JPH09265006A - Resin black matrix, black paste and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a black matrix excellent in electric insulating property and light shielding property, having such superior characteristics as low reflectance and high resolution and having an almost neutral black hue by dispersing a specified light shielding material in a resin and imparting specified specific resistance or above. SOLUTION: A light shielding material is dispersed in a resin to obtain the objective black matrix having >=7×10<4> Ω.cm specific resistance or >=1×10<8> Ω.cm surface resistance per 1μm thickness. The light shielding material is carbon black in which at least one of the concns. of COOH, OH and SO3 H groups in the surface has a molar ratio of >=0.005 to all carbon atoms and/or carbon black surface-grafted with a high molecular compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin black matrix used for a color filter of a liquid crystal display device, a black paste for producing the same, and a color filter using the same. A resin black matrix with excellent electrical insulation and light-shielding properties, low reflectivity, high resolution, and almost neutral black hue, a black paste for producing the same, and a color filter using the same It is about.

[0002]

2. Description of the Related Art Color filters for color separation used in liquid crystal display devices and the like are composed of red, green, and
It is composed of pixels of the three primary colors of blue. A color filter having a light-shielding region (generally called a black matrix) having a constant width in each pixel is known, and is disclosed in, for example, Japanese Patent Application Laid-Open No. 62-254103.

A black matrix of a color filter in a liquid crystal display device or the like is required to have a light-shielding property and an electrical insulating property in order to apply a voltage to each liquid crystal cell for each filter pixel.

As the black matrix, Cr, Ni, which is formed by the vacuum deposition method or the sputtering method,
A method for patterning a metal single-layer structure thin film such as Al or a multi-layer structure thin film composed of a metal, a metal oxide, a metal nitride or the like by photoetching, for example, as disclosed in JP-A-62-14103. A transparent resin is patterned by photolithography and then dyed with a black dye, for example, JP-A-2-196.
No. 284 and JP-A-2-239204, a method of patterning by a photolithography method using a binder resin containing a black dye such as carbon black is disclosed in JP-A-4-13105. As shown, at least two or more pigments having a complementary color relationship with each other are dispersed in a resin, and patterning is performed by a photolithography method.
As disclosed in JP-A-181474, the light-shielding layer has a two-layer structure, and the first layer of the light-shielding layer is a conductive film formed by vapor deposition, sputtering, or a film in which conductive particles are dispersed in a polymer. A method of providing light-shielding property and a method of providing high insulation with a film in which organic pigments or electrically insulating oxide particles are dispersed in a polymer in the second layer, and in a stripe pixel, both ends of each color pixel are partially overlapped. Therefore, a color overlapping method and the like for forming a light-shielding area is known.

[0005]

The purpose of the black matrix used in the color filter is to improve the display quality of the liquid crystal display device by first improving the contrast of the displayed image. Therefore, the black matrix is required to have a high light-shielding property.

In an active matrix driving system using a TFT (thin film transistor) in which a non-linear element (switching element) is arranged in each pixel, which has been developed in various fields in recent years, the black matrix causes an error of the switching element due to a light leak current. It is also used for the purpose of suppressing the operation, and the black matrix in this case is also required to have a high light-shielding property. In addition, an IPS (In-Plane S) also called a super TFT with an improved viewing angle.
In the driving method, the display electrode and the common electrode are arranged on the glass substrate on the TFT array side, and the liquid crystal is driven by the horizontal electrolysis in the parallel direction on the glass substrate to obtain a wide viewing angle. Since it is necessary to suppress vertical electrolysis perpendicular to the substrate, the black matrix of the color filter side substrate is required to have high light shielding properties and electrical insulation properties.

Furthermore, a simple matrix driving method in which time division driving is performed, and MIM (Me
In the active matrix driving method in which a total insulator (Tal Insulator Metal) is arranged, the transparent electrodes on the color filter are formed in stripes. In this case, the conduction between the transparent electrode and the black matrix or the conduction between the counter electrode is performed. It is easy to cause defective images.
Therefore, the black matrix is required to have high light insulation and high electrical insulation.

In the above-mentioned method of patterning a metal single-layer structure thin film or a metal multi-layer structure thin film by photoetching, a high light-shielding property is obtained, but the manufacturing cost is high and the electrical insulation is insufficient, so that the transparent electrode There is a problem that image defects are likely to occur due to conduction between the black matrix and the black matrix or conduction between the counter electrode and the black matrix.

In the method of dyeing with a black dye and the color superimposing method of forming a light-shielding region by partially overlapping both ends of color pixels, although high electric insulation is obtained, the light-shielding property is insufficient and the image contrast is reduced. There is a problem that improvement is insufficient. In the color overlapping method, there are problems that it is more difficult to flatten the surface of the color filter and color unevenness easily occurs.

