KR20080056158A - Manufacturing method of metal fine particle dispersion, metal fine particle dispersion, coloring composition using the same, photosensitive transfer material, shading image attachment substrate, color filter and liquid crystal display device - Google Patents

Abstract

A method for producing a metal fine particle dispersion in which metal ions are reduced in the presence of an alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms to form metal fine particles.

A method for producing a metal particulate dispersion, a metal particulate dispersion and a coloring composition using the same, a photosensitive electronic material, a light shielding image attachment substrate, a color filter and a liquid crystal display device.

Description

METHOD FOR PRODUCING METAL PARTICLE DISPERSION, METAL PARTICLE DISPERSION, AND COLORED COMPOSITION, PHOTOSENSITIVE TRANSFERFER MATERIAL, SUBSTRATE WITH LIGHT-BLOCKING IMAGE, COLOR FILTER AND LIQUID CRYSTAL DISPLAY EACH USING SUCH METAL PARTICLE DISPERSION}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a metal fine particle dispersion including metal fine particles, a metal fine particle dispersion and a colored composition using the same, a photosensitive transfer material, a light shielding image attachment substrate, a color filter, and a liquid crystal display device.

Conventionally, coloring compositions for black materials include printing inks, inkjet inks, etching resists, solder resists, barrier ribs of plasma display panels (PDPs), dielectric patterns, electrode (conductor circuit) patterns, wiring patterns of electronic components, conductive pastes, and conductive films. It is widely used for shading images such as black matrix and the like. The light shielding image is a black edge formed at a periphery of a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, or a black part of a grid or stripe between red, blue, and green pixels, and also for TFT light blocking. In addition to the so-called black matrix (hereinafter sometimes referred to as "BM") such as a dot pattern or a black pattern in a line, various light shielding images are included.

BM can generally be used to improve display contrast. In addition, in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), BM can be used to prevent image degradation caused by leakage of current through light, and high light shielding properties (3 or more in optical density OD) are required. It is becoming.

On the other hand, liquid crystal display devices have recently been applied to televisions (hereinafter sometimes referred to as "TV"). In TV applications, a color filter having a low transmittance and high color purity can be used, and the luminance of the backlight tends to be high in order to obtain high luminance. For this reason, high light-shielding property is calculated | required by BM in order to prevent the fall of contrast and the transparency of the peripheral picture frame part.

In addition, TVs that can be used for home use, installation, and the like are often installed in a room where sunlight is incident for a long time, and there is concern about deterioration of TFTs to sunlight. Moreover, in TV use, (1) an image with high OD has a feeling of tension. That is, since the contrast is high and (2) the whiteness of a liquid crystal is not seen by external light, high light shielding property is calculated | required by BM also from a related viewpoint.

As BM, what has a metal film, such as chromium, as a light shielding layer, for example is mentioned. As a method of forming BM using a metal film such as chromium as a light shielding layer, for example, a metal thin film is produced by a vapor deposition method or a sputtering method, a photoresist is applied on the metal thin film, and then a photomask having a pattern for BM is applied. The photoresist layer is exposed to light, and then the exposed metal thin film is etched, and finally, the BM is formed by peeling the resist layer on the metal thin film (for example, see Non-Patent Document 1). .

The method of manufacturing BM using this photoresist has the advantage that a high light shielding effect can be obtained even if the film thickness is thin because a metal thin film is used. However, there is a problem that a vacuum film forming step or an etching step such as a vapor deposition method or a sputtering method is required and the cost is high. In addition, since the light shielding layer is a metal film, there is a problem that the reflectance is high and the display contrast is low under strong external light.

On the other hand, there is a means of using a low reflection chromium film (such as a metal chromium and two layers of chromium oxide) as the metal thin film. In addition, the etching process has a large drawback that the environmental load is large because the waste liquid containing the metal ions is discharged. In particular, chromium, which is best used in the above method, is harmful and has an enormous environmental load. Now, as represented by the EU's ELV directive and RoHS directive, social interest in reducing the environmental burden is increasing. It is becoming.

As another BM formation method, the method of using the photosensitive resin composition containing a light-shielding pigment, for example, carbon black, is also known. As the above method, for example, after forming R, G, and B pixels on a transparent substrate, a carbon black-containing photosensitive resin composition is coated on the pixels, and the entire surface is formed from the R, G, and B pixel non-forming surfaces of the transparent substrate. The BM formation method of the self-alignment system exposed to is known (for example, refer patent document 1).

The method has a lower manufacturing cost than the method by the metal film etching, but has a problem that the film thickness becomes thick in order to obtain sufficient light shielding properties. As a result, overlapping (stepping) of BM, R, G, and B pixels occurs, flatness of the color filter worsens, and cell gap stains of the liquid crystal display are generated, resulting in poor display such as display stains.

The display stain refers to a phenomenon in which the alignment of the liquid crystal is disturbed when the surface of the black matrix substrate is not smooth, which causes the display stain, and is a faint stain observed when a gray test signal is input to the liquid crystal display. "Linear nonuniformity", which appears to be a relatively clear near face, occurs when forming projection alignment control projections such as thickness irregularities, exposure stains, developmental stains, and heat-treated stains when forming the photosensitive resin layer and functions as a liquid crystal display device. In this case, unevenness caused by the interaction between the alignment control projection and the liquid crystal is considered, but the mechanism is not certain.

On the other hand, a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate, exposed and developed through a photomask having a BM pattern to form a relief on the transparent substrate, and the transparent substrate is used as a catalyst for electroless plating. After contacting with an aqueous solution of a metal compound, containing the metal compound in a relief, drying, heat treatment, and then contacting the relief on the transparent substrate with an electroless solution, light-shielding metal particles having a particle diameter of 0.01 to 0.05 µm are formed therein. A method of producing BM uniformly dispersed has been proposed (see Patent Document 2, for example). Nickel, cobalt, iron, copper, and chromium have been described as the metal particles, and nickel is exemplified only as a specific example.

However, this method refers to imparting-heat treatment-electroless plating of a relief-forming electroless plating catalyst including an exposure developing process, and has many cumbersome treatment steps for handling water. As a result, the BM cannot be expected at low cost.

Moreover, although the example which used the magnetic filler for the coloring composition which manufactures a black pattern is proposed (for example, refer patent document 3), these examples have a film thickness of 10 micron or more, the density near unit film thickness is low, It is not possible to produce a shading image having high shading performance at a low cost.

In addition to the above, a method of using metal fine particles is known as a method of obtaining a black matrix having a low environmental load and a high optical density in a thin film (see Patent Documents 4 and 5, for example). According to these methods, a black matrix having low environmental load and high optical density in a thin film can be obtained.

However, when the light shielding film is manufactured using the coloring composition containing the said metal fine particles, and the high-definition matrix was formed by patterning exposure and the development process, the unevenness | corrugation by the aggregate of metal fine particles or the coloring composition prepared when manufacturing the light shielding film was prepared. As the stability deteriorated over time, there was a problem in that it could not be manufactured stably, and thus technical improvement was required.

On the other hand, the method of stably dispersing metal fine particles is proposed (for example, refer patent document 6 and 7). The related method discloses a method for producing a metal particulate dispersion using a polymeric pigment dispersant or a non-aqueous thiol compound, which is used as a dispersant, as a dispersant. However, the dispersant improves dispersibility by improving monodispersion when forming particles. As a light shielding film, the light shielding ability was low and the performance which was satisfactory when a light shielding film was produced was not able to be exhibited.

Patent Document 1: Japanese Patent Application Laid-Open No. 62-9301

Patent Document 2: Japanese Patent No. 3318353

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-13678

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-334180

Patent Document 5: Japanese Patent Application Laid-Open No. 2005-17322

Patent Document 6: Japanese Patent Application Laid-Open No. 2003-193118

Patent Document 7: Japanese Patent Application Laid-Open No. 2004-346429

Non-Patent Documents: Published by Public Publications, Inc. "Color TFT LCD Monitor," pages 218-220 (April 10, 1997)

An object of the present invention is to provide a method for producing a thick metal particle dispersion having a high dispersion stability with stability over time, a metal particle dispersion, a coloring composition using the same, and a photosensitive transfer material. Another object of the present invention is to provide a light blocking image attachment substrate having a light blocking image including a thick black film or a black matrix, or an image including a high density colored film in a thin film, a color filter having excellent flatness and a low display stain, and a liquid crystal display device. do.

[1] A method for producing a metal fine particle dispersion, wherein metal ions are reduced in the presence of an alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms to form metal fine particles.

[2] The method for producing a metal particulate dispersion according to [1], wherein the alkali-soluble polymer has an acidic group.

[3] The method for producing a metal particulate dispersion according to [2], wherein the acidic group of the alkali-soluble polymer is a carboxyl group.

[4] The method according to any one of [1] to [3], wherein the organic / inorganic ratio (I / O value) is 0.44 or more and 1.65 or less in the organic conceptual diagram of the alkali-soluble polymer.

[5] The method for producing a metal fine particle dispersion according to any one of [1] to [4], wherein the metal fine particles contain one or two or more metals selected from Groups 2 to 14 of the periodic table.

[6] A metal fine particle dispersion containing an alkali-soluble polymer having at least one sulfur atom and / or a nitrogen atom and metal fine particles.

[7] The metal particulate dispersion according to [6], which is black.

[8] The metal particulate dispersion according to [6] or [7], wherein the alkali-soluble polymer has an acidic group.

[9] The metal particulate dispersion according to [8], wherein the acidic group of the alkali-soluble polymer is a carboxyl group.

[10] The metal particulate dispersion according to [6] to [9], wherein the organic / inorganic ratio (I / O value) is 0.44 or more and 1.65 or less in the organic conceptual diagram of the alkali-soluble polymer.

[11] The metal particulate dispersion according to [6] to [10], wherein the metal particulate contains one or two or more metals selected from Groups 2 to 14 of the periodic table.

[12] A colored composition containing the metal particulate dispersion according to any one of [6] to [11].

[13] The colored composition according to [12], which is black.

[14] A photosensitive transfer material having at least one photosensitive light shielding layer formed on a support, wherein the photosensitive light shielding layer is formed using the metal particulate dispersion according to any one of [6] to [11].

[15] A light shielding image attachment substrate having a light shielding image formed by using the metal particulate dispersion according to any one of [6] to [11].

[16] A light shielding image attachment substrate having a light shielding image produced by using the photosensitive transfer material of [14].

[17] A color filter formed by using the metal particulate dispersion according to any one of [6] to [11].

[18] A liquid crystal display device formed using the metal particulate dispersion according to any one of [6] to [11].

According to the present invention, it is possible to provide a method for producing a thick metal particle dispersion having a high stability of dispersion with stability over time, a metal particle dispersion, a colored composition using the same, and a photosensitive transfer material. Further, according to the present invention, a light shielding image attachment substrate having a light shielding image including a thick black film or a black matrix or an image containing a high concentration of a color film in a thin film, a color filter and a liquid crystal display device having excellent flatness and low display stain can be provided. have.

The method for producing a metal fine particle dispersion of the present invention is to reduce metal ions in the presence of an alkali soluble polymer having one or more sulfur atoms and / or nitrogen atoms (hereinafter, referred to as "alkali soluble polymer" in the present invention). To form metal fine particles.

In addition, the metal fine particle dispersion of the present invention contains an alkali-soluble polymer and metal fine particles having one or more sulfur atoms and / or nitrogen atoms.

In addition, the colored composition of the present invention contains the metal fine particle dispersion of the present invention, and if necessary, the colored composition of the present invention may be a resin or a precursor thereof, a pigment fine particle, a polymer to be a binder, a monomer, an initiator, a solvent, and the like. It may contain.

According to the fine particle dispersion and the coloring composition of the present invention, it is possible to prepare a rich metal particulate coloring composition having high dispersion stability, and black seed density (thinning performance) in the thin film because there are few seeds having high stability over time of the coating liquid. It is possible to stably produce an image including a high-density colored film in a light shielding image or a thin film containing a high black film or a black matrix.

