here, the above formulas (2) and (3) represent the ideal lower limit of Q, and the above formula (4) represents the ideal upper limit of Q. It is shown by the above formula 3 that it must be at least P ≧ 40, and the degree of freedom of Q is increased as P increases, particularly in the region of P ≧ 60. Further, it is preferable to display at least one organic pigment selected from yellow, orange, red or brown in (100-Q)% by weight in the coloring material.

The pigment used in the present invention is advantageous in finishing the particle size by the granulation treatment. A conventional method can be used as the granulation treatment, and examples thereof include a salt polishing method, a solvent salt polishing method, an acid paste method, and an acidic slurry method, but are not limited thereto. The average particle diameter of the pigment sized as described above is preferably 10 to 500 nm, more preferably 50 to 200 nm. Here, in the state where the average particle diameter of the pigment is excessively small, the concealing force is lowered, so that it is not easy to obtain sufficient light-shielding property. Conversely, in an excessively large state, the pigment particles become obstacles and the surface smoothness is not easily obtained. Hardened film. In addition, the specific surface area as the display of the average particle size index of the known pigments; pigment used in the surface area of the present invention is preferably 10 ~ 150m ² / g, it is more desirable is 30 ~ 100m ² / g. In addition, the pigment used in the present invention is considered to be included in the state in which other pigmented materials are blended in addition to the benzimidazolone dioxazine pigment represented by the general formula (1). This pigment (even if it is the same, it is the same).

Further, the pigment used in the present invention is for improving dispersion stability. Therefore, it is preferable to carry out surface treatment. As the surface treatment system, a conventional method can be used, and examples thereof include rosin treatment, pigment derivative treatment, and acid. Alkali treatment, plasma treatment, encapsulation treatment, etc., but are not limited thereto.

In the light-shielding composition of the present invention, in order to easily form a cured film, a resin can be blended. The resin which can be used is not particularly limited as long as it is a conventional polymer compound or a high-viscosity compound, and examples thereof include a vinyl resin (acrylic acid (co)polymer, methacrylic acid (co)polymer, and butylene Diacid (co)polymer, styrene (co)polymer, etc., polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, epoxy resin, etc. However, it is preferable to have an alkali-soluble functional group such as a carboxyl group or a phenolic hydroxyl group in the structure, and to have a base developability or a reactive functional group such as a glycidyl group or an isocyanate group, and to have thermosetting property. . The amount of the resin is not particularly limited, but is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the solid content. In addition, the resin mentioned here also contains the photosensitive resin mentioned later.

In the light-shielding composition of the present invention, in order to stably disperse the coloring material such as the pigment, a dispersing agent can be blended. The dispersing agent to be used is not particularly limited as long as it is a conventional dispersing agent or a dispersing accelerator, and examples thereof include a cationic polymer dispersing agent, an anionic polymer dispersing agent, and a nonionic polymer system. a dispersing agent, a pigment derivative-type dispersing agent (dispersing aid), etc., but particularly preferably as an adsorption point for a pigment, it has an imidazole group, a pyrrolyl group, a pyridyl group, a first stage, and a second A cationic polymer-based dispersant having a cationic functional group such as a tertiary or tertiary amino group and having an amine valence of 1 to 100 mgKOH/g and an average molecular weight of 1 to 100,000. An example of such a cationic polymer-based dispersing agent is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-169821. The amount of the dispersing agent is not particularly limited, and is preferably 1 to 25% by weight, and more preferably 2 to 15% by weight, based on the solid content. Further, such a resin-based high-viscosity substance generally has a function of stabilizing dispersion. However, those who do not have a dispersion-promoting ability are not used as a dispersing agent, but are not restricted for the purpose of stable dispersion. Further, in the state in which the pigment derivative-type dispersant described above has a coloration due to the pigment skeleton, the pigment-derivative-type dispersant also functions as a part of the coloring material.

