JP4667969B2 - Black composition, photosensitive transfer material, substrate with light-shielding image, color filter, liquid crystal display element, and method for producing light-shielding image - Google Patents

Description

  The present invention relates to a black composition, a photosensitive transfer material using the black composition, a substrate with a light-shielding image on which a light-shielding image is formed with the black composition, a color filter, a liquid crystal display element, and a method for producing a light-shielding image.

Black composition includes printing ink, inkjet ink, etching resist, solder resist, plasma display panel (PDP) partition, dielectric pattern, electrode (conductor circuit) pattern, wiring pattern of electronic parts, conductive paste, conductive film, black Widely used for shading images such as matrix. Examples of the light-shielded image include black edges provided at the periphery of display devices such as liquid crystal display devices, plasma display devices, EL display devices, and CRT display devices, and grids or stripes between red, blue, and green pixels. Various shaded images such as a so-called black matrix, such as a black portion of the shape, and further a dot-like or linear black pattern for shielding the TFT.
The black matrix is used to improve display contrast, and in the case of an active matrix driving type liquid crystal display device using a thin film transistor (TFT), is used to prevent deterioration in image quality due to light current leakage. Property (optical density OD of 3 or more) is required.

  On the other hand, in recent years, liquid crystal display devices have been applied to TVs. However, since TVs have low transmittance and high luminance is obtained using high color purity color filters, the luminance of the backlight is high. The black matrix is required to have a high light-shielding property in order to prevent a decrease in contrast and see-through of the peripheral frame portion.

  Furthermore, since the TV is installed in a room where sunlight is incident for a long period of time, there is a concern about deterioration of the TFT due to sunlight, and (1) a high OD makes the image feel tight, that is, contrast. The black matrix is also required to have high light-shielding properties in the sense that it is high and (2) the white color of the liquid crystal becomes inconspicuous under external light.

  As a method for forming a black matrix using a metal film such as chromium as a light shielding layer, for example, a metal thin film is produced by vapor deposition or sputtering, a photoresist is applied on the metal thin film, and then a black matrix pattern is formed. There is a method of forming a black matrix by exposing and developing a photoresist layer using a photomask having the same, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film (for example, non-patent literature) 1).

  Since this method uses a metal thin film, there is an advantage that a high light shielding effect can be obtained even if the film thickness is small. However, there is a problem that a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required, which increases the cost and cannot be ignored. In addition, since it 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, as the metal thin film, there is a means of using a low-reflective chromium film (such as two layers of metal chromium and chromium oxide), but it cannot be denied that the cost is further increased.

As another black matrix forming method, a method using a light-sensitive pigment, for example, a photosensitive resin composition containing carbon black is also known. As the method, for example, after forming R, G, B pixels on a transparent substrate, a carbon black-containing photosensitive resin composition is applied onto the pixels, and the R, G, B pixel non-formation surface of the transparent substrate is applied. There is known a self-alignment black matrix forming method in which the entire surface is exposed from the side (see, for example, Patent Document 1).
Although this method is lower in manufacturing cost than the method by etching the metal film, there is a problem that the film thickness is increased in order to obtain a sufficient light shielding property. As a result, there is an overlap (step) between the black matrix and the R, G, and B pixels, the flatness of the color filter is deteriorated, and the cell gap unevenness of the liquid crystal display element occurs, leading to display defects such as color unevenness. become.

On the other hand, a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate, and exposed and developed through a photomask having a black matrix pattern to form a relief on the transparent substrate. By contacting with an aqueous solution of a metal compound serving as a catalyst for electroplating, containing the metal compound in the relief, drying, applying heat treatment, and then bringing the relief on the transparent substrate into contact with the electroless plating solution, There has been proposed a method for producing a black matrix in which metal fine particles for light shielding having a diameter of 0.01 to 0.05 μm are uniformly dispersed therein (see, for example, Patent Document 2). Nickel, cobalt, iron, copper, and chromium are described as the metal fine particles, and nickel is shown as a specific example.
However, this method has many troublesome processing steps for handling water, such as relief formation including exposure and development steps, application of an electroless plating catalyst, heat treatment, and electroless plating. Therefore, it cannot be expected to produce a black matrix at a low cost.

  In addition, there is an example in which a magnetic filler is used in a colored composition for producing a black pattern (see, for example, Patent Document 3). However, these examples are thick films of 10 microns or more and have a low concentration per unit film thickness. Therefore, it is impossible to produce a light-shielded image with a thin film and high light-shielding performance at low cost.

In addition, there is an example in which metal fine particles having an aspect ratio of 2 or more are used as a coloring composition for producing a black pattern (see, for example, Patent Document 4), but the prepared black color filter has low heat resistance and color tone. There was a problem of change and density reduction. Therefore, it cannot be said to be sufficient as a black matrix substrate.
JP-A-62-9301 Japanese Patent No. 3318353 JP 2001-13678 A JP 2005-17322 A Published by Kyoritsu Shuppan Co., Ltd. “Color TFT LCD”, pp. 218-220 (April 10, 1997)

  The present invention has been made in view of the problems as described above, and its purpose is to provide a black composition having high heat resistance and effectively suppressing color change and density reduction, and the black composition. It is to provide a photosensitive transfer material used. Further, a method for producing a light-shielded image having high heat resistance and capable of effectively suppressing color change and density reduction, a substrate with a light-shielded image provided with the light-shielded image, and using the substrate The object is to provide a color filter and a liquid crystal display element.