The metal particulate dispersion and the colored composition of the present invention may be used for printing ink, inkjet ink, photomask fabrication material, printing proof fabrication material, etching resist, solder resist, barrier rib of plasma display panel (PDP), dielectric pattern, electrode (conductor circuit) ), A wiring pattern of an electronic component, a conductive paste, a conductive film, and a light shielding image such as a black matrix. For example, the metal fine particle dispersion and the colored composition of the present invention form a light shielding image on the gap portion, the peripheral portion, and the external light side of the TFT due to the improved display characteristics of the color filter used in the color liquid crystal display device and the like. Therefore, it can use suitably. In addition, black edges formed in the periphery of the display device such as a liquid crystal display device, a plasma display device, an EL display device, and a CRT display device, or a black part of a grid or stripe between red, blue, and green pixels, It can be used especially suitably as black matrices, such as a dot pattern and a linear black pattern.

`` Metal particle dispersion of the present invention ''

EMBODIMENT OF THE INVENTION Hereinafter, in describing this invention in detail, the metal fine particle dispersion of this invention is demonstrated in detail. The metal fine particle dispersion of the present invention contains alkali soluble polymer and metal fine particles having one or more sulfur atoms and / or nitrogen atoms.

(Composition of metal fine particles)

In the present invention, the metal of the metal fine particles is not particularly limited, and any metal may be used. In the present invention, the metal fine particles may be used in combination of two or more metals, or may be used as an alloy. In the present invention, the metal fine particles may be a metal compound, or may be a composite particle of a metal compound and a metal.

Among them, in the present invention, the metal fine particles are preferably formed of a metal and / or a metal compound, and particularly preferably formed of a metal.

In particular, in the present invention, it is preferable to include, as a main component, a metal selected from the group consisting of the fourth, fifth and sixth periods of the long periodic table IUPAC9999. In the present invention, the metal fine particles preferably contain a metal selected from the group consisting of Groups 2 to 14, and include Group 2, Group 8, Group 9, Group 10, Group 11, and Group 12 More preferably, the metal selected from the group consisting of Group 13 and Group 14 is included as a main component.

Preferred examples of the dispersed metal particles as the metal particles are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, for example. And at least one selected from titanium, bismuth, antimony, lead or alloys thereof. More preferred metals are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium or alloys thereof, more preferred metals are at least 1 selected from copper, silver, gold, platinum, tin or alloys thereof. It's a species.

In the present invention, the metal fine particles can be obtained by reducing metal ions in the presence of an alkali-soluble polymer. Specifically, in the present invention, the metal particles can be obtained by adding and mixing a solution containing a metal salt and a reducing agent in the presence of an alkali-soluble polymer and reducing the metal ions. The metal salt can be used without particular limitation, and examples thereof include metal salts such as chlorides, nitrates, nitrites, sulfates, ammonium salts and acetates.

Moreover, as said reducing agent, if it is normally used, it will not specifically limit, For example, Boron hydride metal salts, such as sodium borohydride and potassium borohydride; Aluminum hydride salts such as lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, aluminum magnesium hydride, aluminum hydride calcium, hydrazine compounds, dextrins, hydroquinone, hydroxylamine, citric acid and salts thereof, succinic acid and salts thereof And ascorbic acid and salts thereof.

In the production method of the metal fine particle dispersion of the present invention, the addition method of the metal salt and the reducing agent, the reaction temperature and the like are not particularly limited and can be appropriately adjusted in accordance with the conditions for producing the metal fine particles for the purpose of preparation.

Metal Compounds

The "metal compound" used in the present invention is a compound of the above metals and elements other than metals.

Examples of the compound of the metal and other elements include oxides, sulfides, sulfates, carbonates, and the like of the metals. Of these, sulfides are particularly preferred because they easily form color tone or fine particles. Examples of these metal compounds include copper (II) oxide, iron sulfide, silver sulfide, copper sulfide (II), titanium black, and the like, but silver sulfide is particularly preferable from the viewpoint of stability because of easy color tone and fine particle formation. .

Compound fines

In the present invention, "composite fine particles of a metal compound and metal" refers to a single particle in which the metal and the metal compound are combined. For example, such composite fine particles include ones having different compositions in the interior and the surface of the particles, and those in which two kinds of particles are combined. The metal compound and the metal constituting the composite fine particles may be one kind or two or more kinds. Specific examples of the composite particles of the metal compound and the metal include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper oxide (II), and the like.

Core shell

In the present invention, the metal fine particles may be a core-shell composite particle. The core-shell composite particle coats the surface of the core material with a shell material. Examples of shell materials that can be used for the core-shell composite particles include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, Se At least one semiconductor selected from Te, CuCl, CuBr, CuI, TlCl, TlBr, TlI, solid solutions thereof, and solid solutions containing 90 mol% or more thereof; Or copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead or alloys thereof At least 1 type of metals mentioned are mentioned.

As a preferable example of the said core material, at least 1 sort (s) chosen from copper, silver, gold, palladium, nickel, tin, bismuth, antimony, lead, or these alloys is mentioned, for example.

The said shell material can be used suitably also as a regulator of a refractive index in order to reduce a reflectance.

There is no restriction | limiting in particular in the manufacturing method of the composite fine particle which has a core-shell structure, For example, the method of forming a metal compound shell on the surface continuously in the process of manufacturing a metal fine particle, etc. can be used. As such a method, for example, a reducing agent is added to a metal salt solution, a part of metal ions are reduced to form metal fine particles, and then sulfides such as sodium sulfide and ammonium sulfide are added, and metal sulfides are formed around the produced metal fine particles. There is a way to form.

Shape of Metal Particles

"Advanced Materials" 2002, 14, 80-82 or "J.Phys.Chem.B." As described in 2003. 107, 2466-2470, etc., it is known that the color of the metal particles changes depending on the particle shape. In the present invention, the shape of the metal fine particles is not particularly limited and may be any shape, but it is preferable to include metal fine particles having different aspect ratios. In the present invention, the main shapes of the metal particles are adzuki beans, potatoes, rods (needles, cylinders, cuboids such as cubes, rugby balls, etc.), flat plates (scale pieces, elliptical plates, plates), fibrous, Japan A star candy, a coil, etc. may be sufficient, Preferably it is a plate-shaped particle and rod shape (rod).

In the present invention, the "aspect ratio" of the metal fine particles means a value obtained by dividing the major axis length of the metal fine particles defined as described later by a short axis length, and is defined as an average value of the values measured for 100 metal fine particles.

In addition, the projection area of a particle | grain can be obtained by measuring an area on an electron microscope photograph, and correcting a photographing magnification.

In the metal fine particles, the diameter (long axis length, short axis length) is assumed to be a box (cuboid) in which one metal fine particle is suitably (exactly) accommodated as the triaxial diameter of the metal fine particles, and the box has a length L, a width b, and a height. Or thickness t, defined by the dimensions of this metal particulate.

In the present invention, the number average particle diameter of the metal fine particles is not particularly limited as long as it does not exceed the formed film thickness, but the number average particle diameter of the metal fine particles is preferably in the range of 10 nm to 100 nm, more preferably in the range of 10 nm to 500 nm. The range of 10nm to 200nm is more desirable.

In the present invention, when the number average particle diameter of the metal fine particles is less than 1 Onm, it is difficult to produce, and the color filter manufactured by using the metal fine particles having the number average particle diameter is observed to be visually dark brown (not black) in view of its characteristics. It may not be desirable. In addition, in the present invention, when the number average particle diameter of the metal fine particles exceeds 100Onm, the stability of the dispersion in which the particles are dispersed may deteriorate and the light shielding property may deteriorate.

In addition, the "particle diameter" used here means the diameter when the electron microphotographic image of particle | grains is called a circle of the same area, and the "number average particle diameter" means the said particle diameter about many particle | grains, and means 100 average values thereof. . In addition, in the present invention, the metal fine particles are not particularly limited as to the particle size distribution.

(Method for Producing Metal Particulate Dispersion of the Present Invention)

Hereinafter, the manufacturing method of the metal fine particle dispersion of this invention is demonstrated.

The metal fine particle dispersion of the present invention can improve the dispersion stability of metal fine particles by reducing metal ions in the presence of an alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms, and forming metal fine particles. Here, in the present invention, reducing the metal ions in the "in the presence" of the alkali-soluble polymer generally means adding a salt containing a metal and a reducing agent in a container in which the alkali-soluble polymer is dissolved in advance. A salt containing a noble and a reducing agent may each be dissolved in separate containers, and these may be added simultaneously to a separately prepared reaction vessel. In the present invention, since the alkali soluble polymer has an effect of improving the dispersion stability of the metal fine particles, it is preferable that the alkali soluble polymer is present in the reaction vessel before or immediately after the metal fine particles are formed.

Dispersion of Metallic Particles

In the present invention, the metal fine particles are dispersed in the metal fine particle dispersion of the present invention. Although the presence state of a metal fine particle at the time of dispersion is not specifically limited, It is preferable that a metal fine particle exists in the stable dispersion state, for example, it is more preferable that it is a colloidal state.

Solvent replacement of metal particulates

In addition, the metal fine particle dispersion of the present invention may be solvent-substituted after preparing the metal fine particles. In solvent substitution, pH is set to 7.5 or less by adding acid to the metal fine particle dispersion, and the aggregated nanoparticles by soft coagulation of the metal fine particles are precipitated. Subsequently, the supernatant is removed, washed repeatedly with water several times, and the solvent is sequentially substituted by gradually adding a nonpolar solvent from water. When redispersing after solvent replacement, it is preferable to perform mechanical dispersion using an ultrasonic wave, a bead mill disperser, or the like. By redispersing in this way, impurities such as the remaining reducing agent can be removed or solvent replacement can be performed. Instead of supernatant separation, means such as suction filtration and centrifugation may be used.

Although the solvent used at the time of performing the said solvent substitution can use without a restriction | limiting especially, it is preferable that SP value is 9.O or more especially. "SP value", also called solubility parameter, is expressed as the square root of the cohesive energy density. In the present invention, the SP value means what is described on page 838 of "Adhesive Handbook" (Journal of the Japanese Adhesion Society, published by Japan Industrial Daily, published in 1971).

The SP value is, for example, n-hexane / 7.3, toluene / 8.9, ethyl acetate / 9.1, methyl ethyl ketone / 9.3, acetone / 10.0, ethyl alcohol / 12.7, methyl alcohol / 14.5, water / 23.4 and the like. The unit of SP value is "(㎈ / cm <3>) ^1/2 " here.

When the solvent is redispersed, dispersibility becomes particularly good when an SP value of 9.0 or more is used, and methyl ethyl ketone, 2-propanol, 1-propanol, 1-methoxy-2-propyl acetate, cyclohexanone, acetone, N-methylpyrrolidone, a mixture thereof, etc. can be illustrated suitably.

In the metal fine particle dispersion of the present invention, the content of the metal fine particles is preferably 70% by mass or more, more preferably 80% by mass or more based on the total solids, from the viewpoint of more effectively exhibiting the effects of the present invention. It is preferable and 85 mass% or more is especially preferable.

(Alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms)

Next, an alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms in the present invention will be described. According to the method for producing a metal fine particle dispersion of the present invention, the dispersion stability of the metal fine particles can be further improved by preparing the metal fine particles in the presence of an alkali soluble polymer.

In the present invention, the alkali-soluble polymer may be a polymer including both a sulfur atom and a nitrogen atom, a polymer having either a sulfur atom or a nitrogen atom, and both can obtain the effects of the present invention.

The polymer having a sulfur atom is preferably one having a thioether group, a mercapto group, a sulfide group, or a thixo group, and the polymer having a nitrogen atom is preferably an amino group, an imino group, or a nitrogen-containing heterocyclic compound.