In the light-shielding composition of the present invention, in order to improve the dispersion stability of the coloring material or the coating property of the light-shielding composition, a solvent can be blended. The solvent can be used without any particular limitation, and examples thereof include esters of ethyl acetate, butyl acetate, propylene glycol diacetate, γ-butyrolactone, methyl isobutyl ketone, and cyclohexane. Ketones such as ketones and isophorones, esters of monoglyme, diglyme, triglyme, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, etc. Ether ethers such as glycol ether, methyl glycol ether, carbitol, methyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol ethyl acetate, propylene glycol monomethyl Ether esters such as ether ether acetate, 3-methoxybutyl acetate, etc., alcohol esters such as methyl glycolate, ethyl lactate, butyl lactate, etc., toluene, xylene, cumene, etc. a nitrogen-based solvent such as an aromatic solvent, 2-pyrrolidone, N-methyl-2-pyrrolidone or N,N-dimethylmethyletheramine . The amount of the solvent is not particularly limited, but is preferably 100 to 1900% by weight (50 to 95% by weight in the light-shielding composition), more preferably 150 to 900% by weight based on the solid content. (60 to 90% by weight in the light-shielding composition).

Further, the light-shielding composition of the present invention may contain any component as needed, and for example, a filler or an additive may be blended. Further, as the additive series, a curing agent, a crosslinking agent, a surfactant, a decane coupling agent, a viscosity adjusting agent, a wetting agent, an antifoaming agent, an oxidation preventing agent, and the like are exemplified, but are not limited thereto.

The method for producing the light-shielding composition of the present invention is not particularly limited. For example, a method in which a coloring material such as a pigment is dispersed in a resin or a solvent (preferably, a dispersing agent) is used. Further, as a method of dispersing the coloring material, a conventional method can be used, and for example, a dispersion processing treatment by a kneader, an attritor, a roller pulverizer, a particle pulverizer, a paint shaker, a disperser, or the like can be cited. However, it is not limited to these.

The light-shielding composition for a color filter of the present invention is characterized in that it contains 5 to 50% by weight of a photosensitive resin in a solid component, and contains a photopolymerization initiator 1 to 10 in a solid component. The weight is %, and the light lithography can be used to form an image. Here, the so-called photolithography refers to coating. The coating film obtained by drying the light-shielding composition is selectively irradiated with light (image exposure) through a mask or the like, and after the light irradiation portion is cured by light energy, the image is removed by development. A method of obtaining an image by performing a portion irradiated with light; in particular, a method called negative photolithography.

The benzimidazolone dioxazine pigment used in the present invention and represented by the formula (1) has permeability in an ultraviolet wavelength region of less than 380 nm. Therefore, the light-shielding composition for color filters of the present invention is very suitable for photolithography caused by ultraviolet irradiation. The color filter using carbon black as a coloring material is widely used as a light-shielding composition. However, the carbon black system hardly transmits ultraviolet rays, and therefore, it is not easy to perform light microscopy by ultraviolet irradiation. Shadow. In particular, in the case where the image formation of a relatively high film thickness of 1.5 μm or more is in the state in which carbon black is used as the coloring material, it is impossible to perform photocuring on the deep portion of the coating film, which is extremely hindered. However, the light-shielding composition for a color filter of the present invention can be easily formed by image formation and can be sufficiently light-cured to the deep portion of the coating film even at such a high film thickness, and can be suitably used for thick thickness. The formation of a black matrix of the film. An example of such a thick film black matrix is the formation of a color filter by an ink jet method, and it is necessary to have a function as a partition wall of a pixel.

