KR20000028936A - Colouring composition, method for preparing the same, and colour filter, electrode substrate and liquid crystal display using the same - Google Patents

Abstract

PURPOSE: A coloring composition which has high insulating property and is also excellent in light fastness, light resistance and dispersion stability, and a color filter, an electrode substrate and a liquid crystal display device using the same are provided. CONSTITUTION: A coloring composition comprises a coloring agent containing titanium black, a resin and an insulating material. Preferably, the insulating material is in an amount of 1 - 35 wt.% based on the coloring agent and the coloring agent is coated with the insulating material. Preferably, the insulating material also contains at least one selected from the group consisting of silica, alumina and zirconia. The coloring agent can further comprise, in addition to dispersing agent and solvent, photopolymerization monomer and photopolymerization initiator, or cross linking agent and mineral acid generator, or photopolymerization monomer and diazo or azide compound. The coloring composition has high insulating property and is most suitable for the formation of black matrix. Liquid crystal display device with high quality can be obtained by using the black matrix.

Description

Colored composition, its manufacturing method and color filter, electrode substrate, and liquid crystal display device using the same {COLOURING COMPOSITION, METHOD FOR PREPARING THE SAME, AND COLOUR FILTER, ELECTRODE SUBSTRATE AND LIQUID CRYSTAL DISPLAY USING THE SAME}

The present invention relates to a coloring composition excellent in insulation, a color filter, an electrode substrate, and a liquid crystal display device using the same, and to provide a coloring composition suitable for a liquid crystal display device requiring high display quality.

2. The liquid crystal display device generally has a liquid crystal drive electrode plate 31, a common electrode electrode plate 32 disposed to face the liquid crystal drive electrode plate 31, as shown in the sectional view of the main part of FIG. And the liquid crystal material 33 enclosed in the gap between these two electrode plates 31 and 32.

The liquid crystal drive electrode plate 31 is electrically connected to a substrate 31a, a pixel electrode 31b provided independently of each other in correspondence with each pixel of a display screen, and each of the pixel electrode 31b. And a switching element 31c which energizes each pixel electrode 31b in accordance with the screen display signal. The common electrode plate 32 is provided with a transparent substrate 32a and a transparent common electrode 32b commonly provided on all the pixels of the display screen on the transparent substrate 32a.

In addition, as shown in Fig. 2, when the device is a full-color liquid crystal display device displaying a full-color screen, the transmitted light passing through the pixel for each pixel of the electrode plate 32 for common electrodes is changed to each color. The color filter 34 to color is provided. In this kind of liquid crystal display device, the switching element 31c is energized in accordance with a pixel display signal to energize each pixel electrode 31b, and the pixel electrode 31b and the transparent common electrode 32b which are energized. The liquid crystal material 33 is driven by a voltage between them to control the transmission and impermeability of light rays to display the screen.

In such a liquid crystal display device, transmitted light is scattered at the site where the switching element 31c is installed under the influence of the switching element 31c, and as a result, the contrast of the display screen is lowered and the quality thereof is deteriorated. Thus, the black matrix 35 is provided on the electrode plate 32 for the common electrode in order to block the light incident on the portion and to prevent the quality deterioration of the display screen.

In this case, even when an error occurs in the relative position between the black matrix 35 and the switching element 31c due to the liquid crystal display manufacturing process, the black matrix 35 exists at a position corresponding to the switching element 31c. There is a need. As a cause of this error, when the black matrix 35 is formed on the electrode plate 32 for the common electrode and the position accuracy error when the switching element 31c is formed on the liquid crystal drive electrode plate 31. Relative errors (up to about 5 μm) between the two electrode plates 31 and 32 based on the positional accuracy error of the liquid crystal drive electrode plate 31 and the common electrode electrode plate 32 are assembled and integrated. There is a position matching error (up to about 5 µm) of these electrode plates 31 and 32 at the time. For this reason, the black matrix 35 is formed larger by about 10 micrometers (20 micrometers in total) compared with the switching element 31c.

By the way, in recent years, it has been strongly requested to refine the pixels of the liquid crystal display device to increase its pixel precision and to increase the density and high quality of the display pixels. Since it cannot be miniaturized, the opening ratio (the ratio of the total area of the pixel part which occupies a pixel display area) falls with the refinement | miniaturization and the precision of a pixel, and there existed a problem that the brightness of a display screen fell.

Therefore, it is desired to develop an electrode substrate capable of reducing the relative positional accuracy between the black matrix 35 and the switching element 31c and increasing the aperture ratio. As such a technique, there is a method of forming a black matrix on the array substrate side disclosed in, for example, Japanese Patent Laid-Open No. 6-130218.

On the other hand, the conventional black matrix was formed of metal. In the formation of the black matrix 35, first, a metal thin film of Cr, Ni, Al or the like is formed on a substrate such as glass by vapor deposition, sputtering, vacuum deposition, or the like, and then a photoresist is applied on the metal thin film. After irradiating an ultraviolet-ray through the photomask which formed the desired pattern, it develops and obtains a resist pattern. Then, a metal thin film portion other than the resist portion is removed by means of etching or the like, and finally, the resist is peeled off to form a black matrix.

However, when a liquid crystal panel was produced using the color filter using these metal black matrices, it became conductive with the liquid crystal drive electrode, and as a result, there existed a problem of a liquid crystal not working or a malfunction. For this reason, it is necessary to form an insulating black matrix, and various methods which do not use a metal thin film are examined.

For example, Japanese Patent Laid-Open No. 2-239204 (A) proposes a method of dispersing a light shielding agent in a polyimide resin and forming a black matrix using an etching method. Moreover, the composition which added the light-shielding agent directly to the photosensitive resin composition is also reported. Most of these materials use carbon black to improve light shielding. For example, Japanese Patent Application Laid-Open No. 4-63870 (A) discloses a method of forming a black matrix by dispersing carbon black and an organic pigment in a photopolymerization compound. Is proposed.