The said subject is solved by the following means. That is, the present invention
<1> A black composition comprising black rod-shaped metal fine particles, at least one of a resin or a precursor thereof, a monomer and an initiator. The metal particles include metals, metal compounds, are formed from one of the composite fine particles of the metal compound and a metal, the elemental silver or Kanemoto element.
<2> The black composition according to <1>, wherein the metal fine particles are silver fine particles, gold fine particles, fine particles having a silver sulfide shell in the core of silver fine particles, or silver tin alloy fine particles. .

<3> long axis length of the rod-shaped metal fine particles (L), said that satisfies the width (b) and thickness (t) of the following conditions (1) to (3) <1> or The black composition as described in <2> .
(1) The major axis length (L) is 10 nm or more and 1000 nm or less.
(2) Long axis length (L)> Width (b) ≧ Thickness (t)
(3) The ratio (b / t) of the width (b) to the thickness (t) is 2.0 or less.

< 4 > The particle size distribution of the rod-shaped metal fine particles is 1.2 or more and less than 20 in the particle size distribution width (D90 / D10) of the number average particle diameter obtained by approximating the particle distribution to a normal distribution. The black composition according to any one of <1> to <3> .

  <5> The black composition according to any one of <1> to <4>, further including a pigment.

  <6> The black composition according to <5>, wherein the pigment is at least one selected from carbon black, titanium black, and graphite.

< 7 > The black composition according to any one of <1> to < 6 >, wherein the black composition is used for production of a light-shielding image.

< 8 > A photosensitive transfer material having at least a photosensitive light-shielding layer provided on a support, wherein the photosensitive light-shielding layer is formed of the black composition described in < 7 >. Transfer material.

< 9 > A light-shielding image-attached substrate comprising a light-shielding image produced using the black composition according to < 7 >.

< 10 > A substrate with a light-shielding image, comprising a light-shielded image produced using the photosensitive transfer material according to < 8 >.

< 11 > A color filter comprising a colored layer on a light-transmitting substrate and having two or more pixel groups exhibiting different colors, each pixel constituting the pixel group being separated from each other by a light-shielding image In the color filter, the light-shielded image is produced using the black composition described in < 7 > or the photosensitive transfer material described in < 8 >.

< 12 > In a liquid crystal display device comprising at least one of a pair of light-transmitting substrates and at least one of a color filter, a liquid crystal layer, and a liquid crystal driving means, the color filter is the color filter according to < 11 > It is a liquid crystal display element characterized by being.

< 13 > A step of forming a light-shielding layer on the light-transmitting substrate using the black composition according to the above < 7 >, and a step of exposing and developing the light-shielding layer. It is a manufacturing method of a shading image.

< 14 > The photosensitive transfer material according to < 8 >, wherein at least a photosensitive light-shielding layer is provided on a support, and the photosensitive transfer layer is in contact with the photosensitive light-shielding layer on a light-transmitting substrate. A step of laminating a material, a step of peeling the support from a laminate of the photosensitive transfer material and a light transmissive substrate, and a step of exposing and developing the photosensitive light-shielding layer. This is a method for producing a light-shielded image.

  ADVANTAGE OF THE INVENTION According to this invention, while having high heat resistance, the black composition which suppressed the color change and the density | concentration fall effectively, and the photosensitive transfer material using this black composition can be provided. A method for producing a light-shielded image capable of obtaining a light-shielded image having heat resistance and effectively suppressing color change and density reduction, a substrate with a light-shielded image provided with the light-shielded image, a color filter using the substrate, In addition, a liquid crystal display element can be provided.

Black composition of the present invention includes a rod-shaped metal fine particles of black, and at least one resin or its precursor, characterized in that it comprises a monomer and initiator, and also optionally, pigment particles, and a binder comprising polymer may contain solvent like.

  The black composition includes printing ink, inkjet ink, photomask preparation material, printing proof preparation material, etching resist, solder resist, plasma display panel (PDP) partition, dielectric pattern, electrode (conductor circuit) pattern, It can be used for light-shielded images such as wiring patterns of electronic parts, conductive paste, conductive film, black matrix, and the like. Preferably, in order to improve the display characteristics of a color filter used in a color liquid crystal display device or the like, it can be suitably used to provide a light-shielded image on the spacing portion of the colored pattern, the peripheral portion, the outside light side of the TFT, and the like. Particularly preferably, a black edge provided at the 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 grid or stripe between red, blue, and green pixels. The black portion is more preferably used as a black matrix such as a dot-like or linear black pattern for shielding a TFT.

≪Black composition≫
Hereinafter, in describing the present invention in detail, first, the black composition will be described in detail.
<Bar-shaped metal fine particles>
In the present invention, that the metal fine particles are “bar-shaped” means that when the particles are regarded as a rectangular parallelepiped having the X axis, the Y axis, and the Z axis by the following method, an elongated bar shape is formed. . That is, when it is regarded as a cuboid with a triaxial diameter, it means to exclude particles that are flat and particles that are regular side bodies (for example, particles having a shape of a true sphere, a cube, etc.).
Specifically, the shape of the particles themselves, for example, particles such as needles, cylinders, rectangular prisms such as cuboids, rugby balls, fibers, coils, etc., are mentioned as rod-shaped metal fine particles in the present invention, Among these, particles having a needle shape, a cylindrical shape, a rectangular column shape such as a rectangular parallelepiped, or a rugby ball shape are more preferable.