Examples of the nitrogen-containing heterocycle include 2-mercaptobenzimidazole, pyrrole, pyrrolidine, oxazole, thiazole, imidazole, pyrazole, pyridine, piperidine, pyridazine, pyrimidine, pyrazine, Indole, quinoline, benzimidazole, and these groups may be unsubstituted or substituted.

In the present invention, the alkali-soluble polymer may have a group containing the sulfur atom or the nitrogen atom as a polymer (including a copolymer) described later or a side chain terminal group of the polymerizable compound, or may have it other than the side chain terminal. It is preferable to have it as a side chain terminal group. Hereinafter, a polymer (including a copolymer) or a polymerizable compound is also referred to simply as a polymer.

In the present invention, "alkali solubility" means that it is not dissolved in distilled water (H ₂ O) and can be dissolved in an aqueous alkali solution of pH 10-13.

For example, the water-soluble high molecular compound shows solubility in aqueous alkali solution, but also shows solubility in distilled water, and thus is excluded from the polymer in the present invention.

In this invention, determination of "alkali solubility" can be determined, for example by the following evaluation methods.

First, 0.2 g of the compound to be evaluated is added to 20 ml of an aqueous NaOH solution adjusted to pH 12.0 and stirred vigorously. Next, it is left to stand in a constant temperature layer at 25 degreeC for 6 hours, and solubility is confirmed. At the same time, 0.2 g of the compound to be evaluated is added to 20 ml of distilled water and stirred vigorously. Solubility is confirmed after standing in a constant temperature layer at 25 ° C. for 6 hours. At this time, if the cloudy and sediment is confirmed, it is determined as "insoluble", and if the cloudy and sediment is not confirmed, it is "available". By this evaluation method, since it is soluble in the NaOH aqueous solution adjusted to pH12.0, "alkali solubility" can be confirmed by selecting an insoluble thing in distilled water.

In this invention, what has an acidic group is mentioned suitably as an alkali-soluble polymer, for example. There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably. As said acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boric acid, a phenol, a sulfoamide, etc. are mentioned, for example, A carboxyl group is preferable among these. In addition, in this invention, the introduction amount of the structural unit which has the said alkali-soluble group in an alkali-soluble polymer will not be specifically limited if the alkali-soluble polymer of this invention can melt | dissolve in the aqueous alkali solution of pH10-13 by presence of the said alkali-soluble group. Do not.

There is no restriction | limiting in particular in the acid value of an alkali polymer in this invention, Although it can select suitably according to the objective, For example, 70-300 (mgKOH / g) is preferable and 90-250 (mgKOH / g) is more preferable. In addition, 100-200 (mgKOH / g) is especially preferable from a dispersion stability viewpoint.

Examples of the polymer having a carboxyl group as the acidic group include vinyl copolymers having a carboxyl group, polyurethane resins, polyamic acid resins, modified epoxy resins, and the like. Among these, solubility in a coating solvent and an alkali developer. The vinyl copolymer which has a carboxyl group is preferable from a viewpoint of solubility, synthetic suitability, and easy adjustment of film | membrane property. Also preferred is at least one copolymer of styrene and styrene derivatives.

The vinyl copolymer having the carboxyl group can be obtained by copolymerizing at least (1) a vinyl monomer having a carboxyl group and (2) a monomer copolymerizable with the vinyl monomer of (1).

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and monomers having a hydroxyl group (for example, , Addition product of 2-hydroxyethyl (meth) acrylate and cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride), ω-carboxypolycaprolactone mono (meth) Acrylates and the like. Among these, (meth) acrylic acid is especially preferable from a viewpoint of copolymerizability, cost, and solubility. In addition, in this specification, "(meth) acrylic acid" means acrylic acid and methacrylic acid generically, and the case of its derivative is also the same.

As a precursor of the carboxyl group, a monomer having anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride may be used.

There is no restriction | limiting in particular as a monomer copolymerizable with the vinyl monomer of said (1), Although it can select suitably according to the objective, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes (for example, styrene, styrene derivatives, etc.), (meth) acrylonitrile Heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamide-2-methylpropanesulfonic acid, monophosphate (2-acryloyloxyethyl ester), monophosphate (1-methylacryloyloxyethyl ester), functional group (for example, urethane group, urea group, Sulfonamide groups , A vinyl monomer having a phenol group, an imide group), and the like, and styrenes are preferred among these.

As said (meth) acrylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acryl Rate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butyl cyclohexyl (meth) acrylate, 2-ethyl (Meth) acrylate, tert-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydrate Oxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy Ci-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethyl Glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol mono Ethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxy ethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl ( Meta) acrylate, perfluoroctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromope Nyloxyethyl (meth) acrylate etc. are mentioned.

As said crotonic acid ester, crotonic acid butyl, a crotonic acid hexyl, etc. are mentioned, for example.

As said vinyl ester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, etc. are mentioned, for example.

As said maleic acid diester, dimethyl maleate, diethyl maleate, dibutyl maleate, etc. are mentioned, for example.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate, and the like.

Examples of the itaconic acid diesters include dimethyl itaconic acid, diethyl itaconic acid and dibutyl itaconic acid.

As said (meth) acrylamide, it is (meth) acrylylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-iso, for example. Propyl (meth) acrylamide, Nn-butylacryl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) Acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl mol Porin, diacetone acrylamide, etc. are mentioned.

As said vinyl ether, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy ethyl vinyl ether, etc. are mentioned, for example.

Examples of the vinyl alcohol esters include vinyl versatate, vinyl acetate, vinyl formate, vinyl propionate and vinyl butyrate.

Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene and dichloro styrene. And hydroxystyrene protected with bromostyrene, chloromethylstyrene, a group which can be deprotected by an acidic substance (for example, tert-butyloxycarbonyl group, etc.), methyl vinylbenzoate, α-methylstyrene, and the like. .

There is no restriction | limiting in particular as molecular weight of an alkali-soluble polymer in this invention, Although it can select suitably according to the objective, From a viewpoint of the dispersion stability of metal fine particles, 2,000-300,000 are preferable as a weight average molecular weight, for example, 4,000- 150,000 is more preferable, and 6000-100,000 are especially preferable.

In the present invention, the organic / inorganic ratio (I / O value) in the organic conceptual diagram of the alkali-soluble polymer is preferably 0.44 or more and 1.65 or less, and more preferably 0.5 or more and 0.6 or less. When the said I / O value is too low, it will be soluble in water, and when the said I / O value is high, it will become insoluble in alkaline aqueous solution.

In this invention, when an alkali-soluble polymer has a sulfur atom, 0.5 mass%-20 mass% are preferable, and, as for the sulfur atom content in a polymer from a viewpoint of the dispersion stability of a metal fine particle, 1.0 mass%-10.0 mass% are more preferable. In the present invention, when the alkali-soluble polymer has a nitrogen atom, the content of nitrogen atoms in the polymer is preferably 0.5% by mass to 20% by mass, and 1.0% by mass to 10.0% by mass from the viewpoint of dispersion stability of the metal fine particles. More preferred. In the present invention, when the alkali-soluble polymer has both a sulfur atom and a nitrogen atom, the mass ratio (s / n) of the sulfur atom (s) and the nitrogen atom (n) is preferably 0.01 to 200 from the viewpoint of dispersion stability of the metal fine particles. 0.1-20 are more preferable.

As a specific example in the case where an alkali-soluble polymer contains a sulfur atom in this invention, the high molecular compound which has at least 1 sort (s) of the repeating unit represented by following General formula (1) is mentioned, for example.

일반식(1)

General formula (1)

In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, sec-butyl group, isobutyl group, tert-butyl group, and the like. Is preferred.

In General Formula (1), R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms, and this alkyl group, aryl group, and Aralkyl groups may each independently be unsubstituted or may have a substituent, or may form a saturated or unsaturated cyclic structure.

The alkyl group having 1 to 18 carbon atoms represented by R ² may be unsubstituted or may have a substituent, for example, methyl, ethyl, normal propyl, isopropyl, normal butyl, sec-butyl or iso. Alkyl groups, such as a butyl group, tert- butyl group, hexyl group, octyl group, dodecyl group, and a stearyl group, are mentioned. As a substituent in the case of having a substituent, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, ester group, sulfonyl group, etc. are preferable, for example.

In the above, as the alkyl group represented by R ² , an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, and tert- Butyl groups are particularly preferred.

The aryl group represented by said R <^2> may be unsubstituted or may have a substituent, and the C6-C14 aryl group is preferable, For example, aryl groups, such as a phenyl group, toluyl group, xylyl group, a naphthyl group, and anthracenyl Can be mentioned. As a substituent in the case of having a substituent, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, ester group, sulfonyl group, etc. are preferable, for example.

In the above, as an aryl group which R <^2> represents, a C6-C10 aryl group is preferable and a phenyl group is especially preferable.

The aralkyl group represented by R ² may be unsubstituted or may have a substituent, and an aralkyl group having 7 to 16 carbon atoms is preferable, and examples thereof include a benzyl group, a phenethyl group, a naphthyl methyl group and an anthracenylmethyl group. Aralkyl group is mentioned. As a substituent in the case of having a substituent, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, ester group, sulfonyl group, etc. are preferable, for example.

In the above, the aralkyl group represented by R ² is preferably an aralkyl group having 7 to 11 carbon atoms, and particularly preferably a benzyl group.

In the said General formula (1), Z represents -O- or NH-. In addition, Y represents the bivalent coupling group of 1-8 carbon atoms.

The divalent linking group having 1 to 8 carbon atoms represented by Y is an alkylene group (e.g. methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (e.g. ethenylene, propenylene), an alkynylene group ( Eg, ethynylene, propynylene), arylene group (e.g. phenylene), divalent heterocyclic group (e.g. 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2, 4-diyl group, quinoxaline-2,3-diyl group, pyridazin-3,6-diyl), -O-, -CO-, -NR- (R is a hydrogen atom, an alkyl group or an aryl group) or these Is preferably a combination of (eg, -NHCH ₂ CH ₂ NH-, -NHCONH- and the like).

In the above, the alkylene group, the alkenylene group, the alkynylene group, the arylene group, the divalent heterocyclic group, the alkyl group of R, or the aryl group may have a substituent. Examples of the substituent are the same as those of the aryl group. The alkyl group and aryl group of R are the same as above.

Among the divalent linking groups having 1 to 8 carbon atoms represented by Y, divalent linking groups having 1 to 6 carbon atoms are preferable, and among them, an ethylene group, a propylene group, a butylene group, a hexylene group, and -CH ₂ -CH (OH ) -CH _2- , -C ₂ H ₄ -OC ₂ H ₄ -are particularly preferred.

The polymer dispersant according to the present invention may be a polymer compound containing two or more sulfur atoms by copolymerizing not only one type of repeating unit represented by the general formula (1) but two or more types. Moreover, the thioether structure which comprises a side chain can be made into the side chain which has two or more sulfur atoms by configuring not only one sulfur atom but the said Z and R <^2> by the group which has a sulfur atom.

The polymeric dispersant according to the invention introduces a thioether structure into the desired polymer compound (preferably as a side chain), or homopolymerizes a monomer having a thioether group (preferably in a side chain), or a thioether group (preferably It can obtain by copolymerization of the monomer which has in the side chain), and another monomer. Preferably, a thioether structure is introduced into the side chain of the ethylenically unsaturated monomer, or homopolymerization of the ethylenically unsaturated monomer containing the thioether structure in the side chain, or other copolymerization with an ethylenically unsaturated monomer containing the thioether structure in the side chain. It can obtain by copolymerization of a component.

Hereinafter, the specific example of the repeating unit represented by the said General formula (1) is shown. However, this invention is not limited to these.

Among these, in particular, R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, an ethyl group, a normal propyl group, a normal butyl group, a tert-butyl group, a phenyl group, Z is -0-, and Y is an ethylene group or a phosphorus compound. This is preferred.