Further, in the method of forming a black matrix on the array substrate side described above (Japanese Patent Laid-Open No. 6-130218 (A)), a black resist obtained by dispersing conductive carbon black as a black pigment as a light shielding material for forming a black matrix ( At least two or more of three types of color filter forming resists of red, green, and blue are mixed and mixed. (Iii) A blackened resist mixture is used.

However, carbon black has higher conductivity than other organic pigments having light shielding properties, and when the carbon black is added too much in the photosensitive resin to increase the light shielding properties, the formed black matrix itself also has conductivity. For this reason, even if a color filter is manufactured using these materials, it may be electrically connected with a liquid crystal drive electrode, and the problem of a liquid crystal not working or malfunctioning could not be fully controlled.

On the other hand, there is also a method of dispersing a metal oxide pigment in a resin as a light shielding agent to form a black matrix. However, also in a metal oxide pigment, the problem which has voltage dependence or light-shielding property by an applied voltage arises.

Therefore, development of the coloring composition which has higher insulation property, and has light resistance, light shielding property, and dispersion stability than before, and the development of the color filter, electrode substrate, and liquid crystal display device using such a coloring composition are desired.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a coloring composition having high insulation and excellent light resistance, light shielding properties, and dispersion stability, a color filter, an electrode substrate, and a liquid crystal display device using the same, and further comprising a black matrix and a switching element. It is an object of the present invention to provide an electrode substrate and a liquid crystal display device having a large aperture ratio of a display screen by reducing the relative positional accuracy therebetween.

1 is a cross-sectional view showing a main portion of an example of a liquid crystal display device;

2 is a cross-sectional view showing the main parts of an example of a liquid crystal display device.

<Description of the code | symbol about the principal part of drawing>

10 liquid crystal display device 11 transparent substrate

11a: transparent substrate 11b: pixel electrode

11c: switching element 12: black matrix

21b: color filter

MEANS TO SOLVE THE PROBLEM The present inventors came to this invention as a result of earnestly researching in order to solve the said subject.

The coloring composition of this invention is characterized by containing the coloring agent containing titanium black, resin, and an insulating substance.

It is preferable that the said insulating substance is 1 to 35 weight% of a coloring agent.

The coloring composition of the present invention further comprises a colorant comprising a titanium black coated with an insulating material and a resin, wherein the insulating material is 1 to 35% by weight of the colorant.

It is preferable that the said insulating substance contains at least 1 sort (s) chosen from a silica, an alumina, and a zirconia.

It is preferable that an insulating substance is 1 to 35 weight% of a coloring agent.

It is preferable that the said resin is photosensitive resin.

It is preferable to contain a dispersing agent, a photoinitiator, a photoinitiator, and a solvent in the said coloring composition further.

Or it is preferable that the said coloring composition also contains a dispersing agent, a crosslinking agent, a photoacid generator, and a solvent.

Or in the said coloring composition, it is also preferable to contain a dispersing agent, a photopolymerization monomer, a diazo type, or an azide type compound, and a solvent.

It is preferable that the said resin consists of (meth) acrylic-type resin.

The resin is a vinyl copolymer comprising 10 to 40% by weight of a compound having one vinyl group and a hydroxyl group, 10 to 30% by weight of a compound having one vinyl group and a carboxyl group and 30 to 75% by weight of a compound having one vinyl group. It is preferable that it is the acid value 50-150 photosensitive resin obtained by making 5-25 mol% correspond to the compound which has an isocyanate group and at least 1 or more vinyl group with respect to 100 mol% of a compound.

Moreover, it is preferable that the said resin is photosensitive resin which has the unit structure shown by following General formula (1) and / or (2) as a main component.

(Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R ₃ is a hydrogen atom or a methyl group, X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, or the following formula (3) or absent: Y represents an acid anhydride residue, Z Represents residues of acid dihydrate, m and n are integers of 1 or more.)

It is preferable that the said coloring composition has a volume resistivity of 10 ⁷ Ωcm or more.

Moreover, the manufacturing method of the coloring composition of this invention mixes a coloring agent and an insulating substance, obtains the coloring agent coat | covered with an insulating substance, and is then mix | blended resin with this coloring agent. It is characterized by the above-mentioned.

The color filter of the present invention is characterized in that a black matrix is formed using the coloring composition.

The liquid crystal display of the present invention is characterized in that the color filter is used.

The electrode substrate of the present invention is an electrode substrate comprising a switching element and a pixel electrode on a transparent substrate, and a black matrix made of the coloring composition is formed on at least the switching element.

The liquid crystal display device of this invention uses the said electrode substrate, It is characterized by the above-mentioned.

<Embodiment of the Invention>

Hereinafter, the present invention will be described in detail.

The coloring composition of this invention is characterized by including the colorant containing titanium black, resin, and an insulating substance, It is preferable that the said insulating substance is 1 to 35 weight% of the said coloring agent.

It is preferable to use the colorant containing titanium black, when this film strength becomes high, when a film is formed with the obtained coloring composition. In addition, high insulation can be obtained even with a small amount of insulating material. That is, since high insulation can be obtained without reducing the light-shielding property which titanium black has, it is preferable.

As resin, photosensitive resin or (meth) acrylic-type resin is preferable. It is more preferable that these resins are excellent in dispersibility, heat resistance, and transparency, and have a volume resistivity of 10 ⁷ cm 3 or more. As a monomer which comprises (meth) acrylic-type resin, what is represented by following General formula (4) is mentioned normally.

Moreover, the (meth) acrylic-type resin comprised specifically, the monomer of the following description is preferable.

However, it goes without saying that they are not limited to these, and these may be used alone or in combination of two or more. Among them, (meth) acrylic resins synthesized with monomers selected as necessary are preferably used.

Examples of the (meth) acrylic resins include dimethylaminoethyl methacrylate, benzyl acrylate, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidine, and tetrahydrofurfuryl methacrylate in addition to the acrylic monomers. Monomers, such as these, can be selected suitably and used.

As a photosensitive resin, the vinyl system which consists of 10-40 weight% of compounds which have one vinyl group and a hydroxyl group, 10-30 weight% of compounds which have one vinyl group and a carboxyl group, and 30-75 weight% of compounds which have one vinyl group The thing of the acid value 50-150 obtained by making 5-25 mol% of compounds which have an isocyanate group and at least 1 or more vinyl group react with respect to 100 mol% of copolymerization compounds is preferable.