The photosensitive resin to be used in the present invention may be selected from at least one of a photopolymerizable resin, a photopolymerizable monomer, and a photopolymerizable oligomer. However, it may be a resin in a cured state, or may be in a The state of hardening contains only the resin-free component such as a monomer or an oligomer. As the photosensitive resin, it is preferable to use a photopolymerizable resin, a photopolymerizable monomer, and a photopolymerizable oligomer, and it is particularly preferable to use acrylic acid and methacrylic acid (hereinafter, it is called Examples of the derivative of "(meth)acrylic acid" or the like include diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(methyl). (meth)acrylates such as acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy di(meth)acrylate, Bisphenol F type epoxy di(meth)acrylate, bisphenolphthalein type epoxy di(meth)acrylate, bisphenol novolac type epoxy poly(meth)acrylate, cresol novolac type epoxy poly(( (meth)acrylic acid epoxy esters such as methyl) acrylate. Further, it is also suitable as a reaction product of the above-mentioned (meth)acrylic compound and a compound having (preferably a plurality of) isocyanate groups or acid anhydride groups in the structure. Further, a main chain or a side chain of a conventional resin such as a vinyl resin, a polyester resin, a polyamide resin, a polyimide resin, a polyurethane resin, or a polyether resin may be used. A resin (meth)acryloyl group or the like is introduced by an ester bond, a guanamine bond, a urethane bond or the like. Further, in addition to the (meth)acrylic acid derivative, a maleic acid derivative, a maleic anhydride imide derivative, a crotonic acid derivative, an itaconic acid derivative, a cinnamic acid derivative, or a vinyl alcohol can also be used. Derivatives, etc. The photosensitive resin may be appropriately selected in accordance with the exposure sensitivity of the light-shielding composition for a color filter, etc., and may be used alone or in combination of two or more. It has an alkali-soluble functional group such as a carboxyl group or a phenolic hydroxyl group and has alkali developability. The amount of the photosensitive resin to be incorporated is preferably 5 to 50% by weight in the solid content, but is preferably 7 to 40% by weight, more preferably 10 to 30% by weight. Here, in a state where the amount of the photosensitive resin is excessively small, the photosensitivity of the light-shielding composition is lowered, and it is not easy to obtain an image by photolithography. On the other hand, in the state where the amount of the photosensitive resin is excessively excessive, the color is relatively colored. The amount of the material is reduced, and the light shielding property is insufficient.

As a photopolymerization initiator, it is preferred to use a conventional photopolymerization initiator, and examples thereof include acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyldiene. Ethylene benzophenone, benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzol, such as methyl ketal Benzophenones such as ketones, benzoin ethers, benzoin-tert-butyl ether, etc., 2-methyl-1-[4-(methylsulfonyl)phenyl]- α-Amino group such as 2-morpholinopropan-1-one, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinylphenyl)butan-1-one Alkyl phenones, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-[3,4-(methylenedihydroxy)phenyl 1-4,6 - triazines such as bis(trichloromethyl)-1,3,5-triazine, etc., 3,3',4,4'-tetrakis(tert-butylperoxycarbo)benzophenone, etc. Sulfur compounds such as organic peroxides, thioxanthone, 2,4-diethylthioxanthone, (2,4,6-trimethylphenylhydrazine) diphenylphosphine oxide, double (2, Phosphorus compounds such as 4,6-trimethylphenyl ether)phenylphosphine oxide, 1-[4-(benzene Sulfhydryl)phenyl]octane-1,2-dione-2-O-phenylene ether, 1-(9-ethyl-6-(2-methylbenzoquinone)-9H-carbazole-3-醯) oxime esters such as ethane-1-O-diethyl ether oxime, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2- Bi-diimidazoles such as diimidazole and the like are preferred, but triazines or oxime esters are particularly preferred in terms of obtaining high photosensitivity. The photopolymerization initiator may be appropriately selected in accordance with the exposure sensitivity of the light-shielding composition for a color filter, etc., and may be used alone or in combination of two or more. The amount of the photopolymerization initiator to be used is preferably from 1 to 10% by weight in the solid content, but is preferably from 2 to 8% by weight, more preferably from 3 to 6% by weight. Here, in photopolymerization In the state where the amount of the starting agent is excessively small, the photosensitivity of the light-shielding composition is lowered, and it is not easy to obtain an image by photolithography. On the other hand, in a state where the amount of the photopolymerization initiator is excessively increased, the amount of the relatively colored material is reduced, and the light shielding property is insufficient.