In the method of patterning a binder resin containing a black pigment such as carbon black, a black matrix having low reflection and high light-shielding properties can be obtained, but carbon black, for example, has insufficient electrical insulation because of its conductivity. I have a problem to do. Further, in the method in which the light-shielding layer has a two-layer structure and the first layer has a light-shielding property and the second layer has an electrical insulating property, there are problems that the manufacturing cost is high and the manufacturing process is complicated.

The present invention was devised in view of the drawbacks of such a technique, and its purpose is to have a high light-shielding property and an electrical insulating property, a low reflectivity, a high resolution, and a hue of almost neutral black. The present invention relates to a resin black matrix which has excellent characteristics such as certain characteristics and can display an excellent image when incorporated in a liquid crystal display device, a black paste for producing the same, and a color filter using the same, and a low production rate. To achieve these goals at cost.

[0012]

In order to achieve the above object, the present invention is a black matrix in which a light-shielding agent is dispersed in a resin and has a specific resistivity of 7 × 10 ⁴ Ω.
cm or more, or the sheet resistance value per 1 μm film thickness is 1 ×
It is composed of a resin black matrix having a resistance of 10 ⁸ Ω / cm ² or more and a color filter using the resin black matrix.

In the present invention, as a light-shielding agent to be dispersed in a resin, surface carboxyl group concentration [COOH], surface hydroxyl group concentration [OH], surface sulfonic acid group concentration [S].
At least one of O ₃ H] is a carbon black having a molar ratio per total carbon atoms of more than 0.005 and / or carbon black grafted with a polymer compound on the surface. Consists of.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The black matrix of the present invention is obtained by finely dispersing a specific carbon black as a light-shielding agent in a resin in order to obtain high electrical insulation, light-shielding properties and low reflectivity. The specific carbon black means that at least one of the surface carboxyl group concentration [COOH], the surface hydroxyl group concentration [OH], and the surface sulfonic acid group concentration [SO ₃ H] is 0 in molar ratio per total carbon atom. .0
Carbon black larger than 05, more preferably larger than 0.01, and / or aziridine group, oxazoline group, N-hydroxyalkylamide group, isocyanate group, epoxy group, vinyl group, acryl group, methacryl group, etc. To carbon black whose surface is grafted with a polymer compound containing one or more reactive groups.
In carrying out the graft reaction, substances other than the above-mentioned polymers such as polymer components, monomers, organic solvents may be present.

As a method for quantifying the carboxyl group concentration, hydroxyl group concentration and sulfonic acid group concentration on the surface of carbon black, X-ray photoelectron spectroscopy called XPS or ESCA can be used. It is particularly effective to use X-ray photoelectron spectroscopy in combination with the chemical modification method. For example, it is possible to quantify the concentration of the carboxyl group based on the F1S peak intensity detected by X-ray photoelectron spectroscopy by labeling by reacting trifluoroethanol or the like with the carboxyl group.

As a method for providing a carboxyl group and a hydroxyl group on the surface of carbon black, after the carbon powder is produced, it is contacted with free oxygen at a high temperature to oxidize it, or it is oxidized with an oxidizing agent such as ozone or NO ₂ , With bromine and water, there is a method of treating under normal pressure or under pressure, a method of oxidizing with an oxidizing solution such as nitric acid or sulfuric acid, and a carboxyl group on the powder surface of carbon black,
Provide acidic groups such as phenolic hydroxyl groups. Also, these methods may be combined. Further, the sulfonic acid group can be provided by a chemical reaction such as sulfonation with fuming sulfuric acid. By adjusting the degree of these treatments, the concentration of carboxyl groups on the surface of carbon black,
The hydroxyl group concentration and sulfonic acid group concentration can be controlled.

Carbon black is channel black,
Roller black, those produced by the contact method called Disk Black, those produced by the Farnest method called Gas Furnest Black, Oil Farnest Black, thermal black, called acetylene black The one produced by the thermal method may be used, but channel black, gas farnest black and oil farnest black are preferable, and farnest black is particularly preferable.

As the light-shielding agent, other than the above-mentioned specific carbon black, various light-shielding agents may be added as long as the light-shielding property is not deteriorated. 40% of carbon black
It is preferably at least 50% by weight, more preferably 50
It is desirable that the content be at least wt%, more preferably at least 60 wt%.

The two types of specific carbon blacks used in the present invention may be used alone or in combination. When two kinds of carbon blacks are used in combination, it is desirable that the amount of carbon black having an increased acidic group concentration is 50% by weight or more, and more preferably 60% by weight or more of the total carbon black.

As a light-shielding agent other than carbon black,
In addition to metal oxide powders such as titanium oxide and iron tetroxide, metal sulfide powders, and metal powders, a mixture of pigments such as red, blue, green, and purple can be used.

In order to improve the light-shielding property of the resin black matrix, it is preferable to use carbon black having a small particle diameter, the average primary particle diameter is 5 to 40 nm, and the average secondary particle of carbon black in the resin black matrix is used. The diameter is preferably 5 to 100 nm. In the specific carbon black, the aggregation of carbon black in the resin black matrix is small, and the average secondary particle size is close to the average primary particle size.