As a specific example in the case where an alkali-soluble polymer contains a nitrogen atom in this invention, the high molecular compound which has at least 1 sort (s) of the repeating unit shown below is mentioned, for example.

Although the specific example of the alkali-soluble polymer which contains a sulfur atom or a nitrogen atom in this invention is given to the following, it is not limited to these. The following compounds PO-1 to PO-34 are copolymers having repeating units represented by A, B and C. In addition, a, b, and c represent the mass% ratio of each of repeating units A, B, and C.

Moreover, you may mix | blend a surfactant, an antiseptic | preservative, a dispersion stabilizer, etc. with the metal fine particle dispersion of this invention suitably.

As the surfactant, any of anionic, cationic, nonionic and betaine surfactants can be used, and anionic and nonionic surfactants are particularly preferable. It is preferable that the HLB value of surfactant is about 3-6 because the solvent of a coating liquid is a nonpolar solvent.

In addition, about the said HLB value, it describes in the "surfactant handbook" (Yoshida Tokiyuki, Shinto Shinichi, Yamanaka Kiyoshi, Showa 62). Specific examples of the surfactant include propylene glycol monostearic acid ester, propylene glycol monolauric acid ester, diethylene glycol monostearic acid ester, sorbitan monolauryl acid ester, polyoxyethylene sorbitan monolauric acid ester and the like. Examples of surfactants are also described in the above "surfactant handbook".

As the dispersion stabilizer, for example, those described in "Pigment Dispersion Technology (Technical Information Association, 1999)" can be used.

<< Coloring composition of this invention >>

The coloring composition of this invention contains at least the above-mentioned metal particle dispersion of this invention, and also contains at least 1 sort (s) of resin or its precursor, a photoinitiator, a solvent, etc. You may contain a pigment fine particle as needed.

In addition, the metal particulate dispersion of the present invention and the colored composition of the present invention is preferably a black black composition. Here, "black" refers to a color having a chromaticity shift of ΔE within 100 from the achromatic point (x = 0.333, y = 0.333, Y = 0). In addition, "black composition" means the total metal atom concentration contained in the fine metal particle dispersion of the invention 4.0 × 10 ^- that is non-absorbing at a wavelength of 450nm and 550nm when a dispersion solution as a ⁴ mol / ℓ,

Blackness means the composition whose k = Abs (450 nm) / Abs (550 nm) is the range of 0.5-2.0. Absorption of the black composition can be measured using Hitachi U-3410 type magnetic spectrophotometer.

(Resin or precursor thereof)

As a resin which can be added to the coloring composition of this invention, the polymer which has a carboxylic acid group in a side chain, for example, Unexamined-Japanese-Patent No. 59-44615, Unexamined-Japanese-Patent No. 54-34327, Japan Patent No. 58 Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid described in JP-A-12577, JP-A-54-25957, JP-A-59-53836 and JP-A-59-71048 The copolymer, the crotonic acid copolymer, the maleic acid copolymer, the partially esterified maleic acid copolymer, and the cellulose derivative which has a carboxylic acid group in a side chain are mentioned. Moreover, what added the cyclic anhydride to the polymer which has a hydroxyl group can also be used preferably. In particular, copolymers of benzyl (meth) acrylate and (meth) acrylic acid, benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4139391 are preferably mentioned.

As said resin, it is preferable to select and use the thing of the acid value of 30-400 mgKOH / g range, and the weight average molecular weight of 1000-300000 range. In addition, in order to improve various performances, for example, the strength of a cured film, you may add alkali-soluble polymer in the range which does not adversely affect developability. As these alkali-soluble polymers, alkali-soluble polymers may be used in the present invention, and other alcohol-soluble nylons and epoxy resins may be mentioned.

As a precursor of the said resin, the photopolymerizable monomer etc. which become an resin by having an ethylenically unsaturated double bond and hardening by addition polymerization (it may be called "photopolymerizable monomer" hereafter) by light irradiation are mentioned. These are mentioned later.

(Initiator)

As an initiator added to the coloring composition of this invention, the photoinitiator etc. which generate | occur | produce a radical by light irradiation are mentioned. This will be described later.

(menstruum)

Although it can be used without a restriction | limiting in particular as a solvent which can be added to the coloring composition of this invention, The same solvent used when substituting the said metal particulate solvent is preferable also from a viewpoint of metal fine particle dispersion stability, and it is the SP value of 9.0 or more in particular. desirable.

For example, methyl ethyl ketone, 2-propanol, 1-propanol, 1-methoxy-2-propyl acetate, cyclohexanone, acetone, N-methylpyrrolidone, or a mixture thereof is mentioned suitably.

(Pigment particulate)

The coloring composition of the present invention can be made to have a color close to black by containing pigment fine particles in addition to the metal fine particle dispersion.

As pigment fine particles which can be contained in the coloring composition of this invention, carbon black, titanium black, or graphite is mentioned as a preferable thing.

As an example of the carbon black, Pigment Black (Pigment Black) 7 (carbon black C.I.No.77266) is preferable. Commercially available products include "Mitsubishi Carbon Black MAl00" (manufactured by Mitsubishi Chemical Corporation) and "Mitsubishi Carbon Black # 5" (Mitsubishi Chemical Corporation).

Examples of the titanium black TiO _2, TiO, preferably TiN or a mixture thereof. As a commercial item, the brand names "12S" and "13M" which are Mitsubishi Battery Rs make products are mentioned. In addition, the particle diameter of the titanium black that can be used is preferably 40 to 100nm.

As an example of the said graphite, it is preferable that particle diameter is 3 micrometers or less as a stoke diameter. When graphite exceeding 3 micrometers is used, the contour shape of a light shielding pattern may become uneven, and sharpness may worsen. Moreover, it is preferable that most (preferably 95% or more) of particle diameters are 0.1 micrometer or less.

The colored composition of the present invention may use other known pigment fine particles in addition to the pigment fine particles. Pigments are generally classified into organic pigments and inorganic pigments, but organic pigments are preferred in the present invention. Examples of the organic pigments suitably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxadine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. As the color of the organic pigment, for example, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, a black pigment, and the like are preferable.

Specifically as the pigment fine particles, the color material described in Japanese Patent Application Laid-Open No. 2005-17716, the pigment described in Japanese Patent Application Laid-Open No. 2005-361447, and Japanese Patent Laid-Open No. 2005-17 The coloring agent of Unexamined-Japanese-Patent No. 17521-[0088] can be used suitably. However, this invention is not limited to these.

In addition to the above-mentioned colorants, it may be suitably used by referring to the "pigment handbook, Japanese Pigment Technology Association, Seongmun Kwangwangsa, 1989", "COLOUR INDEX, THE SOCIETY OF DYES & COLOURIST, THIRD EDITION, 1987".

In addition, it is preferable to use the pigment fine particles having a color complementary to the color of the metal fine particles in the present invention. In addition, pigment fine particles may be used by 1 type, and may be used in combination of 2 or more type. Preferred combinations of pigments include a combination of pigment mixtures having a complementary color relationship of red and blue colors and a pigment mixture of complementary colors of yellow and purple colors, or a combination of further adding a black pigment to the mixture, or a blue system. And combinations of violet and black pigments.

The pigment fine particles are preferably dispersed uniformly in the composition. 5 nm-5 micrometers are preferable, and, as for the arithmetic mean particle diameter of the said pigment fine particle, 10 nm-1 micrometer are especially preferable. When using the coloring composition of this invention as a color filter use, the arithmetic mean particle diameter of the said pigment fine particle is 20 nm-0.5 micrometer.

Shading Image Coloring Composition

The case where the coloring composition of this invention is used especially as a coloring composition of a light-shielding image effect (henceforth a "light-shielding coloring composition") is demonstrated in detail below.

When forming a light shielding layer (layer before patterning) using the said light shielding coloring composition, it is preferable that the optical density per 1 micrometer of film thicknesses of a light shielding layer becomes one or more. For example, when considering the prevention of fusion of the metal fine particles during post-baking, such as when manufacturing a color filter, the content of the metal fine particles in the light-shielding colored composition is 10 to 90 to the total solids of the light shielding layer to be formed. It is preferable to adjust so that it may become mass%, Preferably it is about 10-80 mass%. In addition, it is preferable to carry out the said content in consideration of the fluctuation | variation of the optical density by the average particle diameter of a metal fine particle.

In addition, in the light-shielding coloring composition which has a photosensitivity mentioned later, content of a metal fine particle is also the same.

As used herein, the term "shading image" can be used in the sense of including a black matrix. The term "black matrix" refers to black edges formed on the periphery of display devices such as liquid crystal display devices, plasma display display devices, EL display devices, CRT display devices, black portions of a lattice or stripe between red, blue, and green pixels, and TFT light shielding. The black matrix is a dot pattern or a linear black pattern, and the definition of this black matrix is described, for example, in Kanno Taihei, "Liquid Crystal Monitor Manufacturing Equipment Dictionary", Second Edition, Daily Industrial Newspaper, 1996, p.64. It is. Examples of the light shielding image include an organic EL display (for example, Japanese Patent Application Laid-Open No. 2004-103507), a front panel of a PDP (for example, Japanese Patent Application Laid-Open No. 2003-51261), and a light shielding for a backlight in PALC. have.

Black matrix has high light shielding properties (3 or more in optical density OD) to improve display contrast and to prevent image degradation due to light leakage in an active matrix drive type liquid crystal display device using a thin film transistor (TFT). This is necessary.

<Photosensitive Shading Image Processing Coloring Composition>

As for the said light-shielding imaging agent coloring composition, it is more preferable to have photosensitivity. Specifically, the photosensitive property can be imparted by adding the photosensitive resin composition to the colored composition of the present invention. The form in which the said photosensitive resin composition contains the polymer used as a binder, a photoinitiator, a photopolymerizable monomer, etc. is mentioned preferably.

The photosensitive resin composition may be developable in an aqueous alkali solution and developable in an organic solvent. From the viewpoint of safety and cost of the developer, it is preferable that the aqueous alkali solution can be developed. In order to give an alkali aqueous solution developability to the said photosensitive resin composition, it is preferable to make the polymer of a binder an alkali-soluble polymer.

The said photosensitive resin composition may be a negative composition which hardens the part which receives radiation, such as light, an electron beam, etc. mentioned above, and the positive composition which a radiation non-accommodating part hardens | cures may be sufficient.

Examples of the positive photosensitive resin composition include those using a noblock resin. As said noblock-type resin, the alkali-soluble noblock resin system of Unexamined-Japanese-Patent No. 7-43899 can be used, for example. Further, a positive photosensitive material according to Japanese Patent Application Laid-Open No. 6-148888, that is, a mixture of an alkali-soluble resin of the above-described publication and 1,2-naphthoquinone diazide sulfonic acid ester as a photosensitive agent and a thermosetting agent according to the publication is disclosed. The positive type photosensitive material containing can be used. Moreover, the composition of Unexamined-Japanese-Patent No. 5-262850 can also be utilized.

As a negative photosensitive resin composition, the photosensitive resin which consists of negative diazo resin and a binder, the photopolymerizable composition, the photosensitive resin composition which consists of an azide compound, and a binder, cinnamic acid type photosensitive resin composition, etc. are mentioned. Especially, the photopolymerizable composition containing a photoinitiator, a photopolymerizable monomer, and a binder as a basic component is especially preferable. As the photopolymerizable composition, "polymerizable compound B", "polymerization initiator C", "surfactant", "adhesive aid" and other compositions described in JP-A-11-133600 can be used.

For example, the photosensitive resin composition which is a negative photosensitive resin composition and which can develop an aqueous alkali solution is mentioned as the main component, The photosensitive resin composition containing a carboxylic acid group containing binder (alkali-soluble binder), a photoinitiator, and a photopolymerizable monomer is mentioned. Moreover, as said alkali-soluble binder, resin illustrated as said resin or its precursor can be used as a suitable thing.