The cured film of the light-shielding composition for a color filter of the present invention preferably has a volume resistivity of 10 ¹⁴ Ω. More than cm. The volume resistivity is an index of insulation, and it can be said that the higher the volume resistivity, the higher the insulation. The measurement of the volume resistivity can be carried out by a conventional method. However, it is preferable to sandwich the cured film by a conductive metal deposition film, and to connect the electrodes to the respective metal deposition films by a micro galvanometer (ADVANTEST). The company's "R8340A" and other methods are used for measurement. In addition, in the state in which the coloring material is used without using a benzimidazolone dioxazine pigment and carbon black is used to form a light-shielding composition for a color filter, the insulating property is generally lowered, and the volume resistivity of the cured film is less than 10 ¹⁴ Ω. Cm.

The method for producing a light-shielding composition for a color filter of the present invention is not particularly limited. However, it is advantageous to prepare a dispersion of a coloring material such as a pigment (preferably using a dispersing agent) in a solvent or the like in advance. A method of producing a light-shielding composition for a color filter by using a photosensitive resin or a photopolymerization initiator. In addition, there is a method in which a light-shielding composition for a color filter is prepared by dispersing a coloring material in a photosensitive resin composition in which a photosensitive resin or the like is dissolved in a solvent, but a light-shielding composition for a color filter obtained is obtained. In terms of stability, it is better to be the former method.

The light-shielding composition for a color filter of the present invention can be cured by being applied to a substrate or the like by ultraviolet irradiation, heat baking, or the like. A cured film is obtained. As a method of applying a light-shielding composition for a color filter, a conventional method can be used, and for example, coating by a spin coater, a bar coater, a slit coater or the like can be mentioned. Further, it is preferable to dry the light-shielding composition for a color filter by using a hot plate or a vacuum dryer after coating. However, the method of coating and drying is not limited to the foregoing description.

The curing method by ultraviolet irradiation may be a conventional method, and for example, ultraviolet irradiation using a xenon lamp, a halogen lamp, a tungsten lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp or the like as a light source may be mentioned. When such ultraviolet irradiation is performed, the image is exposed by using a mask or the like, and the image is processed by the developer to form an image on the substrate. The developer is not particularly limited as long as it does not dissolve the unexposed portion and does not dissolve the exposed portion. However, an aqueous alkali solution containing various additives is preferred. Here, examples of the alkali component of the developer include an alkali metal carbonate, an alkali metal hydroxide, and a quaternary ammonium hydroxide. Examples of the additive include an organic solvent, a surfactant, and defoaming. Agent, anti-fungal agent, etc. Even in the case of the development method, a conventional method can be used, and examples thereof include immersion development, spray development, wipe development, ultrasonic development, and the like. The method of ultraviolet irradiation and development is also not particularly limited.

Further, in order to increase the strength of the cured film, it is preferred to carry out heat baking after ultraviolet irradiation. The method of heating and baking may be a conventional method, and may be, for example, a treatment by a hot plate, a hot air oven or the like, but is not limited thereto.

The curing condition of the light-shielding composition for a color filter is not particularly limited, but in terms of photohardening, it is preferably 10 to 1000 mJ/cm ² of ultraviolet light, and in terms of heat hardening, it is preferable. It is heated at 200~250°C for 20~60 minutes.

Moreover, as a method of producing a color filter using the cured film of the light-shielding composition for color filters mentioned above, the well-known method can be utilized.

[Effects of the Invention]

The light-shielding composition of the present invention is a component of a coloring material by using a benzimidazolone dioxazine pigment, thereby achieving high light-shielding property and becoming excellent in insulation property or dispersion stability. Extremely useful. Further, the color filter formed by using the light-shielding composition for a color filter of the present invention has a black matrix characterized by high light-shielding property and high insulation property, and therefore, particularly, it is possible to manufacture an IPS driving method or The STN-driven high-quality liquid crystal display has become extremely useful. In addition, the light-shielding composition for a color filter of the present invention is easy to form an image even if it is a relatively high film thickness of 1.5 μm or more. Therefore, a thick film required for an inkjet method or the like can be suitably used. The formation of the black matrix. Further, the light-shielding composition for a color filter of the present invention also has a feature that the dielectric constant is extremely low, and therefore, it is also suitable for formation of a color filter formed on an array substrate (color filters are on the array). .