Here, as a compound which has one vinyl group and a hydroxyl group, 2-hydroxyethyl ester, 2-hydroxyoctyl ester, 2-hydroxypropyl ester, etc. of acrylic acid or methacrylic acid (henceforth (meth) acrylic acid), etc. are mentioned. N-methylol acrylamide, allyl alcohol, etc. are mentioned.

Acrylic acid, methacrylic acid, itaconic acid, etc. are mentioned as a compound which has one vinyl group and a carboxyl group.

Examples of the compound having one vinyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. Stearyl meta), methoxy ethyl (meth) acrylate, ethoxy ethyl (meth) acrylate, butoxy ethyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, acrylonitrile, ( Methyl) methyl acrylate, etc. are mentioned.

As a compound which has an isocyanate group and at least 1 or more vinyl groups, 1 mol of polyisocyanate compounds which have n (is 2 or more) isocyanate groups in at least 1 molecule, and the group which reacts with 1 isocyanate group in 1 molecule, for example, a hydroxyl group And a compound obtained by reacting a vinyl compound (n-1) mole having at least one or more vinyl groups at 40 to 100 ° C, or isocyanate ethyl methacrylate, methacryloyl isocyanate, or the like can be used. .

Here, as a polyisocyanate compound, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4, 4'- diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, water addition 4, 4'- Diphenylmethane diisocyanate, water addition toluene diisocyanate, etc. are mentioned. As a vinyl compound which has one hydroxyl group made to react with a polyisocyanate compound, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 2-hydroxyoctyl ester, etc. of (meth) acrylic acid, N-methylol acrylamide, allyl Alcohol, glycerol di (meth) acrylate, glycerol di (meth) alkylate, glycerol di (meth) acrylate alkenyl, butyl glycidyl ester (meth) acrylate, phenyl glycidyl ether (meth) acrylate , Polyethylene glycol mono (meth) acrylate, polycapronate (meth) acrylate, tetramethylol methane tri (meth) acrylate, and the like.

The vinyl copolymer compound consisting of a compound having one vinyl group, a compound having one vinyl group and a carboxyl group, and a compound having one vinyl group can be produced by a known method, and cyclohexanone and cellosolve acetate It is preferable to manufacture by solution polymerization in solvents, such as diethylene glycol methyl ether, ethylbenzene, ethylene glycol diethyl ether, and xylene. When prepared by solution polymerization, when the vinyl group is introduced into the obtained vinyl copolymer compound through an isocyanate group to form a photosensitive copolymer compound, the reaction can be easily proceeded, and the colored composition using the obtained photosensitive resin can be applied to a thin film on a glass substrate. It is preferable because it is easy.

The copolymerization ratio of the compound which has one vinyl group and one hydroxyl group is 10-40 weight%. If it is less than 10 weight%, the photosensitive device obtained after reaction will decrease and exposure sensitivity will fall, and adhesiveness to a board | substrate will also be bad, and if it exceeds 40 weight%, it will become easy to develop and a resolution will worsen.

The copolymerization ratio of the compound which has one vinyl group and a carboxyl group is 10-30 weight%. If it is less than 10 weight%, developability is bad, and when it exceeds 30 weight%, it will become easy to develop and resolution will worsen.

In addition, the copolymerization ratio of the compound which has one vinyl group is 30 to 75 weight%. If it is less than 30 weight%, exposure sensitivity will fall, and when it exceeds 75 weight%, it will be hard to develop and resolution of a pattern cannot be obtained.

With respect to 100 mol% of this vinyl-type copolymerization compound, the compound which has one isocyanate group and at least 1 or more vinyl groups is reacted at 5-25 mol%, Preferably it is 10-20 mol%, and the photosensitive resin is obtained.

At this time, when the compound which has one isocyanate group and at least 1 or more vinyl groups is less than 5 mol, exposure sensitivity will fall largely and the film thickness change before and behind alkali image development will become large, and heat resistance and solvent resistance will fall. On the other hand, when it exceeds 25 mol%, a halation effect will be exhibited at the time of exposure, the resolution will worsen and flammability will occur at the time of solvent drying.

It is preferable to adjust the acid value of the photosensitive resin to 50-150 in order to make developability by an alkaline developing solution more favorable. If the acid value is less than 50, the development time is long, which does not develop and causes mess. In addition, when the acid value exceeds 150, the development time is too short to obtain a working margin, and a problem occurs such that the pattern shape after development becomes thin or the cross-sectional shape becomes inverted.

It is preferable to mainly make the unit structure represented by the said General formula (1) and / or (2) other than this as photosensitive resin.

In the said general formula (1) and (2), Preferably, R <_1> , R <_2> is a hydrogen atom or a methyl group, and R <_3> is a hydrogen atom.

In addition, the bisphenol component unit containing X is contained in the unit structure shown by the said General formula (1) and (2). As a specific example of such a bisphenol component, what is shown below is mentioned.

Specific examples of the bisphenol component containing -CO- as X include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone and bis (4-hydroxy-3, 5 -dichlorophenyl) ketone, -SO ₂ X a - as including a include bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4- Examples of X containing -C (CF ₃ ) ₂ -as X, such as hydroxy-3 and 5-dichlorophenyl) sulfone, include bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-a-3, 5-dichloro-phenyl), X, etc. hexafluoropropane -Si (CF _{3) 2} - as including a include bis (4- Hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane and the like -CH ₂ -as X As it is, bis (4-hydroxyphenyl) methane, bis (4-hi Is 2, 2-bis as including the (- hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) as a, X such as methane, -C (CH _{3) 2} 4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 2, 2-bis (4-hydroxy-3-chlorophenyl) propane, and the like, and bis (4- Hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dimethylphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether and the like.