The specific carbon black having such a small particle size mainly has a brownish color tone. Therefore, it is preferable to mix a pigment having a complementary color with the specific carbon black so that the hue becomes neutral black. It is preferable that the black matrix is a resin in which a specific carbon black and a light-shielding agent composed of a pigment having a complementary color to the specific carbon black are dispersed. The complementary color of brown is blue or purple. As a complementary color pigment, a blue pigment or a purple pigment, or a mixture of a blue pigment and a purple pigment can be used. However, when a colored resin is used, a pigment complementary to the color mixture of the resin and the specific carbon black is used. Specific examples of typical pigments are indicated by color index (CI) numbers. As a blue pigment or a violet pigment, an organic pigment having a high tinting strength is particularly preferable.
5: 1, 15: 2, 15: 3, 15: 4, 15: 5, 1,
5: 6, 16, 21, 22, 60, 64 and the like, but especially Pigment Blue 15, 15: 1, 15:
2, 15: 6 is preferred. Examples of purple pigments include pigment violet 19, 23, 29, 31, 32, 3
3, 36, 37, 39, 43, 50 and the like, but especially Pigment Violet 23, 31, 33, 4
3,50 is preferable.

The wavelengths 430 to 430 will be described below unless otherwise specified.
When the optical density per 1 μm of the film thickness of the black matrix in the visible light region of 640 nm is defined as the light shielding property, it is preferable that the black matrix has a light shielding property of 2.3 or more. In order to obtain such a high light-shielding property, the ratio of the resin in the black matrix and the specific carbon black contained in the light-shielding agent is preferably 35% by weight or more, more preferably 45% by weight or more, and further preferably 60% by weight. It is desirable to set it to be at least%.

The thickness of the black matrix is 1
It is preferably less than μm, more preferably 0.75
It is not more than μm, more preferably not more than 0.5 μm. The thinner the thickness of the black matrix, the smaller the surface step on the color filter, which is preferable. Further, by setting the film thickness of the black matrix to 0.75 μm or less, the protective layer can be omitted, which is particularly preferable. The lower limit is not particularly limited, but is 0.3 in view of the strength of the black matrix and the dimensional accuracy of the pattern.
μm or more is preferred.

As the resin for the black matrix,
Examples thereof include polyimide resin, acrylic resin, PVA, gelatin, polyester resin, polyvinyl resin and the like. In the processing of color filters, the black matrix is often processed first. Therefore, among these resins, it is preferable to have higher heat resistance than the resin used for the pixel or the protective film, and a polyimide resin having heat resistance of 250 ° C. or higher is preferable. Further, in order to obtain a high-resolution color filter, a polyimide resin is preferable because it is also excellent in fine processing precision. The polyimide resin also includes polyamide-imide and is not particularly limited, but a polyimide precursor (n = 1 to 2) containing a structural unit represented by the general formula (1) as a main component is usually heated or heated with a suitable catalyst. Those that are imidized are preferably used.

[0026]

Embedded image In the general formula (1), R ¹ is a trivalent or tetravalent organic group having at least 2 carbon atoms. From the viewpoint of heat resistance, R ¹ is preferably a trivalent or tetravalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms. Examples of R ¹ include phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group,
Examples thereof include, but are not limited to, a diphenyl ether group, a diphenyl sulfone group, a diphenyl propane group, a benzophenone group, a biphenyl trifluoropropane group, a cyclobutyl group and a cyclopentyl group.

R ² is a divalent organic group having at least 2 carbon atoms, but from the viewpoint of heat resistance, R ² contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle, and A divalent group having 6 to 30 carbon atoms is preferable. Examples of R ² include phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenyl sulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoropropane group, diphenylmethane group, dicyclohexylmethane group, etc. Examples include, but are not limited to: In the polymer having the structural unit (1) as a main component, R ¹ and R ² may each be composed of one type of them, or may be a copolymer composed of two or more types of each. . Further, in order to improve the adhesiveness to the substrate, it is preferable to copolymerize bis (3-aminopropyl) tetramethyldisiloxane having a siloxane structure as a diamine component within a range that does not lower the heat resistance.

Specific examples of the polymer having the structural unit (1) as a main component include pyromellitic dianhydride, 3,3 ',
4,4′-benzophenonetetracarboxylic dianhydride,
3,3 ′, 4,4′-biphenyltrifluropropanepropanecarboxylic acid dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic acid dianhydride, 2,3,3
One or more carboxylic acid dianhydrides selected from the group consisting of 5, -tricarboxycyclopentyl acetic acid dianhydride and the like, and paraphenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3 , 4 'diaminodiphenyl ether, 3,3'-
Polyimide precursor synthesized from at least one diamine selected from the group consisting of diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodiphenylmethane But is not limited to these. These polyimide precursors are synthesized by a known method, that is, by selectively combining tetracarboxylic dianhydride and diamine and reacting them in a solvent.