Further, the light-shielding composition of the present invention is also useful as a coloring component for paints, printing inks, stationery inks, and plastics, in addition to color filters, and can also be used as an insulating material. The use of circuit wiring or the like, or the selection of an absorptive material as a visible light, can also be used for an optical filter or the like.

[Best Embodiment of the Invention]

Hereinafter, the present invention will be specifically described by way of examples. In addition, the following "parts" are all parts by weight.

[Example 1]

(production of light-shielding composition) Practice: Pigment. 60.0 parts by weight of a blue 80 ("Hostaperm Blue R5R VP2548", a coloring material, manufactured by Clariant Co., Ltd.), a cationic polymer dispersing agent ("AJISPER PB821" manufactured by Ajinomoto Fine-Techno Co., Ltd.), 20.0 parts by weight, and propylene glycol monomethyl ether acetate (Solvent) 320.0 parts by weight, and a dispersion treatment was carried out for 3 hours using a paint shaker to prepare a dispersion. Here, 0.4 mm φ of zirconia particles were used in the medium of the paint shaker at a filling rate of 20%. Next, a solution of 56.5 wt% propylene glycol monomethyl ether acetate solution ("V-259ME" manufactured by Nippon Steel Chemical Co., Ltd.) of the alkali-developing photosensitive resin having a bisphenol oxime type epoxy diacrylate structure was prepared. Parts by weight, dipentaerythritol hexaacrylate (photosensitive resin) 6.8 parts by weight, 1-(9-ethyl-6-(2-methylbenzoquinone)-9H-carbazole-3-indole)ethane-1- 5.0 parts by weight of O-acetylhydrazine (photopolymerization initiator), 14.8 parts by weight of propylene glycol monomethyl ether acetate (solvent), 60.0 parts by weight of propylene glycol diacetate (solvent), an anthrone-based surfactant ("FZ-2122" manufactured by Dow Corning Toray Co., Ltd.)  0.5 parts by weight Further, 1.0 part by weight of 3-(glycidoxy) propyltrimethoxydecane (decane coupling agent) was sufficiently stirred to prepare a photosensitive resin composition. Here, the dispersion liquid described above was mixed, and the mixture was sufficiently stirred to prepare 500.0 parts by weight of a light-shielding composition for a color filter having 60% by weight of a color material in a solid content.

(Production of a typical color filter) A light-shielding composition for a color filter described above was applied onto a glass substrate having a thickness of 5 mm and a thickness of 1 mm by using a spin coater to prepare a test piece. At this time, the number of rotations of the rotation was adjusted, and the coating conditions were controlled so that the film thickness of the produced cured film became 1.0 μm. Next, the test piece was treated on a hot plate at 80 ° C for 3 minutes, and the light-shielding composition for the color filter was dried to obtain a coated film. In the coating film, the mask was covered, and the ultraviolet ray of 100 mJ/cm ² was irradiated with a high-pressure mercury lamp to expose the image, and the alkali developer (10-fold dilution of "V-2401ID" manufactured by Nippon Steel Chemical Co., Ltd.) was used. The treatment was carried out, washed with water, and the image was developed. Finally, in a hot air oven at 230 ° C, the test piece was fired for 20 minutes to obtain a cured film, and a typical color filter having a black matrix or a line & space image formed by various line widths was produced. sheet.

When the optical density of the cured film obtained as described above was measured by "D200-II" manufactured by GretagMacbeth Co., the value was 2.0. Further, when the cured film was observed by an optical microscope, the image forming energy was evaluated by the image of the smallest line & space formed, and the value was 5 μm (the value was small). In addition, an aluminum vapor-deposited substrate was used instead of the glass substrate, and a cured film was produced in the same manner, and aluminum was vapor-deposited thereon, and when the volume resistivity was measured by applying a voltage of 5 V by "R8340A" manufactured by ADVANTEST Co., Ltd., Its value becomes 2 × 10 ¹⁵ Ω. Cm. The types and the like of the coloring materials are collectively collected and these results are shown in Table 1.