In addition, as X in formula, the thing containing the said General formula (3) is used preferably, As a specific example of such a bisphenol component, 9, 9-bis (4-hydroxyphenyl) fluorene, 9, 9-bis ( 4-hydroxy-3-methylphenyl) fluorene, 9, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9, 9-bis (4-hydroxy-3- fluorophenyl) fluorene, 9, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9, 9-bis (4- hydride) Hydroxy-3, 5-dichlorophenyl) fluorene, 9, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, etc. are mentioned.

As X which does not exist, 4, 4'-biphenol, 3, 3'-biphenol, etc. are mentioned.

In the formulas (1) and (2), Y and Z represent Y residues of acid anhydrides, and Z represents residues of acid dianhydrides.

As an acid anhydride which can introduce such a residue Y, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endmethylene tetrahydrophthalic anhydride, chloride anhydride Acid, methyl tetrahydro phthalic anhydride, etc. are mentioned. Moreover, as an acid dianhydride which can introduce | transduce residue Z, aromatic polyhydric carboxylic anhydrides, such as a pyromellitic anhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl ether tetracarboxylic dianhydride, are mentioned, for example.

The component which has the unit structure shown by the said General formula (1) and (2) is not limited only to what was mentioned above, In addition, you may use only one of these types, or may mix and use two or more types.

As an insulating substance contained in the coloring composition of this invention, it is preferable that at least 1 sort (s) chosen from silica, alumina, and zirconia is contained. Although there is no restriction | limiting in particular as a raw material of these insulating materials, Liquid substances, such as a silica sol, aqueous sodium silicate solution, an alumina sol, a zirconia sol, and inorganic fine particles, such as amorphous silica, are preferable. By adding these insulating substances, while being excellent in the insulation of a coloring composition, the improvement of surface hardness, the improvement of mechanical strength, the improvement of a thermal characteristic, the improvement of dispersibility, the improvement of light resistance, etc. can also be achieved.

When the insulating substance contains 1 to 35% by weight of the colorant containing titanium black in the coloring composition, the resulting coloring composition has a high insulating property, which is preferable. If it is less than 1% by weight, no apparent addition effect to the volume resistivity can be seen, and if it exceeds 35% by weight, a decrease in light-shielding properties may be observed, or problems such as poor adhesion to the transparent substrate and impact resistance may occur. Preferably it is 1-20 weight%, More preferably, it is 1-10 weight%. Since it is such a small coating amount, high light-shielding property can be obtained.

Although these insulating substances are contained in a coloring composition, the insulation of a coloring composition can be improved, but the coloring composition obtained can implement | achieve higher insulation by coating the coloring agent in a coloring composition with an insulating substance previously.

As a method of coating the colorant in the coloring composition with an insulating material, a known technique can be used in addition to the method of mixing the colorant and the insulating material. In the case of forming a silica coating using sodium silicate as a raw material of the insulating material, Describe.

First, as a 1st process, a colorant is disperse | distributed for 1 hour and a half using a bead mill, and an aqueous slurry is obtained. Next, as a 2nd process, the sodium silicate solution is added to the aqueous slurry of a coloring agent. As a 3rd process, the said solution is stirred well using a homogenizer, and a colorant is grind | pulverized. In the fourth step, the solution is heated. In the fifth step, sodium silicate solution and sulfuric acid are added and stirred well using a homogenizer. This completes the silica coating. In the final step, the colorant is filtered off, and dried to obtain a colorant coated with silica.

The coloring composition is obtained by obtaining a colorant coated with an insulating substance and then mixing the resin with the colorant.

As a preferable aspect of the coloring composition of this invention, the photopolymerization monomer and the photoinitiator, the crosslinking agent, the photo-acid generator, or the photopolymerization in the paste in which the colorant and dispersing agent surface-treated with an insulating substance, and the (meth) acrylic-type resin were disperse | distributed uniformly in the solvent. The photosensitive coloring composition obtained by adding a monomer, a diazo system, and an azide compound is mentioned. Moreover, it is preferable that this coloring composition has a volume resistivity of 10 ⁷ Ωcm or more.

As a dispersing agent, a nonionic surfactant (for example, polyoxyethylene alkyl ether), an ionic surfactant (for example, sodium alkylbenzene sulfonate, poly fatty acid salt, fatty acid alkyl phosphate, tetraalkyl ammonium salt), organic pigment derivative, Polyester etc. are mentioned. These may be used individually by 1 type, or may mix and use two or more types.

As the photopolymerization monomer, as a monofunctional monomer, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acetate, tripropylene glycol acrylate, polyethylene glycol as a bifunctional monomer As diacrylate, tetraethylene glycol diacrylate, and trifunctional monomer, trimethylol propane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, and a polyfunctional monomer are trimethylol propane tetraacryl. Elate, dipentaerythritol penta, hexaacrylate, etc. are mentioned.

As a photoinitiator, a triazine type compound, an imidazole compound, a benzophenone compound, etc. are mentioned. Examples of the triazine-based compound include piperonyl-s-triazine, 2, 4, 6-tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4, 6-bis (trichloro) Romeryl) -s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl)- s-triazine, 2- (p-chlorophenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy-1'-naphthyl) -4, 6- Bis (trichloromethyl) -s-triazine etc. are mentioned. Examples of the imidazole compound include 2- (2, 3-dichlorophenyl) -4, 5-diphenylimidazoleel dimer, 2- (2, 3-dichlorophenyl) -4, and 5-bis (3-methoxy Phenyl) -imidazole dimer, 2- (2, 3-dichlorophenyl) -4, 5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2, 3-dichlorophenyl) -4, 5-bis (4-dichlorophenyl) -imidazole dimer, 2- (2, 3-dichlorophenyl) -4, 5-di (2-furyl) -imidazole, 2, 2'-bis (2-chloro Phenyl) -4, 5, 4 ', 5'-tetraphenyl-1-2'-biimidazole, etc. are mentioned. As the benzophenone compound, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, acrylate benzophenone, 4-benzoyl-4'-methyldilphenyl sulfide, 3, 3'-dimethyl-4-methoxybenzophenone, 4, 4 "-Dimethylaminobenzophenone, 4-dimethylamino benzoate, etc. are mentioned.