Further, a dicarboxylic acid anhydride such as maleic anhydride is usually added to seal the molecular end of the polyimide precursor and stop the polymerization. However, it is more preferable that the molecular end of the polyimide resin is an amine group because the dispersibility of the light-shielding agent is improved. The ratio of the amine terminal at the molecular end is preferably 50% or more, more preferably 80% or more, still more preferably 90% or more. In order to make the terminal of the molecule of the polyimide resin an amine group, when the polyimide precursor is synthesized, the number of moles of the diamine is slightly increased relative to the number of moles of the tetracarboxylic dianhydride, and the reaction is carried out in a solvent. It is preferable. Specifically, tetracarboxylic dianhydride is preferably 100 to 90 mol, and more preferably 98 to 93, relative to 100 mol of diamine.
Mol, more preferably 97 to 95 mol.

Among these polyimide resins, one having a higher light absorption at a wavelength in the visible light region is more preferable because the light-shielding property of the black matrix becomes higher. Specifically, for example, as the tetracarboxylic dianhydride, the higher the electron withdrawing property of the acid dianhydride residue, the more preferable, a ketone type such as a benzophenone group, an ether type such as a diphenyl ether group, Those having a phenyl group, those having a sulfone group such as a diphenyl sulfone group, and the like are preferable. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the like. As the diamine, the stronger the electron donating property of the diamine residue is, the more preferable, and those having a biphenyl group, a diaminodiphenyl ether having a p-, p-substituted or m-, p-substituted structure, methylenedianiline, a naphthalene group, a perylene group, and the like. Preferably 4,4
'Or 3,4' diaminodiphenyl ether, para-phenylenediamine and the like. It is also preferable that these aromatic rings have a structure in which a nitro group is substituted.

The resin black matrix can be formed by various coating methods using a black paste in which a light shielding agent mainly made of specific carbon black is dispersed in a resin solution.

The black paste solvent is usually an amide-based polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide or N, N-dimethylformamide, a lactone-based polar solvent or dimethyl sulfoxide. It is preferably used, but in order to enhance the dispersion effect of the specific carbon black, it is preferable to contain at least an amide polar solvent, and more preferably a solvent in which the amide polar solvent is the main component or the amide polar solvent alone. Is preferably used. Here, the solvent having an amide-based polar solvent as a main component means that a mixed solvent composed of n kinds of solvents contains more than (1 / n) × 100% by weight. For example, in the case of a two-component solvent, the amide polar solvent is contained in an amount of more than 50% by weight. In the case of a ternary solvent, the amide polar solvent is contained in an amount of more than 33% by weight. Say.

When a light-shielding agent other than the specific carbon black is added, it is preferable to contain at least a lactone polar solvent in order to enhance the dispersion effect of the light-shielding agent. In particular, when rosin resin acid is used as a dispersant, it works particularly effectively. The lactones are aliphatic cyclic esters having 3 to 12 carbon atoms, and specific examples thereof include β-propiolactone, γ-butyrolactone, and γ-.
Examples thereof include valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone and the like, and γ-butyrolactone is particularly preferable from the viewpoint of solubility of the polyimide precursor. For this reason, it is more preferable to use a mixed solvent of an amide polar solvent and a lactone polar solvent.

As solvents other than these, solvents having a higher evaporation rate such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, and ethyl lactate, and surface tensions of 26 to 33 dynes / cm are used for improving coating properties. It is preferable to add an ethylene glycol-based or propylene glycol-based ether acetate solvent, preferably 1 to 25% by weight, more preferably 5 to 20% by weight, based on the total solvent. Specific examples include propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethylene glycol ethyl ether acetate, and 3-methoxybutyl acetate. Further, it is better to disperse a light-shielding agent such as specific carbon black in a solution to which these solvents are added, heat generation during dispersion is reduced, gelation is less likely to occur, or dispersibility is improved, preferable.

As a method of dispersing a light-shielding agent such as specific carbon black, for example, a light-shielding agent and a dispersant are mixed in a resin solution, and then three rolls, a sand grinder,
Although there is a method of dispersing in a dispersing machine such as a ball mill, when a light-shielding agent other than the specific carbon black is used, a method of dispersing each light-shielding agent alone and then mixing them is more preferable. When a polyimide precursor is used as the resin, a light shielding agent is first mixed in a solvent to prevent a reaction between the polyimide precursor during dispersion, an increase in viscosity due to a reaction between the light shielding agent and the polyimide precursor, and prevention of gelation. Then, a method of mixing or dispersing the polyimide precursor after the pre-dispersion is more preferable.
Further, a method of dispersing or mixing the specific carbon black and the light-shielding agent other than the specific carbon black with a solvent suitable for dispersion or a polyimide precursor containing the solvent is more preferable. In order to finely disperse the light-shielding agent, it is preferable to appropriately adjust the dispersion intensity, the dispersion time, and the like.