The alkali-soluble binder is usually 10 to 95 mass%, more preferably 20 to 90 mass%, based on the total solids of the photosensitive light-shielding colored composition. When content is in the range of 10-95 mass%, the adhesiveness of the photosensitive resin layer does not become high too much, and the intensity | strength and light sensitivity of the layer formed do not deteriorate.

Examples of the photopolymerization initiator include a bisinal polyketaldonyl compound disclosed in US Patent No. 2367660, an acyloin ether compound described in US Patent No. 2448828, and α-hydrocarbon described in US Patent No. 2722512. Substituted aromatic acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3046127 and 2951758, combinations of triarylimidazole dimers and p-aminoketones described in US Pat. No. 3549367, Japan Benzothiazole compound and trihalomethyl-s-triazine compound described in patent publication No. 51-48516, trihalomethyl-s-triazine compound described in US Pat. No. 4239850, US Patent No. The trihalomethyl oxadiazole compound described in specification 4212976 etc. are mentioned. Especially preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimers.

In addition, "polymerization initiator C" described in JP-A-11-133600 is also preferable.

These photoinitiator or photoinitiator system may be used individually or in mixture of 2 or more types, It is preferable to use 2 or more types especially. Moreover, as for content of the photoinitiator with respect to the total solid of the photosensitive resin composition, 0.5-20 mass% is common, and 1-15 mass% is preferable.

As a combination of the photoinitiator which can be made high without the coloring of yellowing, and can exhibit outstanding display characteristics, the combination of a diazole type photoinitiator and a triazine type photoinitiator is mentioned. Among them, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole and 2,4-bis (trichloromethyl) -6- [4 '-(N, Most preferred is a combination of N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine.

The ratio of these photoinitiators is preferably 95/5 to 20/80, more preferably 90/10 to 30/70, and particularly preferably 80/20 to 60/40 as the mass ratio of the diazole / triazine series. to be. These photoinitiators are described in Japanese Patent Application Laid-Open No. Hei 1-5244949, Japanese Patent Application Laid-Open No. Hei 1-254918, and Japanese Patent Application Laid-Open No. 2-153353.

Moreover, a benzophenone type is mentioned as a preferable example at the time of the said photoinitiation.

Moreover, when the ratio of the pigment to the whole solid content of the photosensitive light-shielding coloring composition is about 15-25 mass%, the coloring of yellowing etc. can also be suppressed and high sensitivity can also be mixed by mixing a coumarin type compound with the said photoinitiator.

As the coumarin-based compound, 7- [2- [4- (3-hydroxymethylbiperidino) -6-diethylamino] triazinylamino] -3-phenylcoumarin is most preferred. As for the ratio of these photoinitiators and a coumarin type compound, 20/80-80/20 are preferable as a mass ratio of a photoinitiator / coumarin type compound, More preferably, it is 30/70-70/30, Most preferably, 40 / 60 to 60/40.

However, the photopolymerizable composition which can be used for this invention is not limited to these, It can select suitably from a well-known thing.

The said photoinitiator is 0.5-20 mass% with respect to the total solid of the photosensitive light-shielding coloring composition, and 1-15 mass% is preferable. If the said content is in the said range, the fall of a light sensitivity and an image intensity can be prevented, and performance can fully be improved.

As said photopolymerizable monomer, a compound whose boiling point is 100 degreeC or more at normal pressure is mentioned. For example, Monofunctional (meth) acrylates, such as polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylolpropane triacrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedioldi (meth) acrylate, trimethyl Allpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin (Meth) acrylated after addition reaction of ethylene oxide and propylene oxide to polyfunctional alcohols such as It may be mentioned polyfunctional (meth) acrylate and the like.

Furthermore, urethane acrylates disclosed in Japanese Patent Application Laid-Open Nos. 48-41708, 50-6034, and Japanese Patent Laid-Open No. 51-37193, Japanese Patent Publication No. 48-64183, and Japanese Patent Publication No. 49- And polyfunctional acrylates and methacrylates such as polyester acrylates disclosed in Gazette Nos. 43191 and 52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acids. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable. The said photopolymerizable monomer may be used individually or in mixture of 2 or more types. As for content with respect to the total solid of the photosensitive light-shielding coloring composition of the said photopolymerizable monomer, 5-50 mass% is common, and 10-40 mass% is preferable. If the said content is in the said range, neither photosensitivity nor the intensity | strength of an image will fall, and the adhesiveness of the photosensitive light shielding layer will not become excessive.

As the photosensitive light-shielding colored composition, it is preferable to further add a thermal polymerization inhibitor in addition to the above components. Examples of the thermal polymerization inhibitor include, for example, aromatic hydrides such as hydroquinone, p-methoxyphenol, pt-butylcatechol, 2,6-di-t-butyl-p-cresol, β-naphthol, pyrogarol, and the like. Quinones such as hydroxy compounds, benzoquinone, p-toluquinone, amines such as naphthylamine, pyridine, p-toluidine, phenothiazine, aluminum salts or ammonium salts of N-nitrosophenylhydroxylamine, chloranyl, nitro Benzene, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. Can be mentioned.

The photosensitive light-shielding colored composition may further contain a known additive, for example, a plasticizer, a surfactant, an adhesion promoter, a dispersant, a deflection agent, a leveling agent, an antifoaming agent, a flame retardant, a brightening agent, a solvent, and the like, as necessary.

As the adhesion promoter, for example, alkylphenol / formaldehyde noblock resin, polyvinyl ethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene, styrene butadiene copolymer rubber, butyl rubber, vinyl chloride-acetic acid Vinyl copolymers, chlorinated rubbers, acrylic resin-based pressure-sensitive adhesives, aromatic, aliphatic or alicyclic petroleum resins, silane coupling agents and the like.

By forming the black matrix using the light-shielding coloring composition (including photosensitive ones) of the present invention, a thin film and a black matrix having high optical density can be produced.

Photosensitive Transfer Material

(Photosensitive light shielding layer)

In this invention, the photosensitive light shielding layer is formed on a support body using the metal particle dispersion of this invention, and it can be set as the photosensitive transfer material of this invention. By using the photosensitive transfer material of the present invention, light blocking images such as black matrices can be produced.

The photosensitive transfer material may have at least one photosensitive light shielding layer formed on the support using the light-shielding coloring composition having the above photosensitivity, and the like, and may form a thermoplastic resin layer, an intermediate layer, a protective layer, or the like as necessary.

The film thickness of the photosensitive light shielding layer is preferably in the range of 0.1 to 4 µm, particularly preferably in the range of 0.1 to 2.0 µm, more preferably 0.2 to 1.0 µm.

(Support)

In the said photosensitive transfer material, well-known support bodies, such as polyester and polystyrene, can be used as a support body. Especially, the polyethylene terephthalate biaxially stretched is preferable from a viewpoint of cost, heat resistance, and dimensional stability. The thickness of the support is about 15 to 200 μm, more preferably about 30 to 150 μm. When the thickness of the support is in the above range, it is possible to effectively suppress the occurrence of wrinkles on the corrugated wall plate due to heat during the lamination process, which is advantageous in terms of cost.

Moreover, you may provide the said support body with the electroconductive layer described in Unexamined-Japanese-Patent No. 11-149008 as needed.

(Thermoplastic layer)

Moreover, it is preferable to form an alkali-soluble thermoplastic resin layer between a support body and the photosensitive light shielding layer, or between a support body and an intermediate | middle layer.

Since the said thermoplastic resin layer plays a role as a cushioning material so that the unevenness | corrugation (including the unevenness | corrugation etc. by the image etc. which are already formed) of the undersurface may be absorbed, it is preferable to have the property which can be deformed according to the unevenness | corrugation.

Examples of the resin included in the alkali-soluble thermoplastic resin layer include a saponified product of ethylene and an acrylic acid ester copolymer, a saponified product of a styrene and a (meth) acrylic acid ester copolymer, a saponified product of a vinyltoluene and a (meth) acrylic acid ester copolymer, and a poly ( It is preferable that it is at least 1 sort (s) chosen from saponified products, such as (meth) acrylic acid ester copolymers, such as a meta) acrylic acid ester, butyl (meth) acrylate, and vinyl acetate. Among the organic polymers used by the "Plastic Performance Handbook" (Japan Plastic Industry Association, All Japan Plastic Molding Industry Association, published by Industrial Society of Japan, published on October 25, 1968), it is also possible to use those which are available in aqueous alkali solution. Moreover, it is preferable that the softening point is 80 degrees C or less among these thermoplastic resins.

As resin contained in the said thermoplastic resin layer, it is preferable to select from the resin contained in the said alkali-soluble thermoplastic resin layer in the range of the weight average molecular weights 300,000-500,000 (Tg = 0-170 degreeC), and also to use The range of average molecular weight 40-200,000 (Tg = 30-140 degreeC) is more preferable. Specific examples of these resins include Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 55-38961, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 61-134756, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-92723, Japanese Patent Publication No. 54-99418, Japanese Patent Publication No. 54-137085, Japanese Patent Publication No. 57-20732, Japanese Patent Publication No. 58 -93046, Japanese Patent Publication No. 59-97135, Japanese Patent Publication No. 60-159743, Japanese Patent Publication No. 60-247638, Japanese Patent Publication No. 60-208748, Japanese Patent Publication No. 60-214354, Japan Patent Publication No. 60-230135, Japanese Patent Publication No. 60-258539, Japanese Patent Publication No. 61-169829, Japanese Patent Publication No. 61-213213, Japanese Patent Publication No. 63-147159, Japanese Patent Publication No. 63- 213837, Japanese Patent Publication No. 63-266448, Japanese Patent Publication No. 64-55551, Japanese Patent Publication No. 64-55550, Japanese Patent Application Laid-Open No. 2-191955, Japanese Patent Publication No. 2-199403, Japan Patent Publication No. 2-199404 call, there may be mentioned a resin that is soluble in Japanese Patent Laid-Open Publication No. Hei 2-208602, an aqueous alkaline solution as described in each publication of Japanese Patent Publication No. 5-241340.

Among these, particularly preferred are methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in Japanese Patent Application Laid-Open No. 63-147159, Japanese Patent Publication No. 55-38961, The styrene / (meth) acrylic acid copolymer as described in each Unexamined-Japanese-Patent No. 5-241340 is mentioned.

In addition, it is possible to add various plasticizers, various polymers, subcooling materials, adhesion improving agents, surfactants or release agents to the thermoplastic resin layer in order to adjust the adhesion between the thermoplastic resin layer and the support. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, and polyethylene. Glycoldi (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycoldi (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol Addition reaction products of mono (meth) acrylate, addition reaction products of organic diisocyanate and polypropylene glycol mono (meth) acrylate, and condensation reaction products of bisphenol A and polyethylene glycol mono (meth) acrylate.

Since content of the plasticizer in the said thermoplastic resin layer is generally 200 mass% or less with respect to the total solid of a reversible resin layer, Preferably it is 20-100 mass%.

Moreover, as for the thickness of the said thermoplastic resin layer, 6 micrometers or more are preferable. If the thickness of the thermoplastic resin is 6 µm or more, the unevenness of the surface of the base can be completely absorbed. In addition, about 100 micrometers or less are generally the upper limit from developability and aptitude, and it is preferably about 50 micrometers or less.

In this invention, as a solvent of the coating liquid used when forming a thermoplastic resin layer, as long as it melt | dissolves resin which comprises this layer, it can use without a restriction | limiting. As said solvent, methyl ethyl ketone, cyclohexanone, a propylene glycol monomethyl ether acetate, n-propanol, i-propanol, etc. are mentioned, for example.

(Middle floor)

In the photosensitive transfer material of the present invention, an intermediate layer may be formed between the support and the photosensitive light shielding layer.