(Triaxial diameter)
The metal fine particles in the present invention are captured as a rectangular solid by the following method, and each dimension is measured. In other words, a rectangular parallelepiped box with a single metal fine particle that fits exactly (tightly) is considered, and the longest length of this box is defined as the long axis length L, with thickness t and width b. This is defined as the size of the metal fine particles. The dimension has a relationship of L> b ≧ t, and the larger of b and t is defined as the width b unless otherwise the same.
Specifically, first, a metal fine particle is placed on a flat surface so that the center of gravity is the lowest and stably remains. Next, the metal fine particles are sandwiched between two parallel flat plates standing at right angles to the plane, and the flat plate interval at the position where the flat plate interval is the shortest is provided. Next, metal fine particles are sandwiched between two parallel flat plates that are perpendicular to the two flat plates that determine the flat plate interval and are also perpendicular to the flat surface, and the distance between the two flat plates is maintained. Finally, the top plate is placed parallel to the plane so as to come into contact with the highest position of the metal fine particles. By this method, a rectangular parallelepiped defined by a plane, two pairs of flat plates and a top plate is formed.
In addition, a coil shape or a loop shape is defined as a value when the measurement is performed in a state where the shape is extended.

(Long axis length L)
The major axis length L of the rod-shaped metal fine particles is preferably 10 nm to 1000 nm, more preferably 10 nm to 800 nm, and most preferably 20 nm to 400 nm (shorter than the wavelength of visible light). When it is 10 nm or more, there are advantages that preparation is easy in production and heat resistance and color are good, and when it is 1000 nm or less, there are advantages that there are few planar defects.

(Ratio of width b to thickness t)
In the present invention, the “ratio between the width b and the thickness t” of the rod-shaped metal fine particles is defined as an average value of values measured for 100 rod-shaped metal fine particles. The ratio (b / t) between the width b and the thickness t of the rod-like fine metal particles is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.3 or less. If the b / t ratio exceeds 2.0, it may be nearly flat and heat resistance may be reduced.

(Relationship between major axis length L, width b, and thickness t)
The major axis length L is preferably 1.2 to 100 times the width b, more preferably 1.3 to 50 times, and more preferably 1.4 to 20 times. Is particularly preferred. When the major axis length L is less than 1.2 times the width b, the characteristics of a flat plate are produced, and the heat resistance may be deteriorated. On the other hand, if the long axis length L exceeds 100 times the width b, the black density may become low and the high density of the thin layer may not be achieved.

  (Measurement of length L, width b, and thickness t)

The length L, width b, and thickness t can be measured with an electron microscope surface observation (× 500000) and an atomic force microscope (AFM), and the average of the values measured for 100 rod-shaped metal fine particles. Value.
The atomic force microscope (AFM) has several operation modes, which are properly used depending on the application. Broadly divided into the following three.
(1) Contact system A system in which a probe is brought into contact with the sample surface and the surface shape is measured from the displacement of the cantilever.
(2) Tapping method A method in which a probe is periodically brought into contact with the sample surface and the surface shape is measured from a change in vibration amplitude of the cantilever.
(3) Non-contact method A method for measuring the surface shape from the change in the vibration frequency of the cantilever without bringing the probe into contact with the sample surface.
On the other hand, the non-contact method needs to detect extremely weak attractive force with high sensitivity. For this reason, it is difficult to detect static force by directly measuring the displacement of the cantilever, and the mechanical resonance of the cantilever is applied.
The above three methods can be mentioned, and any method can be taken according to the sample.

  In the present invention, the electron microscope JEM2010 manufactured by JEOL Ltd. was used as the electron microscope, and measurement was performed at an acceleration voltage of 200 kV. Moreover, the atomic force microscope (AFM) used SPA-400 by Seiko Instruments Inc. In the measurement with the atomic force microscope (AFM), the measurement is facilitated by adding polystyrene beads for comparison.

(Bar metal fine metal)
The metal in the rod-shaped metal fine particles used in the present invention, is used as the silver-containing or Kanemoto element. The metal fine particles may be used in combination of two or more metals, and may be used as an alloy. Specifically, it is formed from any one of metal, a metal compound, and composite fine particles of a metal compound and a metal.
As the rod-shaped metal fine particles, those formed from a metal and / or a metal compound are preferable, and those formed from a metal are particularly preferable.
In particular, in the present invention, a metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long period periodic table (IUPAC 1991) is preferably included as a main component. Moreover, it is preferable to contain the metal chosen from the group which consists of 2-14 groups, 2nd group, 8th group, 9th group, 10th group, 11th group, 12th group, 13th group, and More preferably, a metal selected from the group consisting of Group 14 is included as a main component. Among these metals, the metal fine particles in the present invention are metals of the fourth period, the fifth period, or the sixth period, and are Group 2, Group 10, Group 11, Group 12, or Group 14. Group metals are more preferred, with calcium, gold, silver, copper, platinum, tin or palladium being particularly preferred. Of these, gold, silver, copper, and tin are preferable. However, the requirement to include the street elemental silver or Kanemoto elements of, particularly silver are preferred, and most preferably colloidal silver as silver.

Preferred examples of dispersing metal fine particles as the metal fine particles, for example, silver, gold, or these with copper, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, Examples thereof include at least one selected from niobium, tantalum, titanium, bismuth, antimony, and an alloy with lead. Further preferred metals are silver, gold, or these with copper, platinum, palladium, nickel, tin, cobalt, rhodium, an alloy of iridium, more preferred metals are silver, gold, or with these copper, platinum, tin And at least one selected from alloys thereof.

(Metal compound)
The “metal compound” referred to in the present invention is a compound of a metal and an element other than the metal as described above.
Examples of compounds of metals and other elements include metal oxides, sulfides, sulfates, and carbonates. Of these, sulfide is particularly preferred from the viewpoint of color tone and ease of fine particle formation. Examples of these metal compounds include copper oxide (II), iron sulfide, silver sulfide, copper sulfide (II), and titanium black. Silver sulfide is particularly preferable from the viewpoints of color tone, ease of fine particle formation, and stability. .