The rheological properties of the black paste are as follows:
The yield value according to Casson's flow equation is preferably 0.1 Pa or less, more preferably 0.01 Pa.
Hereafter, it is more preferably 0.001 Pa or less. If the dispersion stability of the light-shielding agent is poor, the yield value will be higher than this, aggregation of the light-shielding agent will occur, and the light-shielding property of the black matrix will decrease, which is not preferable. Since the black paste of the present invention uses a specific carbon black, a low yield value is obtained. S = shear stress, D = shear velocity, τ0 = yield value, μ0 = Casson viscosity,
Flow equation is expressed by Equation 1, the yield value is calculated by the square of the intercept of (S) ^1/2-axis in (S) ^1/2 of graph for ^1/2 (D).

[0037]

[Equation 1] The viscosity is appropriately adjusted according to the coating method, but it is 5 to 1
000 cP is preferable, and more preferably 8 to 150 c
P, and more preferably 10 to 100 cP.

Various additives may be added to the black paste for the purpose of improving the dispersibility of the light shielding agent. In addition, various additives can be added for the purpose of improving coating properties and leveling properties.

Next, a color filter for a liquid crystal display element, which is formed by laminating a resin black matrix, pixels and a protective film in this order on a light transmissive substrate, will be described as an example. First, a black paste is applied on a light transmissive substrate.
The light transmissive substrate is not particularly limited,
Quartz glass, borosilicate glass, inorganic glass such as soda lime glass whose surface is coated with silica, or an organic plastic film or sheet is preferably used. The coating method is dip coating, roll coater,
Spin coating methods such as whalers and spinners are preferably used. After that, it is dried in a hot air oven, a hot plate or the like and semi-cured. The semi-curing conditions are slightly different depending on the kind and the amount of the polyimide precursor used, but it is general that heating is usually performed at 100 to 180 ° C. for 1 to 60 minutes. If a non-photosensitive polyimide precursor is used, then a photoresist is applied, pre-baked, and exposed using an optical mask. After that, the development of the resist and the patterning of the black matrix are continuously carried out by using a developing solution by a dip, shower, paddle method or the like. After this,
The resist is peeled off by a dip, shower, paddle method or the like using a peeling solution. Finally, for imidization, 200 to
Heat at 400 ° C. for 1-60 minutes to cure. An opening of about 20 to 200 μm is usually provided between the black matrices, and pixels are formed in this space in a later step.

Next, pixels of a plurality of colors are formed in the openings of the black matrix. Usually, the color of each pixel is
The colors are red, blue and green, and are colored by a coloring agent. As a coloring agent used for a pixel, an organic pigment, an inorganic pigment, a dye, or the like can be preferably used. As organic pigments, phthalocyanine-based, azilake-based, condensed azo-based, quinacridone-based, anthraquinone-based, perylene-based,
Perinones and the like are preferably used. The resin used for the pixel may be a photosensitive or non-photosensitive resin such as an epoxy resin, an acrylic resin, a polyimide resin, a urethane resin, a polyester resin, a polyvinyl resin, and a dyeable animal protein resin such as gelatin. It is preferable to disperse or dissolve a coloring agent in these resins to perform coloring.

First, a resin paste containing a colorant is applied. In addition to dip coating and roll coater, spin coating methods such as whalers and spinners are preferably used. After this,
The first colored layer is formed on the entire surface of the black matrix by drying with hot air or a hot plate. Since the color filter usually includes pixels of a plurality of colors, unnecessary portions are removed by photolithography to form a desired first color pixel pattern. The pixel film thickness is about 0.5 to 3 μm. Repeat this only for the pixels of the required color to form pixels of multiple colors,
Manufacture color filters.

After that, a protective film is laminated if necessary.
Examples of the protective film include acrylic resin, epoxy resin, silicone resin, and polyimide resin, and are not particularly limited.

Besides this, after forming patterned pixels on the light transmissive substrate in advance, a photosensitive black paste is applied and exposed from the light transmissive substrate side.
There is a method of forming a black matrix between pixels using the pixels as a mask, a so-called back exposure method, and the like.

Finally, if necessary, lamination and patterning of ITO transparent electrodes can be carried out by a general method.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0046]

【Example】

Preparation of Polyimide Precursor Solution 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 147 g N-methyl-2-pyrrolidone 775
It was charged together with g, 95.10 g of 4,4′-diaminodiphenyl ether and 6.20 g of bis (3-aminopropyl) tetramethyldisiloxane were added, and the mixture was added at 60 ° C.
At room temperature for 3 hours to obtain a polyimide precursor solution having a viscosity of 600 poise (25 ° C.). The average degree of polymerization was about 27, and both ends had amine groups. This was applied to a non-alkali glass (“OA-2” manufactured by Nippon Electric Glass Co., Ltd.) substrate with a spinner so that the finished film thickness was 2 μm, and the temperature was 80 ° C. 10
After drying with hot air for 30 minutes, semi-cure at 100 ° C for 3 minutes
It was cured at 00 ° C. for 30 minutes. The original stimulation Y of this polyimide film was 95.