[Examples 2 to 4]

The coloring material used in the first embodiment was changed as shown in Table 1, and the light-shielding composition for a color filter and a typical color filter were produced in the same manner as in the first embodiment. Next, in the obtained cured film, when the optical density, the image forming ability, and the volume resistivity were measured in the same manner as in Example 1, a typical color filter having high light-shielding properties or good insulating properties was obtained. The results are shown in Table 1. Further, for example, in the coloring material used in the second embodiment, "PB80/PY139=70/30" shown in Table 1 means that PB80 contains 70% by weight and PY139 contains 30% by weight in the coloring material. Even if it is outside this, it is the same.

[Example 5]

Practice: Pigment. Blue80 ("Hostaperm Blue R5R VP2548" by Clariant Co., Ltd., coloring material) 35.0 parts by weight, Pigment. Yellow 139 (Paliotol Yellow D 1819, manufactured by BASF Co., Ltd., coloring material), 15.0 parts by weight, cationic polymer-based dispersing agent ("AJISPER PB821" manufactured by Ajinomoto Fine-Techno Co., Ltd.), 16.7 parts by weight, and propylene glycol monomethyl ether acetate (Solvent) 266.7 parts by weight, and the dispersion treatment was carried out in the same manner as in Example 1 to prepare a dispersion. Next, a 56.5 wt% propylene glycol monomethyl ether acetate solution ("V-259ME" manufactured by Nippon Steel Chemical Co., Ltd.) of the alkali-developing photosensitive resin having a bisphenol fluorene-type epoxy diacrylate structure was used. 12. parts by weight of dipentaerythritol hexaacrylate (photosensitive resin), bisphenolphthalein type epoxy resin ("ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), 2.5 parts by weight, 1-(9-ethyl-6) -(2-methylphenylhydrazine)-9H-carbazole-3-indole)ethane-1-O-acetamidopurine (photopolymerization initiator) 4.0 parts by weight, propylene glycol monomethyl ether acetate ( Solvent) 63.6 parts by weight, propylene glycol diacetate (solvent) 60.0 parts by weight, anthrone-based surfactant ("FZ-2122" manufactured by Dow Corning Toray Co., Ltd.) 0.5 parts by weight, and 3-(epoxypropyl oxide) 1.0 part by weight of propyltrimethoxydecane (decane coupling agent) was sufficiently stirred to prepare a photosensitive resin composition. Here, the dispersion liquid described above was mixed, and the mixture was sufficiently stirred to prepare 500.0 parts by weight of a light-shielding composition for a color filter having 50% by weight of a color material in a solid content.

A typical color filter was produced in the same manner as in Example 1 using the above-described light-shielding composition for a color filter. Next, in terms of the obtained cured film, the optical density, the image forming ability, and the volume were measured in the same manner as in Example 1. At the specific resistance, a typical color filter of high quality having good light blocking property or insulating property is obtained. The results are shown in Table 1.

[Examples 6 to 8]

The coloring material used in Example 5 was changed as shown in Table 1, and the light-shielding composition for a color filter and a typical color filter were produced in the same manner as in Example 5. Next, in the obtained cured film, when the optical density, the image forming ability, and the volume resistivity were measured in the same manner as in Example 1, a typical color filter having high light-shielding properties or good insulating properties was obtained. The results are shown in Table 1.