(Composite fine particles)
The composite fine particles of a metal compound and a metal referred to in the present invention are those in which a metal and a metal compound are combined to form one particle. For example, those having different compositions between the inside and the surface of the particles, and those obtained by combining two kinds of particles can be exemplified. Moreover, 1 type or 2 types or more may be sufficient as a metal compound and a metal, respectively. Specific examples of the composite fine particles of the metal compound and metal include composite fine particles of silver and silver sulfide, and composite fine particles of silver and copper (II) oxide.

(Core shell)
Further, the rod-shaped metal fine particles of the present invention may be core / shell type composite particles. The core-shell type composite particles are obtained by coating the surface of a core material with a shell material. Examples of the shell material of the present invention used for the core-shell type composite particles include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe. , Se, Te, CuCl, CuBr, CuI, TlCl, TlBr, TlI, at least one semiconductor selected from these solid solutions or solid solutions containing 90 mol% or more of these, or copper, silver, gold, platinum, palladium, And at least one metal selected from nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or alloys thereof. .
Preferable core materials include at least one selected from copper, silver, gold, palladium, nickel, tin, bismuth, ammotine, lead, or alloys thereof.
The shell material is also preferably used as a refractive index adjusting agent for the purpose of reducing the reflectance.

  There are no particular limitations on the method for producing the composite fine particles having a core-shell structure, and typical methods include the following.

(1) A method of forming a metal compound shell on the surface of metal fine particles produced by a known method by oxidation, sulfurization, etc. For example, metal fine particles are dispersed in a dispersion medium such as water, and sodium sulfide or There is a method of adding a sulfide such as ammonium sulfide. By this method, the surface of the particles is sulfided to form core-shell composite particles.
In this case, the metal fine particles to be used can be produced by a known method such as a gas phase method or a liquid phase method. The method for producing metal fine particles is described in, for example, “Latest Trend II in Technology and Application of Ultrafine Particles II (issued by Sumibe Techno Research Co., Ltd. 2002)”.

(2) A method of continuously forming a metal compound shell on the surface in the process of producing metal fine particles. For example, a reducing agent is added to a metal salt solution to reduce a part of metal ions to form metal fine particles. And then adding a sulfide to form a metal sulfide around the produced metal fine particles.

(Preparation of rod-shaped fine metal particles)
As the metal fine particles, commercially available ones can be used, and they can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
In particular, for rod-shaped silver fine particles, spherical silver fine particles are used as seed particles, and then a silver salt is further added. In the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide), a reducing agent such as ascorbic acid having a relatively low reducing power is added. It is described in Advanced Materials 2002, 14, 80-82 that a silver bar and a wire can be obtained by using. Similar descriptions are made in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189. As a method using electrolysis, Materials Letters 2001, 49, 91-95 and a method of generating a silver bar by irradiating microwaves are described in Journal of Materials Research 2004, 19, 469-473. Journal of Physical Chemistry B 2003, 107, 3679-3683 is an example in which reverse micelles and ultrasonic waves are used in combination.
As for gold, it is also described in Journal of Physical Chemistry B 1999, 103, 3073-3077 and Langmuir 1999, 15, 701-709, Journal of American Chemical Society 2002, 124, 14316-143.
The method for forming the rod-like particles can be prepared by improving the above-described method (adjustment of addition amount, pH control).

The metal fine particles in the present invention can also be obtained by combining various types of rod-like particles in order to approximate an achromatic color.
By changing the particles from a spherical shape or a cubic shape to a rod shape, a higher transmission density can be obtained, which makes it possible to reduce the thickness of the light shielding layer.

(Particle size distribution)
The particle size distribution of the rod-shaped metal fine particles in the present invention is preferably such that the particle distribution approximates a normal distribution, and the particle size distribution width D90 / D10 of the number average particle diameter is 1.2 or more and less than 20. Here, the particle diameter is the major axis length L as the particle diameter, D90 is the particle diameter at which 90% of the particles close to the average particle diameter are found, and D10 is 10% of the particles close to the average particle diameter. Is the particle diameter at which is found. The particle size distribution width is more preferably 2 or more and 15 or less from the viewpoint of color tone. More preferably, it is 4 or more and 10 or less. If the distribution width is less than 1.2, the color tone may be close to a single color, and if it is 20 or more, turbidity may occur due to scattering by coarse particles.

  In addition, the measurement of the particle size distribution width D90 / D10 is specifically performed by measuring 100 metal fine particles in the coating film at random by the above-described method of measuring the triaxial diameter, and the long axis length L Is the particle diameter, the particle size distribution is a normal distribution approximation, the particle diameter that is in the range of 90% by the number of particles close to the average particle diameter is D90, and the particle diameter that is in the range of 10% from the average particle diameter is As D10, D90 / D10 can be calculated.

(Dispersion of rod-shaped fine metal particles)
The rod-shaped metal fine particles in the present invention are desirably dispersed in the black composition. The state of presence of the rod-shaped metal fine particles during dispersion is not particularly limited, but the rod-shaped metal fine particles are preferably present in a stable dispersed state, for example, more preferably in a colloidal state. In the case of a colloidal state, for example, it is preferable that rod-like metal fine particles are dispersed in a substantially rod-like fine particle state.
Here, as the dispersant, a thiol group-containing compound, an amino acid or a derivative thereof, a peptide compound, a polysaccharide, a natural polymer derived from a polysaccharide, a synthetic polymer, a gel derived therefrom, or the like can be used.
The kind of the thiol group-containing compound used here is not particularly limited and may be any compound as long as it has one or more thiol groups. Examples of the thiol group-containing compound include alkyl thiols (eg, methyl mercaptan, ethyl mercaptan, etc.), aryl thiols (eg, thiophenol, thionaphthol, benzyl mercaptan, etc.), amino acids or derivatives thereof (eg, cysteine, glutathione). Etc.), peptide compounds (eg, dipeptide compounds containing cysteine residues, tripeptide compounds, tetrapeptide compounds, oligopeptide compounds containing 5 or more amino acid residues), or proteins (eg, metallothionein or cysteine residues) And the like, but are not limited thereto.