Example 1 A carbon black mill base, a blue pigment mill base, and a purple pigment mill base having the following compositions were dispersed for 1 hour at 7,000 rpm using a homogenizer, glass beads were removed by filtration, and after mixing the whole amount, black A paste was prepared. The black paste had a viscosity of 20 cP and a yield value of 1.4 × 10 ⁻⁴ Pa. As the light-shielding agent, brown carbon black and a mixed system of a blue pigment and a purple pigment as its complementary color pigment were used.

(1) Carbon Black Mill Base Carbon Black 5.0 parts ([COOH] = 0.012, [SO ₃ H] = 0.002, [OH] = 0.003) Polyimide precursor solution 22.4 parts N-methyl-2- Pyrrolidone 22.6 parts Glass beads 50.0 parts (2) Blue pigment Millbase Pigment Blue 15 2.3 parts Polyimide precursor solution 22.4 parts N-methyl-2-pyrrolidone 25.3 parts Glass beads 50.0 parts (3) Purple Pigment Millbase Pigment Violet 2 1.0 part Polyimide precursor solution 22.9 parts N-methyl-2-pyrrolidone 26.1 parts Glass beads 50.0 parts Alkali glass ("OA-" manufactured by Nippon Electric Glass Co., Ltd.) 2 ")
It was applied on a substrate with a spinner, dried with hot air at 80 ° C. for 10 minutes, and then semi-cured at 120 ° C. for 20 minutes. Then, a positive type resist (Shipley "Microposit" RC100 30cp) was applied by a spinner and dried at 80 ° C. for 20 minutes. Exposure machine PL
A-501F (manufactured by Canon Inc.) was used to expose through a photomask, and an alkaline developer (Shipley "Microposit") was used.
351), the positive resist was developed and the polyimide precursor was etched at the same time, and then the positive resist was stripped with methyl cellosolve acetate. In addition, 300
It was cured at 30 ° C. for 30 minutes. In this way, the thickness 0.8
A black and matrice line and space test pattern of μm was obtained.

The light-shielding property of the black matrix of this embodiment has almost no wavelength dependence, and the wavelength is 430 to 640 nm.
Was 2.3 to 2.6 (optical density / μm). The specific resistance value ratio of the resin black matrix is 5.0 × 10 ⁵ Ω · cm or more, and the sheet resistance value is 1.0 × 10 ⁹
Ω / cm ² or more. The resolution obtained by this black matrix test pattern is 1.0μ.
m. In addition, aluminum vapor deposition plate ("T" manufactured by Sigma Koki Co., Ltd.)
The reflectance was 7.6 as measured with FA -20 S03 ") as a reference.

Example 2 The same composition as in Example 1 was used, except that the carbon black mill base used in Example 1 was changed to the following composition. The black paste has a viscosity of 18 cP and a yield value of 2.4.
It was × 10 ^-5 Pa. As the light-shielding agent, brown carbon black and a mixed system of a blue pigment and a purple pigment as its complementary color pigment were used.

(1) Carbon black mill base Carbon black (grafting treatment with an acrylic group-containing polymer) 3.6 parts Polyimide precursor solution 24.4 parts N-methyl-2-pyrrolidone 22.0 parts Glass beads 50.0 Parts (3) Blue pigment and purple pigment mixed mill base Pigment Blue 15 2.5 parts Pigment Violet 2 1.1 parts Polyimide precursor solution 24.4 parts γ-Butyl lactone 22.0 parts Glass beads 50.0 parts or less, In the same manner as in Example 1, a lattice-shaped resin black matrix was obtained. The light-shielding property of the black matrix has almost no wavelength dependence, and was 2.4 to 2.5 (optical density / μm) at a wavelength of 430 to 640 nm. Moreover, the specific resistance of the resin black matrix is 5.0 × 1.
0 ⁵ Ω · cm or more, surface resistance value 1.0 × 10 ⁹ Ω / cm
² or more. The resolution obtained by the test pattern of this black matrix was 1.0 μm, and the reflectance was 7.0.

Example 3 The same as Example 1 except that the black paste used in Example 1 was mixed with the following two types of carbon black mill bases. The black paste had a viscosity of 18 cP and a yield value of 2.4 × 10 ⁻⁶ Pa. As the light-shielding agent, brown carbon black and a mixed system of a blue pigment and a purple pigment as its complementary color pigment were used.