There is no restriction | limiting in particular as resin which comprises an intermediate | middle layer as long as it is alkali-soluble. Examples of the resins include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. have. Moreover, the resin which copolymerized the monomer which has a carboxyl group and sulfonic acid group in resin which is not alkali-soluble normally like a polyester can also be used.

Among these, polyvinyl alcohol is preferable. As said polyvinyl alcohol, it is preferable that a degree of influence is 80% or more, and it is more preferable that it is 83 to 98%.

It is preferable to mix and use two or more types of resin which comprises an intermediate | middle layer, and it is especially preferable to mix and use polyvinyl alcohol and polyvinylpyrrolidone. The mass ratio of both is preferably in the range of polyvinylpyrrolidone / polyvinyl alcohol = 1/99 to 75/25, and more preferably in the range of 10/90 to 50/50. If the said mass ratio is in the said range, the surface state of an intermediate | middle layer will be favorable, the adhesiveness of the photosensitive light-shielding layer apply | coated on it will be favorable, and oxygen barrier property will fall and it can prevent that a sensitivity falls.

Moreover, additives, such as surfactant, can be added to the said intermediate | middle layer as needed.

As for the thickness of the said intermediate | middle layer, the range of 0.1-5 micrometers, 0.5-3 micrometers is more preferable. If the thickness of the intermediate layer is in the above range, it is possible to prevent the increase of the intermediate layer removal time during development without lowering the oxygen barrier property.

The coating solvent for the intermediate layer is not particularly limited as long as the resin is dissolved. Among them, water is preferable, and a mixed solvent in which the water-miscible organic solvent is mixed with water is also preferable. Specific examples of preferred coating solvents include water, water / methanol = 90/10, water / methanol = 70/30, water / methanol = 55/45, water / ethanol = 70/3, water / 1-propanol = 70/30, water / acetone = 90/10, water / methyl ethyl ketone = 95/5 (meaning mass ratio), etc. are mentioned.

(Production of Photosensitive Transfer Material)

In the photosensitive transfer material of the present invention, a light-shielding colored composition solution having the photosensitivity of the present invention on a support may be formed by using an applicator such as a spinner, a filler, a roller coater, a curtain coater, a knife coater, a wire bar coater or an injection machine. It can produce by apply | coating and drying and forming a photosensitive light shielding layer. Moreover, also when forming an alkali-soluble thermoplastic resin layer, it can form in a similar way.

In the photosensitive transfer material of the present invention, since the photosensitive light shielding layer is formed using the light shielding color composition of the present invention at the above time, a thin film and a light shielding layer having high optical density can be produced.

`` How to make shading images ''

(Formation method of light shielding layer)

In the present invention, the light shielding image is produced by patterning a light shielding layer formed using the metal particulate dispersion of the present invention, a colored composition containing the same or a photosensitive transfer material. At this time, it is preferable that the film thickness of the said light shielding layer is about 0.2-2.0 micrometers, and is 0.9 micrometer or less. Since the said light shielding layer is what disperse | distributed metal fine particles in this invention, it can exhibit sufficient optical density (O.D3.5 or more) also in a thin film at the time mentioned above.

In addition, the method for producing (patterning) the light-shielding image using the metal fine particle dispersion of the present invention, a colored composition containing the same or a photosensitive transfer material is not particularly limited. An example of the pattern formation method of a black matrix is given below.

The first method first comprises a metal fine particle in the present invention and an alkali-soluble polymer in the present invention, and the light-shielding coloring composition of the present invention having photosensitivity is applied to a substrate to provide the metal fine particles and the alkali-soluble polymer in the present invention. The photosensitive light shielding layer contained is formed. The first method is a method of pattern formation by removing the light shielding layer of the portion other than the pattern after the exposure phenomenon to obtain a light shielding image. The same composition layer as the above intermediate layer may be formed on the photosensitive light shielding layer to form a protective layer. In this case, application | coating of a coating liquid can be apply | coated using the said applicator, Especially, it is preferable by the spin coat method.

The second method first contains a metal fine particle in the present invention and an alkali-soluble polymer in the present invention, and applies a non-photosensitive colored composition of the present invention to a substrate, and contains a metal fine particle and an alkali-soluble polymer in the present invention. A light shielding layer is formed. Thereafter, a photosensitive resist liquid is applied onto the light shielding layer to form a resist layer. In the second method, the resist layer is exposed to light by exposure to form a pattern in the resist layer, and then the non-pattern portion of the light shielding layer is dissolved in accordance with this pattern to form a pattern in the light shielding layer. Finally, the resist layer is removed to form a light shielding image.

In the third method, a coating layer is formed on a portion other than the pattern on the substrate in advance, and the fine particle-containing layer is coated by applying the non-photosensitive light-shielding coloring composition of the present invention containing metal fine particles and an alkali-soluble polymer in the present invention. A light shielding layer is formed. Next, the coating layer formed initially is removed together with the above light shielding layer to produce a light shielding image.

In the manufacturing method of a light shielding image using the said photosensitive transfer material, the said photosensitive transfer material is arrange | positioned so that the photosensitive light shielding layer of a photosensitive transfer material may contact | abut on a light transmissive substrate, and is laminated | stacked. Next, the support is peeled off from the laminate of the photosensitive transfer material and the light transmissive substrate, after which the layer is exposed and then developed to form a light shielding image.

The manufacturing method of this light-shielding image does not need to perform a cumbersome process, and is low cost.

(Exposure and development)

Next, the exposure and development steps will be described.

A process of disposing a predetermined mask above the light shielding layer formed on the substrate, then exposing from above the mask, developing with a developing solution, obtaining a patterned image, and subsequently washing with water as necessary. The light shielding image of this invention can be obtained. In addition to the method of arranging the mask as described above, the exposure may be performed by relative scanning of the exposure light based on the image data directly through the mask to obtain a pattern image.

Here, as a light source of the said exposure, if the light (for example, 365 nm, 405 nm, etc.) of the wavelength range which can harden | cure the photosensitive resin layer can be irradiated, it can select suitably and can use. Specifically, ultra high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, LD, ultra high pressure mercury lamp, YAG-SHG solid laser, KrF laser, solid laser and the like can be given. As an exposure amount, it is about 5-20mJ / cm <2> normally, Preferably it is about 10-10mJ / cm <2>.

Although the exposure machine used at this time is not specifically limited, A scattering ray exposure machine, a parallel ray exposure machine, a stepper, a laser exposure, etc. can be used other than the proximate exposure machine exposed through the said mask.

There is no restriction | limiting in particular as said developing solution, Well-known developing solutions, such as those of Unexamined-Japanese-Patent No. 5-72724, can be used, In this invention, the lean aqueous solution of alkaline substance is used preferably. In detail, it is preferable that, as for a developing solution, the photosensitive resin layer has the melt | dissolution type developing behavior. Moreover, you may add a small amount of the organic solvent which has miscibility with water.

Moreover, it is preferable to spray pure water with a shower nozzle etc. before the said image development, and to be able to uniformly wet the surface of the said photosensitive light-shielding layer.

In the forming method by applying the light-shielding image and the forming method using the photosensitive transfer material, examples of the alkaline substance include alkali metal hydroxides (for example, sodium hydroxide and potassium hydroxide) and alkali metal carbonates (for example, Sodium carbonate, potassium carbonate), alkali metal bicarbonates (e.g. sodium bicarbonate, potassium hydrogen carbonate), alkali metal silicates (e.g. sodium silicate, potassium silicate), alkali metal methsilicates (e.g. Sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanol amine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, etc. are mentioned. . 0.01-30 mass% is preferable, and, as for the density | concentration of an alkaline substance, 8-14 are preferable.

Examples of the "water miscible organic solvent" include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monon-. Butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butylollactone, dimethylformamide, dimethyl acetamide, hexamethylphosphoamide, ethyl lactate, methyl lactate, ε-capro Lactam, N-methylpyrrolidone, etc. are mentioned preferably. As for the density | concentration of water and a miscible organic solvent, 0.1-30 mass% is preferable. Moreover, a well-known surfactant can also be added and 0.01-10 mass% is preferable as a density | concentration of the said surfactant.

The developer can be used either as a solution or as a spray solution. When removing the uncured portion of the light shielding layer, a method such as rubbing with a rotary brush or a wet sponge in the developer can be combined. As for the liquid temperature of a developing solution, 40 degreeC is preferable normally from room temperature. The developing time depends on the composition of the light shielding layer, alkalinity and temperature of the developing solution, and the type and concentration of the organic solvent, but is usually about 10 seconds to 2 minutes. If too short, the development of the non-exposed part will be insufficient, and the absorbance of the ultraviolet light will be insufficient, and if it is too long, the exposed part will be etched. In either case, it is difficult to say that the light shielding image shape is preferable. In this developing step, a light shielding image is formed.

<< shading image board >>

The light-shielding image attachment substrate of the present invention is formed by patterning a light-shielding layer formed on the light-transmitting substrate using the metal particulate dispersion of the present invention or the coloring composition of the present invention or the photosensitive transfer material of the present invention as described above. Is produced.

In this light-shielding image attachment substrate (preferably a black matrix substrate), the film thickness of the light-shielding image is preferably 0.2 to 2.0 m, particularly preferably 0.2 to 0.9 m. In the black matrix substrate, since the light shielding layer disperses metal particles in the present invention, the thin film as described above has sufficient optical density.

The light-shielding image attachment substrate of the present invention can be applied without particular limitation to applications such as mobile phones, digital cameras, automobile navigation, and the like for televisions, PCs, liquid crystal projectors, game machines, and cellular phones. Moreover, it can use suitably also in preparation of the following color filter.

<< color filter >>

The color filter of the present invention comprises a color layer formed on a light-transmissive substrate and has two or more pixel groups showing different colors, and each pixel constituting the pixel group is partitioned by a light shielding image (black matrix). Has a configuration. The black matrix is produced using the metal particulate dispersion of the present invention or the coloring composition or photosensitive transfer material of the present invention using the same. The pixel group may be two, three, or four or more. For example, in three cases, three colors of red (R), green (G), and blue (B) can be suitably used. In the case of arranging three types of pixel groups of red, green, and blue, an arrangement such as a mosaic type or a triangle type is preferable. In the case of arranging four or more types of pixel groups, any arrangement may be used.

As the light transmissive substrate, a known glass plate or plastic film such as a soda glass plate, a low-expansion glass plate, a non-alkali glass plate, a quartz glass plate, or the like having a silicon oxide film on its surface can be used.

In order to produce the color filter of the present invention, after forming a group of two or more pixels on a transparent substrate by a conventional method, a black matrix may be formed as described above, or a black matrix is first formed, and then You may form two or more pixel groups.

Since the color filter of this invention is equipped with the high density black matrix in the thin film at the time mentioned above, display contrast is high and it is excellent in flatness.

<< display element >>

The metal fine particle dispersion of this invention can be used suitably for a display element. Examples of the display element include a plasma display display device, an EL display device, a CRT display device, a liquid crystal display device, and the like. Among these, when used in a liquid crystal display device, the effect of the metal particulate dispersion of the present invention is remarkably exhibited. For the definition of the display elements and the explanation of each display device, for example, "Electronic display device (Aki Sasaki, published by the Industrial Engineering Society, 1990)", "Display device (Ibuki Cooking Yukizu, Industrial Books, 1989)" "And the like.

The liquid crystal display device of the present invention is an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer in addition to the color filter. It is generally comprised from various members, such as a viewing angle compensation film, an antireflection film, a light-diffusion film, and an anti-glare film. In the present invention, the light shielding image can be applied to a liquid crystal display device composed of these known members. For these members, for example, the market for '94 liquid crystal display peripheral materials and chemicals (Kenta Shima Kentaro Co., Ltd. 1994), and the current status and future prospects of the 2003 liquid crystal display market (Seoul) Is issued by Fuji Kimera Research Institute, Inc. 2003), and examples of the LCD include STN, TN, VA, IPS, OCS, and R-OCB.