  Polymers used in the dispersant include protective colloidal polymers such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropyl cellulose, polyalkyleneamine, polyacrylic acid partial alkyl esters, polyvinylpyrrolidone (PVP), and polyvinylpyrrolidone. There are copolymers. The polymer that can be used as the dispersant is described in, for example, “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000).

  In addition, a hydrophilic polymer, a surfactant, a preservative, a stabilizer, or the like may be appropriately added to the dispersion. As the hydrophilic polymer, any polymer may be used as long as it can be dissolved in water and can substantially maintain a solution state in a diluted state. For example, proteins and protein-derived substances such as gelatin, collagen, casein, fibronectin, laminin, and elastin; derived from polysaccharides and polysaccharides such as cellulose, starch, agarose, carrageenan, dextran, dextrin, chitin, chitosan, pectin, mannan Natural polymers such as substances; synthetic polymers such as poval (polyvinyl alcohol), polyacrylamide, polyvinyl pyrrolidone polyacrylate, polyethylene glycol, polystyrene sulfonic acid, polyallylamine; or gels derived therefrom can be used. When gelatin is used, the type of gelatin is not particularly limited, and examples thereof include beef bone alkali-treated gelatin, pig skin alkali-treated gelatin, beef bone acid-treated gelatin, beef bone phthalated gelatin, and pig skin acid-treated gelatin. Can be used.

  As the surfactant, any of anionic, cationic, nonionic, and betaine surfactants can be used, and anionic and nonionic surfactants are particularly preferable. The HLB value of the surfactant cannot be generally specified depending on whether the solvent of the coating solution is aqueous or organic solvent, but is preferably about 8 to 18 when the solvent is aqueous, and about 3 to 6 when the solvent is organic. Are preferred.

  The HLB value is described in, for example, “Surfactant Handbook” (Tokiyuki Yoshida, Shinichi Shindo, Yoshiyoshi Yamanaka, published in Engineering Book Co., Ltd. 1987). Specific examples of the surfactant include propylene glycol monostearate, propylene glycol monolaurate, diethylene glycol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, and the like. Examples of the surfactant are also described in the aforementioned “Surfactant Handbook”.

<Resin or its precursor>
Examples of the resin contained in the black composition of the present invention include polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer as described in JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048 And crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 is also available. Can be mentioned.

It is preferable to select and use the resin having an acid value in the range of 30 to 400 mgKOH / g and a weight average molecular weight in the range of 1000 to 300,000. In addition to the above, in order to improve various performances, for example, the strength of the cured film, an alkali-soluble polymer may be added within a range that does not adversely affect developability and the like. Examples of these alkali-soluble binder polymers include alcohol-soluble nylon and epoxy resin.
Examples of the resin precursor include a monomer that becomes a resin by curing. These will be described later.

<Pigment>
In addition to rod-shaped metal fine particles, the black composition of the present invention can contain pigment fine particles to make the hue close to black.
Suitable examples of the pigment to be included in the black composition of the present invention include carbon black, titanium black, and graphite.
As an example of the carbon black, Pigment Black 7 (carbon black CI No. 77266) is preferable. Commercially available products include Mitsubishi Carbon Black MA100 (Mitsubishi Chemical Corporation) and Mitsubishi Carbon Black # 5 (Mitsubishi Chemical Corporation).

As an example of the titanium black, TiO ₂ , TiO, TiN and a mixture thereof are preferable. As commercial products, trade names: 12S and 13M manufactured by Mitsubishi Materials Corporation are listed. The particle size of titanium black used is preferably 40 to 100 nm.

  As an example of the graphite, those having a particle diameter of 3 μm or less as the Stokes diameter are preferable. Use of graphite exceeding 3 μm is not preferable because the contour shape of the light shielding pattern becomes non-uniform and sharpness deteriorates. Further, most of the particle diameter is desirably 0.1 μm or less.

  In addition to the pigment, a known pigment can also be used. In general, the pigment is roughly classified into an organic pigment and an inorganic pigment. In the present invention, the organic pigment is preferable. Examples of pigments that can be suitably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The hue of the organic pigment is preferably, for example, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, or a black pigment. The pigments (colorants) used in the black composition are listed below, but are not limited thereto.

  Specific examples of the colorant used in the present invention include the coloring materials described in JP 2005-17716 A [0038] to [0040] and JP 2005-361447 A [0068] to [0072]. The pigment described in JP-A-2005-17521 and the colorants described in [0080] to [0088] can be suitably used.

  In addition to the above-mentioned colorants, refer to those described in “Handbook of Pigments, Japan Pigment Technical Association, Seibundo Shinkosha, 1989”, “COLOUR INDEX, THE SOCIETY OF DYES & COLORIST, THIRD EDITION, 1987”. Can be used as appropriate.

  It is desirable to use a pigment that has a complementary color relationship with the hue of the rod-like metal fine particles. Further, the pigments may be used alone or in combination of two or more. Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. And combinations of blue, violet and black pigments.

  The pigment is preferably uniformly dispersed in the black composition. The average particle size of the pigment is preferably 5 nm to 5 μm, particularly preferably 10 nm to 1 μm, and more preferably 20 nm to 0.5 μm for color filters.