[0053] (1) Carbon black mill base 1 Carbon black 5.5 parts ([COOH] = 0.012, [ SO 3 H] = 0.002, [OH] = 0.003) polyimide precursor solution 22.5 parts N- methyl-2 -Pyrrolidone 22.0 parts Glass beads 50.0 parts (2) Carbon black mill base 2 Carbon black (grafting treatment with acrylic group-containing polymer) 2.5 parts Polyimide precursor solution 23.5 parts N-methyl-2- Pyrrolidone 24.0 parts Glass beads 50.0 parts (3) Blue pigment and purple pigment mixed mill base Pigment Blue 15 3.3 parts Pigment Violet 2 1.1 parts Polyimide precursor solution 23.4 parts N-methyl-2- Pyrrolidone 22.2 parts Glass beads 50.0 parts In the same manner as in Example 1 below, lattice-shaped resin black I got a matrix. The light-shielding property of the black matrix has almost no wavelength dependence, and was 2.4 to 2.5 (optical density / μm) at a wavelength of 430 to 640 nm. Moreover, the specific resistance value of the resin black matrix is 5.0 × 1.
0 ⁵ Ω · cm or more, surface resistance value 1.0 × 10 ⁹ Ω / cm
² or more. The resolution obtained by the test pattern of this black matrix was 1.0 μm, and the reflectance was 7.4.

Example 4 A mill base having the following composition was dispersed for 1 hour at 7,000 rpm using a homogenizer, and then glass beads were removed by filtration.

(1) Millbase 1 carbon black 4.6 parts ([COOH] = 0.0012, [SO ₃ H] = 0.002, [OH] = 0.003) Pigment Red 177 7.3 parts Pigment Green 7 7.3 parts Pigment Blue 15 3.4 parts Acrylic resin ("Marproof" manufactured by NOF CORPORATION) 8.0 parts Butylcellosolve 34.4 parts Glass beads 35.0 parts Next, a photosensitive resin compound having the following composition is used. adjust.

(2) Photopolymerizable monomer (“TMP-A” manufactured by Kyoeisha Oil & Fat Co., Ltd.) 3.5 parts Photopolymerizable oligomer (“EB3700” manufactured by Daicel UCB) 2.2 parts Photopolymerization initiator (“IRGACURE 907” "Ciba Geigy Co., Ltd.) 1.0 part Photopolymerization initiator (" Irgacure 369 "Ciba Geigy Co., Ltd.) 1.0 part Acrylic resin (" Marproof "manufactured by NOF Corporation) 6.0 parts Butyl Cellsolve 86.3 parts This The mill base thus prepared and the photosensitive composition were all mixed to obtain a black paste. This black paste is used as alkali-free glass (“DEN” manufactured by Nippon Electric Glass Co., Ltd.
2 ") coated on a substrate with a spinner and dried with hot air for 10 minutes at 80 ° C. After that, exposure was performed through a photomask using an exposure device PLA-501F (manufactured by Canon Inc.), and etching was performed using monoethanolamine. After performing,
It was cured for 30 minutes. In this way, the thickness is 0.8μ
m black matrix line and space test pattern was obtained.

The light-shielding property of the black matrix of this embodiment has almost no wavelength dependence, and the wavelength is 430 to 640 nm.
Was 1.6 to 2.2 (optical density / μm). Further, the specific resistance value of the resin black matrix is 5.
0 × 10 ⁵ Ω · cm or more, surface resistance value 1.0 × 10 ⁹ Ω /
It was at least cm ² . The resolution obtained by the test pattern of this black matrix was 2.0 μm, and the reflectance was 7.9.

Comparative Example 1 A monochromatic plate of a resin black matrix was obtained in the same manner as in Example 1 except that the carbon black was changed to the following.

Carbon black 3.6 parts ([COOH] = 0.004, [SO ₃ H] = 0.002, [O]
H] = 0.002) The viscosity of the black paste is 32 cP, and the yield value is 1.
It was 0 × 10 ⁻⁴ Pa. Compared with Example 1, the light-shielding property of the black matrix was 2.6 to 2.9 (optical density / μm) at a wavelength of 430 to 640 nm, and a high light-shielding property was obtained, but the specific resistance value at this time was 2.8 x 10 ²
Ω · cm and a surface resistance value of 3.5 × 10 ⁶ Ω / cm ² . The resolution obtained by the test pattern of this black matrix was 1.0 μm, and the reflectance was 5.8.

Comparative Example 2 A monochromatic plate of a photosensitive acrylic resin black matrix was obtained in the same manner as in Example 4 except that the following carbon black was used.

3.6 parts of carbon black ([COOH] = 0.004, [SO ₃ H] = 0.002, [O]
H] = 0.002) The viscosity of the black paste is 16 cP, and the yield value is 1.
It was 0 × 10 ⁻⁵ Pa. Compared with Example 1, the black matrix has a light-shielding property of 1.8 to 2.1 (optical density / μm) at a wavelength of 430 to 640 nm, a low light-shielding property, and a specific resistivity of 3.2 × 10 ² Ω ·. cm, sheet resistance value 4.
It was 0 × 10 ⁶ Ω / cm ² . The resolution obtained by the test pattern of this black matrix was 2.0 μm, and the reflectance was 6.1.