One of the liquid crystal display apparatuses includes at least one of a color filter, a liquid crystal layer, and a liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between at least one substrate that is light transmissive.

As the color filter, a color filter having a plurality of pixel groups as described above and each pixel constituting the pixel group divided by the light shielding image according to the present invention can be suitably used. Since the color filter has a high flatness, a liquid crystal display device including the color filter does not generate a cell gap stain between the color filter and the substrate, and improves the display defect such as color stain.

As another form of the liquid crystal display device, at least one of at least one color filter, a liquid crystal layer, and a liquid crystal driving means is provided between one substrate which is light transmissive, and the liquid crystal driving means has an active element (for example, a TFT). In addition, a black matrix fabricated using the metal particulate dispersion of the present invention, a colored composition using the same, or a photosensitive transfer material is formed between the active elements.

The liquid crystal display device is described, for example, in "next-generation liquid crystal display technology (Tatsuo Uchida editorial, 1994 published by the side industrial cooperative)." There is no restriction | limiting in particular in the display apparatus (liquid crystal display apparatus) of this invention, For example, it is applicable to the liquid crystal display apparatus of various systems described in the said "next-generation liquid crystal display technique." Among these, the present invention is particularly effective for a color TFT type liquid crystal display device.

In addition, the liquid crystal display device of the color TFT system is described in "Color TFT liquid crystal display (public publication, Inc., 1996)". In addition to the present invention, the viewing angle of the transverse electric field driving method such as IPS and the pixel division method such as MVA can be applied to the enlarged liquid crystal display device. These methods are described, for example, on page 43 in "EL, PDP, LCD Display Technology and the Latest Trends in the Market" (Issue Research, Toray Research Center 2001).

Examples of the liquid crystals that can be used in the liquid crystal display device include nematic liquid crystals, correster liquid crystals, smecting liquid crystals, ferroelectric liquid crystals, and the like.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this. In addition, "part" means a "mass part" unless there is particular limitation.

Example 1

(1) alkali soluble polymer test

0.2 g of the polymer compound PO-33 was added to 20 mL of an aqueous NaOH solution adjusted to pH12.0, stirred vigorously, and left for 6 hours in a constant temperature layer at 25 ° C to confirm solubility. At the same time, 0.2 g of the compound to be evaluated (in this case, the polymer compound PO-33) was added to 20 ml of distilled water and stirred vigorously, and the solubility was confirmed after standing for 6 hours in a constant temperature layer at 25 ° C. At this time, when white turbidity and sediment were confirmed, insoluble (x), and when turbidity and sediment were not confirmed, it was determined as soluble ((circle)).

As a result, the high molecular compound PO-33 was soluble in aqueous NaOH solution at pH (○) and insoluble in distilled water (×).

In addition, the polymer compound PO-33 is the following polymer compound PO-25, 7, 11, 20, 23, 19, 32, S-1 (Disperbyk-161 manufactured by BYK Chemie), S-2 (Disperbyk- manufactured by BYK Chemie) 190) and substituted by T-1-4 and performed the same evaluation. The results are shown in Table 1.

Alkali solubility test: Insoluble in (××) H ₂ O, insoluble in alkaline solution

Soluble in (×) H ₂ O, soluble in alkaline solution

(○) Insoluble in H ₂ O, soluble in alkaline solution

                    (Alkali-soluble polymer in the present invention)

(2) Preparation of silver nano particle dispersion: Metal-containing dispersion A-1

3 g of the polymer compound PO-33 was added to 2.5 L of an aqueous solution having a pH adjusted to 12.0 using 1 N aqueous sodium hydroxide solution, followed by stirring at 45 ° C for 30 minutes until complete dissolution.

This solution was temperature-controlled at 45 degreeC, the aqueous solution containing 12 g of ascorbic acid, and the aqueous solution containing 30 g of silver nitrate were simultaneously added simultaneously, and the black silver nanoparticle content liquid was prepared.

Silver fine particles obtained were irregular potato particles with an arithmetic mean particle size of 52 nm and an arithmetic standard deviation of 33 nm.

The prepared silver nanoparticle content liquid was centrifuged (12000 rpm. 30 minutes), the supernatant liquid was discarded, distilled water was added, and water washing was repeated three times. Further, acetone was added to the silver nanoparticle-containing liquid and stirred in a stirrer, followed by centrifugation (12000 rpm. 30 minutes). Thereafter, the supernatant was removed, 1-methoxy-2-propyl acetate was added, and ultrasonic waves at 20 kHz were irradiated for 5 minutes using a "Sonifier II" ultrasonic homogenizer manufactured by Branson. After that, Branson's "Model 200bdc-h 40: 0.8 type ultrasonic homogenizer" was irradiated with 40kHz ultrasonic waves for 10 minutes. The silver nanoparticle dispersion liquid thus obtained had the same shape and color taste as after the particle formation. Further, the Ag content of the obtained silver nanoparticle dispersion was measured by atomic absorption method. As a result, the Ag concentration was 8.0% by mass. Moreover, the density | concentration in the solvent dispersion of the high molecular compound PO-33 obtained by drying loss using TG-DTA (made by Seiko Corporation) was 1.1 mass%. This silver nanoparticle dispersion is referred to as metal-containing dispersion A-1.

The metal-containing dispersion A-1 obtained Ag concentration = 4.0 × 10 ^{- 4} mol / such that ℓ diluted at the right time in acetone solvent, and the spectral absorption using a Hitachi Ltd Product "U-3410 type magnetic minute light Shape" Measured. At wavelengths of 450 nm and 550 nm, the absorption ratio, that is, blackness k = Abs (450 nm) / Abs (550 nm) was 1.4.

(3) Preparation of silver fine particle dispersion: Metal-containing dispersion A-2 to A-14

In the above (2), a metal particle-containing liquid was prepared in the same manner as in (2), except that the high molecular compound PO-33 was replaced with the high molecular compound shown in Table 2 below. The arithmetic mean particle diameter, arithmetic standard deviation, and particle shape of the silver fine particles obtained are shown in Table 2 below.

Subsequently, the metal particle content liquid obtained similarly to said (2) was processed, and the metal particle dispersion liquid of Ag concentration 8.0 mass% was prepared. At this time, the solvent added to the metal particle-containing liquid was selected from 1-methoxy-2-propyl acetate or propyl alcohol in consideration of the solubility of the high molecular compound. Similarly, blackness = k was measured and the results are shown in Table 2 below.

(4) Preparation of silver alloy fine particles (nano particles) dispersion: Metal-containing dispersion A-15

3 g of the polymer compound PO-20 was added to 2.5 L of an aqueous solution in which pH was adjusted to 12.2 using 1 N aqueous sodium hydroxide solution, followed by stirring at 45 ° C for 30 minutes until complete dissolution.

This solution was temperature-controlled at 50 degreeC, the aqueous solution containing 3 g of sodium borohydride, the aqueous solution containing 24 g of silver nitrates, and the aqueous solution containing 24.2 g of gold chlorides were simultaneously added, and the black-brown silver-alloy nanoparticle containing liquid was prepared. The arithmetic mean particle diameter, arithmetic standard deviation, and particle shape of the obtained silver alloy nanoparticles are shown in Table 2 below.

Subsequently, the silver alloy nanoparticle-containing liquid obtained in the same manner as in (2) above was treated, and 1-methoxy-2-propyl acetate was added to the silver alloy nanoparticles having a metal concentration of 0.74 mol / l (total of silver and gold). A particle dispersion was prepared, which was called metal dispersion A-15. Similarly, blackness = k was measured and the results are shown in Table 2 below.

(5) Preparation of silver tin alloy nanoparticle dispersion: Metal-containing dispersion A-16

3 g of the polymer compound PO-20 was added to 2.5 L of an aqueous solution whose pH was adjusted to 12.0 using 1 N aqueous sodium hydroxide solution, followed by stirring at 45 ° C for 30 minutes until complete dissolution.

The solution was temperature-controlled at 50 DEG C, and an aqueous solution containing 23 g of silver acetate (I) and 13 g of tin chloride (II) hydrate was added to the solution of black brown silver tin alloy nanoparticles. A liquid solution was prepared. Table 2 shows the arithmetic mean particle size, arithmetic standard deviation, and particle shape of the silver fine particles obtained.

Subsequently, the metal fine particles obtained in the same manner as in (2) above were treated, and 1-methoxy-2-propyl acetate was added to disperse the silver tin alloy nanoparticle dispersion having a metal concentration of 0.74 mol / L (the sum of silver and tin). It prepared and called this metal-containing dispersion liquid A-16. Similarly, blackness = k was measured and the results are shown in Table 2 below.

(6) Preparation of coating liquid B-1 (coating liquid for shading image forming) for photosensitive light-shielding layer

The following prescription ingredients were mixed to prepare a fine particle-containing composition for a black material (coating liquid B-1 for photosensitive light-shielding layer).

[Furtherance]

Metal-containing dispersion A-1 100.00 parts

Propylene glycol monomethyl ether acetate 25.0 parts

14.0 parts of methyl ethyl ketone

Fluorine-based surfactant O.1 part

(Brand name: F780F, Dainippon Ink & Chemicals Co., Ltd. product)

0.001 part of hydroquinone monomethyl ether

Benzyl methacrylate / methacrylic acid copolymer 2.1 parts

(Molar ratio = 73/27, molecular weight 30000)

Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.1 part

Dipentaerythritol hexaacrylate

(Brand name: KAYARAD DPHA, Nihon Kayaku Co., Ltd.)

* The addition amount of the dipentaerythritol hexaacrylate is 0.9 in the mass ratio when the total mass of the benzyl methacrylate / methacrylic acid copolymer and the polymer compound PO-33 is 1 in the coating liquid. It was in quantity to become.]

(7) Preparation of coating liquid for protective layer

The following composition was mixed and the coating liquid for protective layers was prepared.

[Furtherance]

3.0 parts polyvinyl alcohol

(Brand name: PVA205, Kuraray product)

1.3 parts of polyvinylpyrrolidone

(Brand name: PVP-K30, ISP, Japan company product)

Distilled water 50.7 parts

Methyl alcohol 45.0 parts

(8) Preparation of photosensitive material

The coating liquid B-1 for photosensitive light-shielding layers which passed after 3 hours was prepared on the glass substrate using a spin coater so that a dry film thickness might be set to 1.0 micrometer, and it dried at 100 degreeC for 5 minutes, and formed the photosensitive light-shielding layer. Subsequently, the coating liquid for protective layer was apply | coated so that a dry film thickness might be set to 1.5 micrometers using a spin coater on the photosensitive light-shielding layer, it dries at 100 degreeC for 5 minutes, and forms a protective layer, The photosensitive material P-1 of this invention. Made.

Furthermore, using the photosensitive light-shielding layer coating liquid B-1 which passed after preparation for 3 days, it apply | coated and processed on the glass substrate as mentioned above, and obtained photosensitive material Z-1 which has a protective layer.

(9) Manufacture of Black Matrix

Exposure mask surface and protective layer in a state where the photosensitive material P-1 and the mask (quartz exposure mask having an image pattern) are vertically used, using a proxy type exposure machine (manufactured by Hitachi Electronics Engineer) having an ultra-high pressure mercury lamp. The distance between coating surfaces was set to 200 µm, and the pattern was exposed to an exposure amount of 7 mJ / cm 2. Next, development process (33 degreeC * 20 second) was performed using developing solution TCD (Fuji Photo Film Co., Ltd. product, alkaline developing solution).

This resulted in a black matrix P-1 having a screen size of 10 inches and a pixel count of 480 x 640, a black matrix width of 24 mu m, and an opening in the pixel portion of 86 mu m x 304 mu m.

In addition, the black matrix Z-1 was obtained in the same manner using the photosensitive material Z-1.