Photoacid generators include triazine compounds and onium salt compounds. As a triazine type compound, it is as having described above. As onium salt type compound, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoroate, diphenyl iodonium hexafluoro acetate, diphenyl iodonium trifluoro methanesulfonate, diphenyl iodonium trifluoro acetate , Diphenyl iodonium-p-toluenesulfonate, 4-methoxyphenyl-phenyl iodonium tetrafluoroborate, 4-methoxyphenyl-phenyl iodonium hexafluorophosphonate, etc. are mentioned.

As the crosslinking agent, those having an N-methylol structure are used. For example, methylolated urea, urea resin, methylolated melamine, butylolated melamine, methylolated guanamine, or alkyl ethers of these compounds can be used. An alkyl ether compound is more preferable at this high point. As an alkyl group of this alkyl ether, a C1-C5 alkyl group is preferable. In particular, the alkyl ether compound of hexamethylolmelamine is more preferable as the alkyl ether compound. The crosslinking agent causes a crosslinking reaction with the resin to form a pattern by heating in the presence of oxygen generated after exposure.

As a diazo type compound, the formaldehyde condensate of p-diazo diphenylamine, hexafluorate, tetrafluoro borate, perchlorate, p-toluenesulfonic acid, or 2-hydroxy-4- methoxy benzophenone-5-sulfonic acid There is a diazonium salt obtained by reaction with.

As an azide type compound, 4, 4'- diazide styrenebene, 4, 4'- diazide benzophenone, 4, 4'- diazide chalcone, 4, 4'- diazide diphenylmethane, p-phenylene There is bis-azide.

Examples of the solvent include benzene solvents such as toluene and xylene, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and the like. Propylene glycol monoalkyl ether acetates such as cellosolve acetate esters, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ketone solvents, such as diethylene glycol, such as ether, acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone, etc. are used. These are appropriately selected for dispersion stability or the like, and may be used alone or in combination of two or more.

Next, the preferable compounding ratio of each component of this invention is demonstrated.

Solid content of a coloring composition, ie, the ratio of the component except a solvent, is 5 to 45 weight%, Preferably it is 10 to 35 weight%, More preferably, it is 20 to 30 weight%. When less than 5 weight% or more than 45 weight%, when apply | coating this coloring composition to a board | substrate with application apparatuses, such as a spin coat and a roll coat, it is difficult to obtain a desired film thickness, and applicability | paintability also falls.

The proportion of the coated colorant is 10 to 250% by weight relative to the resin, preferably 20 to 150% by weight. If it is less than 50 weight%, the light-shielding property at the time of forming a black matrix using this coloring composition falls. For this reason, a thick film thickness is calculated | required, and as a result, it may cause trouble at the time of forming a liquid crystal aligning film, and there exists a possibility that liquid crystal display performance may be impaired. When it exceeds 250 weight%, it becomes difficult to disperse | distribute uniformly and even if it forms a black matrix, there exists a possibility that mechanical strength, such as adhesiveness, may fall.

The proportion of the dispersant is preferably 1% by weight or more based on the colorant. If it is less than 1 weight%, it will be difficult to make uniform dispersion | distribution, and it will lack stability.

The addition amount of a photopolymerization monomer is about 20 to 150 weight% of resin.

The addition amount of a photoinitiator is 5-150 weight%, Preferably it is 80-130 weight% of a photoinitiator, A photoinitiator is used individually by adding one type or two or more types.

The coloring composition of this invention can be manufactured by mixing each component mentioned above by a conventional method. For example, the (meth) acrylic resin is diluted with a solvent, a colorant and a dispersant surface-treated with an insulating substance are added to the diluent, and uniformly dispersed in a bead mill disperser, and then the photopolymerizable monomer and It is obtained by adding and uniformly mixing a photoinitiator, a crosslinking agent, a photo-acid generator, or a photopolymerization monomer, a diazo type, and an azide type compound.

Since such a coloring composition has high insulation, the color filter which has a black matrix formed from this coloring composition does not conduct with a liquid crystal drive electrode. Moreover, this coloring composition is excellent also in light resistance, light shielding property, and dispersion stability. Therefore, by using the color filter which has a black matrix using such a coloring composition, it can provide the outstanding liquid crystal display device which has high display quality and was suppressed the problem of malfunction. As such a liquid crystal display device, the liquid crystal display device of the form shown in FIG. 2 is mentioned, for example.

Moreover, you may provide the black matrix formed using such a coloring composition on the switching element of an electrode substrate.

One form of the liquid crystal display device of this invention is demonstrated using FIG.

The liquid crystal display device 10 has an electrode substrate 11 including a switching element 11c and a pixel electrode 11b on a transparent substrate 11a, and is formed of a colored composition on the switching element 11c. The matrix 12 is provided. Moreover, the electrode plate 21 for common electrodes is arrange | positioned facing this liquid crystal drive electrode substrate 11, and this electrode plate 21 for common electrodes is on the transparent substrate 21a and this transparent substrate 21a. It consists of a color filter 21b and a transparent common electrode 21c installed in the. The liquid crystal material 33 is sealed between the electrode substrate 11 and the electrode plate 21 for the common electrode. Here, as the switching element 11c, a thin film transister (TFT) element and a metal insulater metal (MIM) are used. ), A varistor element, etc. can be illustrated.

Thus, by providing the black matrix 12 on the switching element 11c, the relative position precision error between the switching element 11c and the black matrix 12 can be made small. That is, the size of the black matrix 12 can be made smaller than that of the conventional liquid crystal display device obtained by providing the switching element and the black matrix on separate electrode substrates and assembling them, and at the same time, the switching element 11c and the black matrix. The matrix 12 can be reliably corresponded to block incident light.

Therefore, the liquid crystal display device 10 using the electrode substrate 11 provided with the black matrix 12 formed using such a coloring composition on the switching element 11c improves an aperture ratio, and has higher display quality. Have.

<Example>

Hereinafter, an Example demonstrates this invention and it demonstrates concretely. In addition, in an Example and a manufacture example, "part" shows a weight part.