[Embodiment 9]

Practice: Pigment. Blue80 ("HostaPerm Blue R5R VP2548" manufactured by Clariant Co., Ltd., coloring material) 20.0 parts by weight, Pigment. Yellow 139 (Paliotol Yellow D 1819, manufactured by BASF Co., Ltd., coloring material) 20.0 parts by weight, cationic polymer dispersant ("AJISPER PB821" manufactured by Ajinomoto Fine-Techno Co., Ltd.), 13.3 parts by weight, and propylene glycol monomethyl ether acetate (Solvent) 213.3 parts by weight, the dispersion treatment was carried out in the same manner as in Example 1 to prepare a dispersion. Next, a 56.5 wt% propylene glycol monomethyl ether acetate solution ("V-259ME" manufactured by Nippon Steel Chemical Co., Ltd.) of the alkali-developing photosensitive resin having a bisphenol fluorene-type epoxy diacrylate structure was used. 19. parts by weight of dipentaerythritol hexaacrylate (photosensitive resin), bisphenolphthalein type epoxy resin ("ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), 3.9 parts by weight, 1-(9- Ethyl-6-(2-methylphenylhydrazine)-9H-carbazole-3-indene)ethane-1-O-acetamidopurine (photopolymerization initiator) 2.5 parts by weight, propylene glycol monomethyl ether 111.8 parts by weight of acetate (solvent), 60.0 parts by weight of propylene glycol diacetate (solvent), 0.5 part by weight of an anthrone-based surfactant ("FZ-2122" manufactured by Dow Corning Toray Co., Ltd.), and 3-(epoxy) 1.0 part by weight of propyl oxy) propyl trimethoxy decane (decane coupling agent) was sufficiently stirred to prepare a photosensitive resin composition. Here, the dispersion liquid described above was mixed, and the mixture was sufficiently stirred to prepare 500.0 parts by weight of a light-shielding composition for a color filter having 40% by weight of a color material in a solid content.

A typical color filter was produced in the same manner as in Example 1 using the above-described light-shielding composition for a color filter. Next, in the obtained cured film, when the optical density, the image forming ability, and the volume resistivity were measured in the same manner as in Example 1, a typical color filter of high quality having good light-shielding property or insulating property was obtained. The results are shown in Table 1.

[Reference Example 1]

Except that the coating conditions were changed by using the light-shielding composition for a color filter of Example 7, and the film thickness of the cured film to be produced was 1.5, 2.0, 2.5, and 3.0 μm, the same procedure as in Example 1 was carried out. A typical color filter with a film thickness. Next, in the obtained cured film, when the optical density and the image forming ability were measured in the same manner as in Example 1, the optical density was 3.3 (film thickness: 1.5 μm), 4.2 (film thickness: 2.0 μm), and 5.1 (film thickness: 2.5). Μm), 5.9 (film thickness 3.0 μm), image formation energy system 3 μm (film thickness) 1.5 μm), 3 μm (thickness: 2.0 μm), 5 μm (thickness: 2.5 μm), and 5 μm (thickness: 3.0 μm) each gave a typical color filter of a black matrix having a high-quality thick film.

[Reference Example 2]

A light-shielding composition of the color filter of Example 7 was applied onto a copper foil, and a cured film having a film thickness of 2.0 μm was produced in the same manner as in Example 1. When the specific dielectric constant is calculated by measuring the electrostatic capacitance by the LCR meter ("4284A" manufactured by Agilent Technologies, Inc.), the cured film has a value of 3.7 to 2.7 in the range of 20 Hz to 1 MHz. It becomes very low.

[Comparative Examples 1 to 4]

The coloring material used in the first embodiment was changed as shown in Table 1, and the light-shielding composition for a color filter and a typical color filter were produced in the same manner as in the first embodiment. Then, in the obtained cured film, when the optical density, the image forming ability, and the volume resistivity were measured in the same manner as in Example 1, the light-shielding property of the cured film was lowered, and the performance of a typical color filter was insufficient. The results are shown in Table 1.