<Black composition for shading image preparation>
The case where the black composition is used as a black composition for preparing a light-shielding image (hereinafter also referred to as “black composition for light shielding”) will be described in detail below.
When the light shielding layer (layer before patterning) is formed using the black composition for light shielding of the present invention, the optical density per 1 μm of the thickness of the light shielding layer is preferably 1 or more. For example, in consideration of preventing metal fine particles from fusing during post-baking, such as when producing a color filter, the content of rod-shaped metal fine particles in the light-shielding black composition is determined in the light-shielding layer to be formed. It is preferable to adjust so that it may become 10-90 mass%, Preferably it is about 10-80 mass%. The content is preferably determined in consideration of the variation in optical density due to the average particle diameter of the rod-like metal fine particles.
The same applies to the content of rod-shaped metal fine particles in the black composition for light shielding having a photosensitivity described later.

The “light-shielded image” referred to in the present invention is used to include a black matrix. “Black matrix” means a black edge provided around the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or a grid between red, blue and green pixels. And striped black parts, and dot-like and linear black patterns for TFT shading, etc. The definition of this black matrix is, for example, written by Taihei Kanno, “Liquid Crystal Display Equipment Dictionary”, 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64. Examples of the light-shielded 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 PALC for light shielding of a backlight.
The black matrix improves display contrast, and in the case of an active matrix drive type liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, it has high light shielding properties (optical density OD). 3 or more) is required.

<Black composition for photosensitive shading image preparation>
More preferably, the black composition for producing a light-shielding image has photosensitivity. Specifically, photosensitivity can be imparted by adding a photosensitive resin composition. The photosensitive resin composition has a polymer that serves as a binder, a photopolymerization initiator, and a monomer that has an ethylenically unsaturated double bond and undergoes addition polymerization upon irradiation with light (hereinafter sometimes referred to as “photopolymerizable monomer”). ) And the like are preferred.

The photosensitive resin composition includes those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent. From the viewpoint of safety and the cost of the developer, those capable of developing with an aqueous alkali solution are preferred. For this purpose, the binder polymer is preferably an alkali-soluble polymer.
The photosensitive resin composition may be a negative type in which a portion that receives radiation such as light or electron beam as described above is cured, or a positive type in which a radiation non-receptive portion is cured.

  Examples of the positive photosensitive resin composition include those using a novolac resin. For example, an alkali-soluble novolak resin system described in JP-A-7-43899 can be used. Further, a positive photosensitive resin layer described in JP-A-6-148888, that is, an alkali-soluble resin described in the publication and a 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitive agent and a thermosetting agent described in the publication. A photosensitive resin layer containing a mixture can be used. Furthermore, the composition described in JP-A-5-262850 can also be used.

Examples of the negative photosensitive resin composition include a photosensitive resin composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Is mentioned. Among them, particularly preferred is a photopolymerizable composition containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. As the photopolymerizable composition, “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” described in JP-A No. 11-133600, and other compositions can be used.
For example, as a photosensitive resin composition that can be developed in an aqueous alkali solution with a negative photosensitive resin composition, a carboxylic acid group-containing binder (alkali-soluble binder) as a main component, a photopolymerization initiator, a photopolymerizable monomer, The photosensitive resin composition which contains this is mentioned. As the alkali-soluble binder, the resins mentioned in the above <Resin or its precursor> can be preferably used.

  The alkali-soluble binder polymer is usually contained in an amount of 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content of the photosensitive black composition for producing a light-shielding image. In the range of 10 to 95% by mass, the adhesiveness of the photosensitive resin layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.

Examples of the photopolymerization initiator include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512. Aromatic acyloin compounds substituted with α-hydrocarbons described in the specification, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, tria described in US Pat. No. 3,549,367 A combination of a reel imidazole dimer and a p-aminoketone, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, and a trihalomethyl-s described in US Pat. No. 4,239,850 -Triazine compounds, U.S. Pat. No. 4,221,976 Trihalomethyl oxadiazole compounds, and the like that are described in. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or in combination of two or more, and it is particularly preferable to use two or more. Moreover, 0.5-20 mass% is common and, as for content of the photoinitiator with respect to the total solid of the photosensitive resin composition, 1-15 mass% is preferable.

Examples of good display characteristics that are free from yellowing and can improve exposure sensitivity include a combination of a diazole photopolymerization initiator and a triazine photopolymerization initiator. Methyl 5- (p-styrylstyryl) -1,3,4-oxadiazole and 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) -3 The combination of '-bromophenyl] -s-triazine is the best.
The ratio of these photopolymerization initiators is a diazole / triazine mass ratio, preferably 95/5 to 20/80, more preferably 90/10 to 30/70, most preferably 80/20 to 60 /. 40. These photopolymerization initiators are described in JP-A-1-152449, JP-A-1-254918, and JP-A-2-153353.
Furthermore, a benzophenone series is also mentioned as a suitable example.

When the ratio of the pigment to the total solid content of the photosensitive black composition for producing a light-shielding image is about 15 to 25% by mass, the photopolymerization initiator can be mixed with a coumarin-based compound to color yellowing or the like. And high sensitivity can be achieved. As the coumarin compound, 7- [2- [4- (3-hydroxymethylbiperidino) -6-diethylamino] triazinylamino] -3-phenylcoumarin is the best. The ratio of these photopolymerization initiator and coumarin compound is the mass ratio of photopolymerization initiator / coumarin compound, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, most preferably. Is 40/60 to 60/40.
However, the photopolymerizable composition that can be used in the present invention is not limited to these, and can be appropriately selected from known ones.

  The photopolymerization initiator is generally 0.5 to 20% by mass, preferably 1 to 15% by mass, based on the total solid content of the photosensitive black composition for producing a light-shielding image. When the content is within the above range, a decrease in photosensitivity and image intensity can be prevented, and the performance can be sufficiently improved.