(Production Example 1)

20 parts of methacrylic acid, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of methyl methacrylate, 55 parts of butyl methacrylate are dissolved in 300 parts of ethyl cellosolve, and 0.75 parts of azobisnitrile are added under a nitrogen atmosphere. The reaction was carried out at 70 ° C. for 5 hours to obtain an acrylic resin. The dilution of ethyl cellosolve was obtained by diluting with ethyl cellosolve so that the concentration of this resin was 20% by weight. Let this be the diluent ①.

(Production Example 2)

175.0 parts of diethylene glycol dimethyl ether, 43.8 parts of 2-hydroxymethacrylate, 26.3 parts of methacrylic acid, and 105.1 parts of ethyl methacrylate were added to four 1 L flasks, and the mixture was heated to 90 ° C. Subsequently, 145.0 parts of diethylene glycol dimethyl ether, 43.8 parts of 2-hydroxymethacrylate, 26.3 parts of methacrylic acid, 105.1 parts of ethyl methacrylate, and 2.92 parts of Naifer BMT (manufactured by Nippon Oil Holding Co., Ltd.) were prepared in advance. The mixed solution was added dropwise for 3 hours and reacted at 90 ° C for 3 hours. Furthermore, what melt | dissolved 1.75 parts of naper BMT in 10 parts of diethylene glycol dimethyl ether was added, and reaction was continued for 1 hour. Subsequently, the flask internal temperature was 80 degreeC, what dissolved 34.3 parts of IPDI adducts and 0.02 parts of tin octylates in 20 parts of diethylene glycol dimethyl ether was dripped at about 10 minutes, and it reacted for 2 hours after dripping, and obtained the photosensitive resin. The acid value of the reaction product was about 90. It diluted with ethyl cellosolve so that the density | concentration of this resin might be 20 weight%, and the ethyl cellosolve dilution liquid was obtained. Let this be the diluent ②.

(Production Example 3)

76.1 parts of bisphenol fluorene type epoxy resin, 0.0015 parts of triethylbenzyl ammonium chloride, 0.00033 parts of 2,6-di-isobutylphenol, and 23.7 parts of acrylic acid were stirred and heated at a temperature of 90 to 100 ° C, and gradually heated up to 120 ° C, The reaction was carried out for 8 hours to obtain a photosensitive resin. It diluted with ethyl cellosolve so that the density | concentration of this resin might be 20 weight%, and the ethyl cellosolve dilution liquid was obtained. Let this be the diluent ③.

(Production Example 4)

After heating 200 parts of isophorone diisocyanate at 40 degreeC by nitrogen atmosphere, 100 parts of 2-hydroxyethyl methacrylates and 0.13 parts of hydroquinone were reacted for 3 hours, and resin A which has one liquid isocyanate group and one vinyl group was obtained. . Next, 65 parts of acrylic resin (25 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid and acrylic resin obtained by polymerizing 25 parts of methyl methacrylate) and 35 parts of resin A were dissolved in 300 parts of ethyl cellosolve. It reacted at 90 degreeC for 3 hours, and obtained the photosensitive resin (acrylic resin). The dilution of ethyl cellosolve was obtained by diluting with ethyl cellosolve so that the concentration of this resin was 20% by weight. Let this be the diluent ④.

(Example 5)

After adding 200 g of bisphenol fluorene type epoxy resin, 100 g of 1, 2, 3, 6-tetrahydrophthalic anhydride, and 2 kg of ethyl cellosolve, stirring, 150 g of benzophenonetetracarboxylic acid dihydrate and 1 g of tetraethylammonium bromide were added. It reacted at 110 degreeC for 2 hours, and obtained the photosensitive resin. The dilution of ethyl cellosolve was obtained by diluting with ethyl cellosolve so that the concentration of this resin was 20% by weight. Let this be the diluent ⑤.

(Example 6)

As a black colorant, 30 g of titanium black 13R (trade name: manufactured by Mitsubishi Material) was dispersed in 100 g of water using a bead mill to obtain an aqueous slurry. Next, 200 g of a 2% solution of sodium silicate was added to the aqueous slurry, followed by stirring using a homogenizer. Subsequently, sulfuric acid was added to neutralize and the coating reaction treatment was performed. In order to take out the coated colorant, aluminum sulfate solution was added, stirred, and left to stand for one day to precipitate the coated colorant. The coated colorant was filtered, washed with pure water, dried, and the coated black colorant coated with silica was obtained. This coated black colorant was quantitatively analyzed by fluorescence X-ray analysis. As a result, the silica was 2.11 by weight relative to titanium black 100. Let this colorant be covering colorant①.

(Example 7)

A coating black colorant coated with silica was obtained in the same manner as in Production Example 6 except that the concentration of sodium silicate solution was 5%. As a result of quantitative analysis of the coating black colorant in the same manner as in Production Example 6, silica was 4.62 by weight ratio with respect to titanium black 100. This colorant is referred to as coating colorant ②.

(Example 8)

A coated black colorant coated with silica was obtained in the same manner as in Production Example 6 except that the concentration of the sodium silicate solution was 10%. As a result of quantitative analysis of the coated black colorant in the same manner as in Production Example 6, silica was 9.83 in weight ratio with respect to titanium black 100. Let this colorant be covering colorant ③.

(Example 9)

A coated black agent coated with silica was obtained in the same manner as in Production Example 6 except that the concentration of the sodium silicate solution was 20%. As a result of quantitative analysis of the coated black colorant in the same manner as in Production Example 6, silica was 19.4 in weight ratio relative to titanium black 100. This colorant is called coating colorant④.

(Example 10)

A coated black colorant coated with silica was obtained in the same manner as in Production Example 6 except that the concentration of sodium silicate solution was 35%. As a result of quantitative analysis of the coated black colorant in the same manner as in Production Example 6, silica was 33.4 by weight relative to titanium black 100. This colorant is called coating colorant ⑤.

Example 1

38 g of the coating colorant ① obtained in Preparation Example 6 were mixed with 30 g of the diluent 1 obtained in Example 1, 2 g of Sol Pass 20000 (trade name: Zener), and 30 g of ethyl cellosolve, which were used as a dispersant, to cool the bead mill. While dispersed for 1.5 hours.