[Comparative Example 5]

Practice: Pigment. Blue80 ("Hostaperm Blue R5R VP2548" manufactured by C1ariant Co., Ltd., coloring material) 15.0 parts by weight, Pigment. Yellow139 ("Paliotol Yellow D 1819" made by BASF) 15.0 parts by weight, 10.0 parts by weight of a cationic polymer-based dispersant ("AJISPER PB821" manufactured by Ajinomoto Fine-Techno Co., Ltd.), and 160.0 parts by weight of propylene glycol monomethyl ether acetate (solvent), which is the same as in Example 1. The dispersion processing was carried out to prepare a dispersion. Next, a 56.5 wt% propylene glycol monomethyl ether acetate solution ("V-259ME" manufactured by Nippon Steel Chemical Co., Ltd.) of the alkali-developing photosensitive resin having a bisphenol fluorene-type epoxy diacrylate structure was used. 2 parts by weight of dipentaerythritol hexaacrylate (photosensitive resin), bisphenolphthalein type epoxy resin ("ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), 5.1 parts by weight, 1-(9-ethyl-6) -(2-methylphenylhydrazine)-9H-carbazole-3-ether)ethane-1-O-acetamidopurine (photopolymerization initiator) 2.0 parts by weight, propylene glycol monomethyl ether acetate ( Solvent) 160.2 parts by weight, propylene glycol diacetate (solvent) 60.0 parts by weight, anthrone-based surfactant ("FZ-2122" manufactured by Dow Corning Toray Co., Ltd.) 0.5 parts by weight, and 3-(epoxypropyl oxide) 1.0 part by weight of propyltrimethoxydecane (decane coupling agent) was sufficiently stirred to prepare a photosensitive resin composition. Here, the dispersion liquid was mixed, and the mixture was sufficiently stirred to prepare 500.0 parts by weight of a light-shielding composition for a color filter having 30% by weight of a color material in a solid content.

A typical color filter was produced in the same manner as in Example 1 using the above-described light-shielding composition for a color filter. Next, in the obtained cured film, when the optical density, the image forming ability, and the volume resistivity were measured in the same manner as in Example 1, the light-shielding property of the cured film was lowered, and the performance of a typical color filter was insufficient. The results are shown in Table 1.

[Comparative Example 6]

The colored material used in the comparative example 5 was changed to carbon black ("MA100" manufactured by Mitsubishi Chemical Corporation), and the light-shielding composition for a color filter and a typical color filter were produced in the same manner as in Comparative Example 5. Then, in the obtained cured film, when the optical density, the image forming ability, and the volume resistivity were measured in the same manner as in Example 1, the light-shielding property of the cured film was good, but the insulating property was insufficient. The results are shown in Table 1.

[Industrial availability]

The light-shielding composition of the present invention can be suitably used for the formation of a color filter, and is particularly suitable for the formation of a black matrix. In addition, the light-shielding composition of the present invention is useful as, for example, a coating material, a printing ink, a stationery ink, a coloring component for plastics, and the like, and may be used as an insulating material. For use in circuit wiring or the like, or as a visible light selective absorbent material, it can also be used for optical filters and the like.

Claims (5)

A light-shielding composition containing 40% by weight or more of a light-shielding composition in a solid component of a coloring material composed of an organic pigment, wherein the coloring material contains 30% by weight or more of the following formula (1) The optical concentration of the hardened film of the hardenable light-shielding composition of the benzimidazolone dioxazine pigment shown is 1 μm or more, and is 2.0 or more; (However, R ¹ and R ² each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a substituent, and X represents a hydrogen atom or a halogen atom). The light-shielding composition according to the first aspect of the invention, wherein the coloring material contains at least one weight percent of at least one organic pigment selected from the group consisting of yellow, orange, red, and brown. A light-shielding composition for a color filter, which is a light-shielding composition according to the first aspect of the invention, characterized in that the solid component contains 5 to 50% by weight of a photosensitive resin and a photopolymerization initiator. 1 to 10% by weight, an image can be formed by photolithography. The light-shielding composition for a color filter according to the third aspect of the invention, wherein the cured film of the light-shielding composition for curing the color filter has a volume resistivity of 10 ¹⁴ ohms. More than centimeters. A color filter comprising the cured film of the light-shielding composition for a color filter according to the third or fourth aspect of the invention.