  Examples of the photopolymerizable monomer include compounds having a boiling point of 100 ° C. or higher at normal pressure. For example, monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tri Methylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Ethylene oxide and propylene oxide to polyfunctional alcohols such as dimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin And polyfunctional (meth) acrylates such as those obtained by addition reaction of (meth) acrylate.

  Further, urethane acrylates disclosed in JP-B-48-41708, JP-A-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, are disclosed in each publication of No. 52-30490. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable. The photopolymerizable monomers may be used alone or in combination of two or more. The content of the photopolymerizable monomer with respect to the total solid content of the photosensitive black composition for preparing a light-shielding image is generally 5 to 50% by mass, and preferably 10 to 40% by mass. When the content is within the above range, the light sensitivity and the image strength are not lowered, and the adhesiveness of the photosensitive light-shielding layer is not excessive.

  As the photosensitive resin composition, it is preferable to add a thermal polymerization inhibitor in addition to the above components. Examples of the thermal polymerization inhibitor include aromatic hydroxy such as hydroquinone, p-methoxyphenol, pt-butylcatechol, 2,6-di-t-butyl-p-cresol, β-naphthol, pyrogallol and the like. Compounds, quinones such as benzoquinone and p-toluquinone, amines such as naphthylamine, pyridine, p-toluidine and phenothiazine, aluminum salt or ammonium salt of N-nitrosophenylhydroxylamine, chloranil, nitrobenzene, 4,4′-thiobis ( 3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like.

  As the photosensitive resin composition, further known additives as necessary, for example, plasticizers, surfactants, adhesion promoters, dispersants, anti-sagging agents, leveling agents, antifoaming agents, flame retardants, Brighteners, solvents and the like can be added.

  Examples of the adhesion promoter include alkylphenol / formaldehyde novolak resin, polyvinyl ethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene, styrene-butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, chlorinated rubber, Acrylic resin adhesives, aromatic, aliphatic or alicyclic petroleum resins, silane coupling agents and the like can be mentioned.

  Further, when the rod-shaped metal fine particles in the present invention are used as an aqueous dispersion like silver colloid, it is necessary to use an aqueous one as the photosensitive resin composition. Examples of such a photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and commercially available products such as “SPP-” manufactured by Toyo Gosei Kogyo Co., Ltd. M20 "and the like.

  By forming the black matrix using the black composition for preparing a light-shielding image (including a photosensitive material) of the present invention, a black matrix having a thin film and a high optical density can be prepared.

≪Photosensitive transfer material for shading image preparation≫
In the present invention, a light-sensitive image-forming photosensitive transfer material can be prepared using the photosensitive black composition for preparing a light-shielded image, and a light-shielded image such as a black matrix can be produced using the photosensitive transfer material. .
The photosensitive transfer material is provided with a photosensitive light-shielding layer formed using a black composition for producing a light-shielding image having at least the above-described photosensitivity on a support, and a thermoplastic resin layer as necessary. An intermediate layer, a protective layer, or the like can be provided.
The 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, and more preferably 0.2 to 1.0 μm.

<Support>
As the support in the photosensitive transfer material, a known support such as polyester or polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability. The thickness of the support is preferably about 15 to 200 μm, more preferably about 30 to 150 μm. When the thickness of the support is within the above range, it is possible to effectively suppress the occurrence of a wrinkle of a tin plate due to heat during the lamination process, which is advantageous in terms of cost.
Moreover, you may provide the electroconductive layer described in Unexamined-Japanese-Patent No. 11-149008 in the said support body as needed.

<Thermoplastic resin layer>
Moreover, it is preferable to provide an alkali-soluble thermoplastic resin layer between the support and the photosensitive light-shielding layer or between the support and the intermediate layer.
The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness on the base surface (including unevenness due to an image already formed, etc.). It preferably has a property that can be deformed.

  Examples of the resin contained in the alkali-soluble thermoplastic resin layer include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth). Saponified product such as saponified product with acrylic ester copolymer, poly (meth) acrylic acid ester, and (meth) acrylic acid ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. It is preferable that there is at least one. In addition, use organic polymers soluble in alkaline aqueous solutions from the "Plastic Performance Handbook" (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968). You can also. Of these thermoplastic resins, those having a softening point of 80 ° C. or less are preferable. In the present specification, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.

  Among the resins contained in the alkali-soluble thermoplastic resin layer, it is preferable to select and use a resin having a weight average molecular weight of 3,000 to 500,000 (Tg = 0 to 170 ° C.), and further a weight average molecular weight of 4 The range of 1,000 to 200,000 (Tg = 30 to 140 ° C.) is more preferable. Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-44615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP 60-159743, JP 60-247638, JP 60-208748, JP 60-214354, JP 60-230135, JP 60-258539, JP JP 61-1669829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP 64- No. 5551, JP-A 64-55550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-5-241340 Examples thereof include resins that are soluble in an alkaline aqueous solution.

  Of these, methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159, JP-B-55-38961, Examples thereof include styrene / (meth) acrylic acid copolymers described in each publication of No. 5-241340.

  The thermoplastic resin layer includes various plasticizers, various polymers, supercooling substances, adhesion improvers, surfactants, or release agents in order to adjust the adhesive force between the thermoplastic resin layer and the support. Etc. can be added. 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, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono ( Addition reaction product with (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of rate, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate. The amount of the plasticizer in the thermoplastic resin layer is generally 200% by mass or less, preferably 20 to 100% by mass with respect to the thermoplastic resin.

  Further, the thickness of the alkali-soluble thermoplastic resin layer is preferably 6 μm or more. If the thickness of the thermoplastic resin is 6 μm or more, irregularities on the base surface can be completely absorbed. Further, the upper limit is generally about 100 μm or less, preferably about 50 μm or less, from the viewpoint of developability and production suitability.