To 100 g of the colored resin thus obtained, 50 g of the diluted solution ①, 4.0 g of trimethylolpropane triacrylate as the photopolymerization monomer, 5 g of piperonyl-s-triazine as the photopolymerization initiator, and 100 g of ethyl cellosolve as the solvent Was added and stirred well to prepare a coloring composition for forming a black matrix.

This black matrix forming coloring composition was spin-coated at 800 rpm on one side of a substrate on which Cr was deposited on both sides to obtain a film thickness of 1.1 mu m. The cross section after drying of the coating film was wiped off with acetone, and after baking at 230 ° C. for 30 minutes, Cr on both sides was short-circuited with a silver paste to prepare a substrate for volume resistivity measurement. It was 10 ¹² Ωcm when resistance was measured for this board | substrate by the method according to the volume resistivity test of JIS standard (C2103-1991). Moreover, when the 1.0 micrometer-thick coating film was formed on the transparent glass substrate, and optical density was measured, 3.2 was shown. Corning Corporation "7059" was used here as a transparent glass substrate. The results are shown in Table 1.

Further, in the same manner as above, a coating film having a thickness of 1.2 μm was formed on the transparent glass substrate and prebaked at 70 ° C. for 15 minutes, and then the alignment was performed with high precision through a mask with a pixel portion shielded to expose (150 mJ / cm 2), The solution was well washed after development in an aqueous 2.5% sodium carbonate solution. After washing with water, baking was carried out at 230 ° C. for 30 minutes to obtain a black matrix pattern. Due to the photolitho method, the resolution is good and the black matrix can be formed with a line width of 6 μm or less.

In addition, a cross cut was put into the formed coating film so as to make at least 100 checkerboard scales, and then peeling test was performed using a cello tape to evaluate the peeling state of the checkerboard scales under a microscope. This good highly insulating black matrix was obtained.

On the other hand, 40 g of 2-ethylhexyl acrylate, 40 g of methyl methacrylate, methacrylic acid, 300 g of cyclohexanone, and 0.5 g of azobisisobutyronitrile were heated and reacted at 80 ° C. for 5 hours while stirring in a nitrogen stream to have viscosity. While a thick liquid was obtained. To 100 g of this liquid, 25 g of a blue colorant (manufactured by BASF Corporation, phthalocyanine blue), 5 g of a dispersant (Geneker Co., Ltd. product, Solpass 24000), 100 g of cyclohexanone, 20 g of dipentaerythritol hexaacrylate, bis (di 3 g of ethylamino) benzophenone and 5 g of biimidazole derivatives (manufactured by Hotodani Chemical Co., Ltd., B-CIM) were added to obtain a blue photosensitive resin composition.

In addition, a red photosensitive resin composition was obtained using a red colorant (manufactured by Chiba-Geigi Co., Ltd., anthraquinone red) instead of a phthalocyanine blue of a blue colorant, and again a green colorant (manufactured by Hext Ltd., phthalocyanine green). It obtained using the green photosensitive resin composition.

Next, on the black matrix pattern obtained above, a blue photosensitive resin composition was applied to the entire surface using a spin coater so as to have a dry film thickness of 1.5 μm, and baked at 80 ° C. with an ultra high pressure mercury lamp by an Nikon aligner to expose an exposure dose of 100 mJ. The pattern was exposed so that it became / cm <2>. After exposure, it is developed with 0.5 wt% aqueous sodium hydroxide solution to form a blue pattern, and the red photosensitive resin composition is applied to the entire surface by the same method, and the pattern is exposed by the same method to form a red pattern to form red, blue, green The coloring pattern of was formed.

(Examples 2 to 33)

As the coating colorant and the diluent, a colored resin was obtained in the same manner as in Example 1 except that each was used in the combination shown in Table 1.

To 100 g of the colored resin thus obtained, 50 g of the diluents shown in Table 1 and the photopolymerization monomer, the photopolymerization initiator, the photoacid generator, the crosslinking agent, the azide compound and the solvent shown in Table 1 were further added, and the mixture was stirred well and blacked. The coloring composition for matrix formation was produced.

In addition, trimethylol propane triacrylate as a photopolymerization monomer, piperonyl-s-triazine as a photoinitiator, 4-methoxyphenyl- phenyl iodonium hexafluorophosphonate as a photoacid generator, methylolation as a crosslinking agent Guanamine was used as the azide compound, 4, 4'- diazide steelbene, and ethyl cellosolve as the solvent. The volume resistivity and the optical density were measured like Example 1 except having used the obtained coloring composition for black matrix formation. The results are shown in Table 1.

<Table 1>

In addition, a black matrix pattern was obtained in the same manner as in Example 1. Since all are photolithographic methods, the resolution is good and it is possible to form a black matrix with a line width of 6 micrometers or less.

As a result of the peeling test performed in the same manner as in Example 1, no peeling was observed at all and a highly insulating black matrix having good adhesion was obtained. And red, blue and green coloring patterns were formed on the black matrix pattern in the same manner as in Example 1.

(Comparative Example 1)

30 g of the diluted solution ① obtained in Production Example 1, 37.8 g of carbon black MA220 (trade name: manufactured by Mitsubishi Chemical Corporation), 0.2 g of amorphous silica (trade name: manufactured by Nippon Catalyst), 2 g of dispersant Sol Pass 200000 (trade name: manufactured by Zener), ethylcello 30 g of sorb was added and dispersed for 1.5 hours while cooling with a bead mill disperser.

A colored composition for forming a black matrix was produced in the same manner as in Example 1 except that 100 g of the colored resin thus obtained was used, and the volume resistivity and the optical density were measured using the obtained colored composition for forming the black matrix. The volume resistivity was 10 ⁴ Pacm and the optical density was 2.9.

Moreover, the black matrix pattern was obtained by the method similar to Example 1 except having set exposure conditions to 1000 mJ / cm <2>, but the resolution and surface smoothness were bad, and the dispersibility of the coloring composition itself was also bad.