(1O) evaluation

The following evaluation was performed about the obtained black matrix. The results are shown in Table 3 below.

(Stability assessment over time)

The optical concentrations of the black matrices P-1 and Z-1 were measured. The concentration fluctuation value was calculated by subtracting the absolute optical density value of the black matrix P-1 from the absolute optical density value of the black matrix Z-1. In addition, the stability of the coating liquid over time was evaluated according to the following criteria before and after three days from the absolute value of the concentration variation value. Each result is shown in Table 3 below.

[standard]

○: absolute value of OD change is less than 0.4

X: The absolute value of OD change is 0.4 or more and less than 1.0

××: Absolute value of OD change is 1.0 or more

Measurement of optical concentration

The optical density of the black matrix was measured by the following method.

First, 500 mJ / cm <2> exposure was performed to the photosensitive light shielding layer apply | coated on the glass substrate before black matrix manufacture by the said ultrahigh pressure mercury lamp from the application surface side. Furthermore, it baked for 120 minutes at 240 degreeC, and the optical density (OD) after that was measured using the Macbeth densitometer (brand name: TD-904, a Macbeth company make).

In addition, the optical density (OD) of the other glass substrate was measured by the same method, OD ₀ was subtracted from the said OD ₁ , and it was set as the optical density of each black matrix.

<< grace of the black matrix >>

In the black matrix Z-1, the quality (color taste) of the black matrix was visually observed and evaluated according to the following criteria. The results are shown in Table 3 below.

[standard]

(Double-circle): It has a black color of favorable hue, and is excellent in a grade as a black matrix.

(Circle): It satisfies a grade with sufficient blackness of black matrix, but is slightly yellowish.

X: It is yellowish brown, and the quality is not enough as a black matrix.

(11) Black Matrix P2 ~ P16, Z-2 ~ Z-16

In the preparation of the coating solution B-1 for photosensitive light-shielding layer, the black matrix P is corresponding to each dispersion liquid in the same manner except that the metal-containing dispersion liquids A-2 to 16 are used instead of the metal-containing dispersion liquid A-1 in the composition. -2-16 and Z-2-16 were produced and similarly, the stability with time-lapse of the coating liquid, and the quality (color taste) of the black matrix were evaluated. The results are shown in Table 3 below.

In Table 3, in the present invention, the light-shielding colored composition (coating solution) prepared by using an alkali-soluble polymer has a small OD decrease due to deterioration with time, and the OD of the obtained black matrix has a high OD of 3.5 or more. The beauty is black, and the elegance is high as a black matrix.

On the other hand, the light-shielding colored compositions of Comparative Examples B-9 and B-10 have a small OD decrease due to deterioration over time, but have a yellow color, and thus have a low OD of the obtained black matrix and satisfactory performance as a black matrix. Could not exert.

In addition, Comparative Examples B-11 to B-14 were able to form a black matrix having a high performance of OD of 3.5 or more in the light-colored coloring composition before time-lapse, but the performance was greatly deteriorated after time-lapse, and the obtained black matrix was obtained. Could not achieve satisfactory performance.

Example 2

<Production of Liquid Crystal Display Device>

Liquid crystal display using the method described in the first Examples [0079] to [0082] of JP-A-11-242243, using the substrate on which the black matrix Z-1 obtained in Example 1 was formed. When the apparatus R-1 was produced, it confirmed that it displayed without malfunction.

Further, except that the black matrix Z-1 was replaced with the black matrices Z-2 to 16 in Example 1, liquid crystal display devices R-2 to 16 were produced in the same manner, and it was confirmed that the display was performed without malfunction.

`` Stain evaluation ''

The following evaluation was performed about each obtained liquid crystal display device. The results are shown in Table 4 below.

Measurement of stain

When the gray test signal was input to the liquid crystal display device, the display part was visually observed and the loupe was observed to determine the occurrence of the stain. "◎" that the stain was not completely observed, "○" that the stain was found a little, and the stain was markedly. The confirmed thing was called "×".

It was found from Table 4 that the liquid crystal display device using the metal fine particle dispersion of the present invention can provide a liquid crystal display device having better display quality and higher display quality without display stains.

Example 3

`` Production of Photosensitive Transfer Material ''

The coating liquid for thermoplastic resin layer prepared as follows using the glass substrate coater (The FAS Japan company make, brand name: MH-1600) which has a slit-shaped nozzle on the 75 micrometer-thick polyethylene terephthalate film support body surface extended biaxially was carried out. It applied so that thickness might be 15 micrometers, and it dried at 100 degreeC for 5 minutes, and formed the thermoplastic resin layer. Subsequently, the coating liquid for intermediate | middle layers of the composition similar to the coating liquid for protective layers in Example 6 (6) was apply | coated so that a dry film thickness might be 1.5 micrometer on this, and it dried at 100 degreeC for 5 minutes, and formed the intermediate | middle layer. Furthermore, in Example 1 after 3 days of liquid preparation, the coating liquid B-1 for photosensitive light-shielding layers of (6) was applied so that it might be set to a dry film thickness of 1.0 micrometer, and it dried at 100 degreeC for 5 minutes, and formed the photosensitive light-shielding layer. To produce a photosensitive transfer material.

<Preparation of coating liquid for thermoplastic resin layer>

The following composition was mixed and the coating liquid for thermoplastic resin layers was prepared.

58 parts of copolymers (molecular weight 80000) of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid (55 / 11.7 / 4.5 / 28.8)

136 parts of styrene / acrylic acid = 63/37 copolymer (molecular weight 7000)

2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane

(Shin-Nakamura Kagaku Kogyo Co., Ltd., polyfunctional acrylate) 90 parts

1 part fluorine-based surfactant

(Brand name: F780F, Dainippon Ink & Chemicals Co., Ltd. product)

541 parts of methyl ethyl ketone

1-methoxy-2-propanol 63 parts

111 parts methyl alcohol

<< production of photosensitive material >>

The glass substrate and the photosensitive transfer material obtained above were overlapped so that the photosensitive light shielding layer contacted the glass substrate, and both were bonded together using a laminator (manufactured by Hitachi Industries, Inc. (Lamic II type)). Lamination conditions were rubber roller temperature 130 degreeC, linear pressure 100N / cm, and conveyance speed 2.2m / min. Then, the support body (polyethylene terephthalate film) was peeled from the photosensitive transfer material, and photosensitive material G-1 was produced.

<< production of black matrix >>

Exposure was carried out in the same exposure apparatus as Example (9) of Example 1 and under the same exposure conditions. Subsequently, the following three process development processes were carried out, and black matrix H-1 was obtained.

[Processing]

1st process: The image development process was performed on the conditions of the temperature of 30 degreeC and 40 second using the developing solution (brand name: T-PD1, Fujishashin Film Co., Ltd. product, alkaline developing solution).

2nd process: The image development process was performed on the conditions of the temperature of 33 degreeC and 20 second using the developing solution (brand name: T-CD1, a Fuji developer product, the alkaline developing solution).

3rd process: The image development process was performed on the conditions of the temperature of 33 degreeC and 20 second using the developing solution (brand name: T-SD1, Fujishashin Film Co., Ltd. product, alkaline developing solution).

In addition, in said << production of the photosensitive transfer material >>, black matrix H-2-16 was obtained by the same method except having replaced the coating liquid B-1 for photosensitive light-shielding layers with the coating liquids B-2-16 for photosensitive light-shielding layers.

"evaluation"

In the same manner as in Example 1, the optical density and the quality of the black matrix were evaluated. The results are shown in Table 5 below.

From Table 5, all of the black matrices of the present invention had an OD of 3.5 or more, the color taste was also maintained black, and the quality was high as the black matrix.

[Production and Evaluation of Color Filter]

The grid-shaped light shielding image (black matrix) obtained in the present invention and the comparative example was red, green, blue using a transfer type photosensitive resin film described in Japanese Patent Application Laid-open No. 2004-347831. The predetermined size and the coloring pattern of the shape were formed, and the color filter was produced.

In the present invention, it was possible to produce a color filter free of defects as compared with the color filter produced in the comparative example.

<Production and Evaluation of Liquid Crystal Display Device>

The liquid crystal display device was formed using the color filter of this invention and the color filter of a comparative example which were obtained above.

It was confirmed that the liquid crystal display device using the color filter of the present invention exhibited good display characteristics compared with the liquid crystal display device using the color filter of the comparative example.

<Production and Evaluation of Liquid Crystal Display Device>

Using the color filter of the present invention and the color filter of the comparative example obtained above, a thin film transistor and a pixel electrode were formed on a glass substrate corresponding to the RGB pattern, and an active matrix substrate was prepared. Subsequently, ITO and an alignment film were formed on the color filter, and the counter substrate was produced. TN liquid crystal is encapsulated between the active matrix substrate and the counter electrode, bonded through a sealing agent, and polarizers are arranged in cross nicols on both sides of each substrate, and a backlight is disposed on the active matrix substrate side to provide a liquid crystal display device. did.

It was confirmed that the liquid crystal display device using the color filter of the present invention exhibits good display characteristics compared with the liquid crystal display device using the color filter of the comparative example.

All publications, patent applications, and technical specifications described in this specification are incorporated herein by reference to the same extent as if the individual documents, patent applications, and technical specifications were incorporated by reference.

Examples of the metal particle dispersion of the present invention include paints, printing inks, inkjet inks, color filters, light shielding image forming compositions, image forming color compositions, black image attachment substrates, liquid crystal displays, and the like. . In particular, high performance is required, and the practically important ones include light-shielding image forming color compositions, solid compositions for coloring or inkjet inks, and color filters for color filters.

Claims (18)

A method for producing a metal particulate dispersion, wherein the metal ions are reduced in the presence of an alkali-soluble polymer having at least one sulfur atom and / or nitrogen atom to form metal fine particles. The method of claim 1, The alkali soluble polymer has an acidic group, characterized in that the production method of the metal particulate dispersion. The method of claim 2, The acidic group of the alkali-soluble polymer is a carboxyl group. The method of claim 1, The organic / inorganic ratio (I / O value) in the organic conceptual diagram of the said alkali-soluble polymer is 0.44 or more and 1.65 or less, The manufacturing method of the metal particulate dispersion characterized by the above-mentioned. The method of claim 1, The metal particulate is a method for producing a metal particulate dispersion, characterized in that it contains one or more metals selected from Groups 2 to 14 of the periodic table. A metal fine particle dispersion comprising an alkali soluble polymer having at least one sulfur atom and / or a nitrogen atom and metal fine particles. The method of claim 6, Metallic particulate dispersion, characterized in that the black. The method of claim 6, The alkali soluble polymer has an acidic group, characterized in that the metal particulate dispersion. The method of claim 8, The acidic group of the alkali-soluble polymer is a metal particulate dispersion, characterized in that the carboxyl group. The method of claim 6, The organic / inorganic ratio (I / O value) in the organic conceptual diagram of the said alkali-soluble polymer is 0.44 or more and 1.65 or less, The metal particulate dispersion characterized by the above-mentioned. The method of claim 6, The metal particulate is a metal particulate dispersion, characterized in that it contains one or two or more metals selected from Groups 2 to 14 of the periodic table. A coloring composition comprising the metal particulate dispersion according to claim 6. The method of claim 12, Coloring composition, characterized in that the black. A photosensitive transfer material having at least one photosensitive light shielding layer formed on a support; The said photosensitive light shielding layer is formed using the metal-particle dispersion of Claim 6. The photosensitive transfer material characterized by the above-mentioned. The light-shielding image attachment substrate which has a light-shielding image formed using the metal fine particle dispersion of Claim 6. The light-shielding image attachment substrate which has a light-shielding image produced using the photosensitive transfer material of Claim 14. It is formed using the metal particle dispersion of Claim 6. The color filter characterized by the above-mentioned. A liquid crystal display device comprising the metal particulate dispersion according to claim 6.