Table 1 summarizes the carbon blacks used in Examples and Comparative Examples.

[0063]

[Table 1] Table 2 summarizes the specific resistance, surface resistance, optical density, hue, and resolution of each resin black matrix.

[0064]

[Table 2]

[0065]

The resin black matrix of the present invention is
By dispersing a specific carbon black as a light-shielding agent in the resin, it has excellent properties such as excellent electrical insulation and light-shielding properties, low reflectivity, high resolution, etc., and a resin black matrix whose hue is almost neutral black. And a liquid crystal display device having excellent display characteristics can be obtained. An excellent resin black matrix can be obtained by applying a black paste obtained by dispersing a specific carbon black in the resin solution.

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Claims (23)

[Claims] 1. A resin black matrix comprising a resin containing a light-shielding agent and having a specific resistance of 7 × 10 ⁴ Ω · cm or more. 2. A black matrix made of a resin containing a light-shielding agent, having a surface resistance value of 1 × 1 per 1 μm of film thickness.
A resin black matrix having a resistance of at least ⁸ Ω / cm ² . 3. At least one of a surface carboxyl group concentration [COOH], a surface hydroxyl group concentration [OH], and a surface sulfonic acid group concentration [SO ₃ H] as a light-shielding agent, in a molar ratio per total carbon atom, The resin black matrix according to claim 1 or 2, characterized in that carbon black larger than 0.005 is used. 4. A light-shielding agent whose surface has one or more types of reactivity among aziridine group, oxazoline group, N-hydroxyalkylamide group, isocyanate group, epoxy group, vinyl group, acryl group, methacryl group and the like. A resin black matrix comprising carbon black whose surface is grafted with a polymer compound containing a group. 5. The resin black matrix according to claim 1 or 2, wherein the carbon black according to claim 3 or 4 is mixed and used as a light shielding agent. 6. The resin black matrix according to claim 1 or 2, wherein carbon black and a pigment having a complementary color to the carbon black are contained as a light shielding agent. 7. A pigment complementary to carbon black,
The resin black matrix according to claim 6, which is a blue and / or purple pigment. 8. The resin black matrix according to claim 1, wherein the proportion of carbon black in the light-shielding agent is 40% by weight or more. 9. The resin black matrix according to claim 1, wherein the optical density per 1 μm of the film thickness of the black matrix is 2.3 or more in the visible range of wavelength 430 to 640 nm. 10. A C light source or an F in an XYZ color system.
The chromaticity coordinates (x, y) of transmitted light and reflected light of the resin black matrix in 10 light sources are (x−x ₀ ) ² + (y) with respect to the chromaticity coordinates (x ₀ , y ₀ ) of the light source. −
The resin black matrix according to claim 1 or ^{2, wherein} y ₀ ) ² ≦ 0.01. 11. The resin black matrix according to claim 1 or 2, wherein the resin is a polyimide resin. 12. The resin black matrix according to claim 11, wherein the molecular end of the polyimide resin has an amine group. 13. A black paste obtained by dispersing a light-shielding agent in a resin solution, wherein the carbon black according to any one of claims 3 to 5 is used as the light-shielding agent. 14. The black paste according to claim 13, comprising carbon black and a pigment having a complementary color to the carbon black as a light shielding agent. 15. The black paste according to claim 14, wherein the pigment complementary to carbon black is a blue and / or purple pigment. 16. The black paste according to claim 13, wherein the proportion of carbon black in the light shielding agent is 40% by weight or more. 17. A C light source or an F in an XYZ color system.
Chromaticity coordinates (x,
y) with respect to the chromaticity coordinates (x ₀ , y ₀ ) of the light source under the condition that the original stimulus Y is 0.03 ≦ Y ≦ 0.3,
^{_{(X-x 0) 2 +}} (y-y 0) 2 ≦ 0.01 black paste according to claim 13, characterized in that. 18. The black paste according to claim 13, wherein the resin is a polyimide resin. 19. The black paste according to claim 18, wherein the molecular end of the polyimide resin has an amine group. 20. The black paste according to claim 13, wherein an amide-based polar solvent selected from N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide is a main component of the solvent. 21. The black paste according to claim 13, which contains at least a lactone solvent. 22. The black paste according to claim 13, further comprising an ethylene glycol-based or propylene glycol-based ether acetate solvent having a surface tension of 26 to 33 dynes / cm. 23. A color filter having a light-transmitting colored pattern formed on a transparent substrate and having a black matrix made of a resin containing a light-shielding agent between the patterns, wherein the black matrix is the color filter of claim 1. A color filter comprising the resin black matrix according to claim 2.