(Comparative Example 2)

30 g of the diluted solution ① obtained in Preparation Example 1, 38 g of titanium black 13R (trade name: manufactured by Mitsubishi Material), 2 g of dispersant Sol Pass 200000 (trade name: manufactured by Zener), and 30 g of ethyl cellosolve were added to the mixture, followed by cooling with a bead mill disperser. Disperse 1.5 hours.

A colored composition for forming a black matrix was produced in the same manner as in Example 1 except that 100 g of the colored resin thus obtained was used, and the volume resistivity was measured using the obtained colored composition for forming the black matrix. The volume resistivity was 10 ⁴ Pacm and the voltage dependence occurred.

Moreover, the black matrix pattern was obtained by the method similar to Example 1 except having set exposure conditions to 200mJ / cm <2>, The resolution was bad at 15 micrometers, and surface smoothness and pattern shape were also bad.

(Comparative Example 3)

30 g of the diluent 1 obtained in Production Example 1 and 28 g of titanium black 13R (trade name: manufactured by Mitsubishi Material), 5 g of purple lyogen violet RL (trade name: made by Oriental Ink), blue colourant Heliogen blue L6700F (trade name: manufactured by BASF Corporation). 5 g), 2 g of dispersant Solspass 20000 (trade name: Zener) and 30 g of ethyl cellosolve were added and dispersed for 1.5 hours while cooling with a bead mill disperser.

A colored composition for forming a black matrix was produced in the same manner as in Example 1 except that 100 g of the colored resin thus obtained was used, and the volume resistivity and the optical density were measured using the obtained colored composition for forming the black matrix. The volume resistivity was more than 10 ⁹ mm 3, and the optical density was 2.3.

Moreover, the black matrix pattern was obtained by the method similar to Example 1 except having set exposure conditions to 100 mJ / cm <2>, but the resolution and surface smoothness were bad, and the dispersibility of the coloring composition itself was also bad.

(Comparative Example 4)

30 g of the diluted solution ① obtained in Preparation Example 1, 20 g of titanium black 13R (trade name: manufactured by Mitsubishi Material), 2 g of dispersant Sol Pass 20000 (trade name: manufactured by Zener), and 48 g of ethyl cellosolve were added to each other, followed by cooling with a bead mill disperser. Disperse 1.5 hours.

A colored composition for forming a black matrix was produced in the same manner as in Example 1 except that 100 g of the colored resin thus obtained was used, and the volume resistivity and the optical density were measured using the obtained colored composition for forming the black matrix. The volume resistivity was 10 ⁶ dBm, and the optical density was 2.3.

Moreover, the black matrix pattern was obtained by the method similar to Example 1 except having set exposure conditions to 300 mJ / cm <2>, but the resolution and surface smoothness were bad, and the dispersibility of the coloring composition itself was also bad.

Furthermore, a cross cut was put into the formed coating film so as to make at least 100 checkerboard scales, and then peeling test was performed using a cello tape to evaluate the peeling state of the checkerboard scales under a microscope. As a result, about 20 peelings were confirmed.

As described above, the coloring composition of the present invention has high insulation and is excellent in light resistance, light blocking property, dispersion stability and film strength. For this reason, the coloring composition of this invention is optimal for formation of a black matrix, and a high quality liquid crystal display device can be obtained by using this black matrix.

Moreover, in the electrode substrate which comprises a switching element and a pixel electrode on a transparent substrate, the relative positional precision between a black matrix and a switching element is made small by providing the black matrix which consists of the coloring composition of this invention on the said switching element. Accordingly, an electrode substrate having a large aperture ratio of a display screen and a liquid crystal display device can be provided easily.

Claims (17)

A coloring composition comprising titanium black, a resin, and an insulating substance. A coloring composition comprising titanium black, a resin, and an insulating material, wherein the insulating material is 1 to 35% by weight of the colorant. A coloring agent comprising titanium black coated with an insulating material, and a resin, wherein the insulating material is 1 to 35% by weight of the coloring agent. The coloring composition according to claim 1, wherein the insulating material comprises at least one selected from silica, alumina and zirconia. The coloring composition according to claim 1, wherein the resin is a photosensitive resin. The coloring composition according to claim 1, further comprising a dispersant, a photopolymerization monomer, a photopolymerization initiator, and a solvent. The coloring composition of Claim 1 which further contains a dispersing agent, a crosslinking agent, a photo-acid generator, and a solvent. The coloring composition according to claim 1, further comprising a dispersant, a photopolymerization monomer, a diazo- or azide compound, and a solvent. The coloring composition according to claim 1, wherein the resin is a (meth) acrylic resin. The resin according to claim 5, wherein the resin is 10 to 40% by weight of the compound having one vinyl group and hydroxyl group, 10 to 30% by weight of the compound having one vinyl group and carboxyl group and 30 to 75% by weight of compound having one vinyl group. It is an acid value 50-150 photosensitive resin obtained by responding 5-25 mol% of compounds which have an isocyanate group and at least 1 or more vinyl groups with respect to 100 mol% of vinyl copolymer compounds which consist of%. 6. The coloring composition according to claim 5, wherein the resin is a photosensitive resin containing a unit structure represented by the following general formulas (1) and / or (2) as a main component. (Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R ₃ is a hydrogen atom or a methyl group, X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, or the following formula (3) or absent: Y represents an acid anhydride residue, Z Represents residues of acid dihydrate, m and n are integers of 1 or more.) The coloring composition according to claim 1, wherein the coloring composition has a volume resistivity of 10 ⁷ cm 3 or more. A colorant comprising titanium black and an insulating material are mixed to obtain a colorant coated with an insulating material, and then a resin is blended into this colorant. A black filter is formed using the coloring composition of Claim 1. A color filter as claimed in claim 14 is used. An electrode substrate comprising a switching element and a pixel electrode on a transparent substrate, wherein at least the switching element is provided with a black matrix made of the coloring composition of claim 1. The electrode substrate of Claim 16 is used, The liquid crystal display device characterized by the above-mentioned.