  In the present invention, the solvent of the coating solution used when forming the thermoplastic resin layer can be used without particular limitation as long as it dissolves the resin constituting this layer. Examples of the solvent include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.

(Middle layer)
In the photosensitive transfer material of the present invention, an intermediate layer may be provided between the temporary support and the photosensitive light-shielding layer.
The resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble. Examples of the resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. . A resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is not usually alkali-soluble, such as polyester, can also be used.
Of these, polyvinyl alcohol is preferred. The polyvinyl alcohol preferably has a saponification degree of 80% or more, more preferably 83 to 98%.

It is preferable to use a mixture of two or more resins constituting the intermediate layer, and it is particularly preferable to use a mixture of polyvinyl alcohol and polyvinyl pyrrolidone. The mass ratio between the two is preferably polyvinyl pyrrolidone / polyvinyl alcohol = 1/99 to 75/25, more preferably 10/90 to 50/50. When the mass ratio is within the above range, the surface shape of the intermediate layer is good, the adhesiveness with the photosensitive light-shielding layer coated thereon is good, and further, the oxygen barrier property is lowered and the sensitivity is lowered. Can be prevented.
In addition, an additive such as a surfactant can be added to the intermediate layer as necessary.

The thickness of the intermediate layer is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, it is possible to prevent an increase in the intermediate layer removal time during development without decreasing the oxygen barrier property.
The coating solvent for the intermediate layer is not particularly limited as long as the resin is dissolved, but water is particularly preferable, and a mixed solvent obtained by mixing the water-miscible organic solvent with water is also preferable. Specific examples of preferable coating solvents include, for example, water, water / methanol = 90/10, water / methanol = 70/30, water / methanol = 55/45, water / ethanol = 70/30, water / 1-propanol. = 70/30, water / acetone = 90/10, water / methyl ethyl ketone = 95/5 (where the ratio represents a mass ratio) and the like.

<Production of photosensitive transfer material>
In order to produce the photosensitive transfer material of the present invention, the support is prepared by applying, for example, a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, It can form by apply | coating and drying using coating machines, such as a wire bar coater and an extruder. In the case of providing an alkali-soluble thermoplastic resin layer, it can be formed in the same manner.

  Since the photosensitive transfer material of the present invention is provided with a photosensitive light-shielding layer using the black composition for light-shielding image preparation of the present invention as described above, a light-shielding layer having a thin film and a high optical density can be produced. .

≪Method for producing shading image≫
In the present invention, the light-shielding image is produced by patterning a light-shielding layer formed using the black composition or the photosensitive transfer material, and the film thickness of the light-shielding layer is about 0.2 to 2.0 μm. It is preferably 0.9 μm or less. Since the light shielding layer in the present invention is a dispersion of rod-shaped metal fine particles, a sufficient optical density (3.5 or more) can be exhibited even with a thin film as described above.

  Moreover, the method for producing (patterning) a light-shielded image using the black composition for producing a light-shielded image of the present invention is not particularly limited. An example of a black matrix pattern forming method is given below.

  In the first method, first, rod-shaped metal fine particles and resin or at least one of its precursors are contained, and the black composition for producing a light-shielding image of the present invention having photosensitivity is applied to a substrate, and rod-shaped metal fine particles are contained. A photosensitive light-shielding layer is formed. Thereafter, a light shielding image is obtained by forming a pattern by removing the light shielding layer in portions other than the pattern by exposure and development. Further, a protective layer can be formed by forming a layer having the same composition as the above-described intermediate layer on the photosensitive light-shielding layer. In this case, the coating solution can be applied by using the coating machine described in <Preparation of photosensitive transfer material>, but it is preferable to perform the coating by a spin coating method.

  In the second method, first, rod-shaped metal particles containing rod-shaped metal fine particles and a resin or a precursor thereof are coated on a substrate with the non-photosensitive black composition for producing a light-shielding image of the present invention. The contained light shielding layer is formed. Thereafter, a photosensitive resist solution is applied on the light shielding layer to form a resist layer. Next, the resist layer is exposed and developed by exposure to form a pattern in the resist layer, and then the non-patterned portion of the light shielding layer is dissolved according to this pattern to form a pattern in the light shielding layer. Finally, the resist layer is removed to produce a light-shielded image.

  In the third method, a coating layer is formed in advance on a portion other than the pattern on the substrate, and rod-like metal fine particles and at least one of a resin or a precursor thereof are contained on the coating layer, and the present invention is non-photosensitive. The light-shielding layer containing the fine particle-containing layer is formed by applying the black composition for preparing a light-shielding image. Next, the coating layer formed first is removed together with the upper light-shielding layer to produce a light-shielded image.

As a method for producing a light-shielded image using the photosensitive transfer material, the photosensitive transfer material is arranged and laminated on a light-transmitting substrate so that the photosensitive light-shielding layer of the photosensitive transfer material is in contact therewith. Next, the support is peeled off from the laminate of the photosensitive transfer material and the light transmissive substrate, and then the layer is exposed and developed to form a light-shielded image.
This method for producing a light-shielded image does not require a cumbersome process and is low in cost.

Next, the exposure and development process will be described.
(Exposure and development)
A predetermined mask is disposed above the light-shielding layer formed on the substrate, then exposed from above the mask, then developed with a developer to obtain a patterning image, and subsequently subjected to a water washing treatment as necessary. The light-shielded image of the present invention can be obtained by the process of. In addition to the method of arranging the mask as described above, the pattern image may be obtained by performing relative scanning of the exposure light directly based on the image data without using the mask.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an LD, an ultrahigh pressure mercury lamp, a YAG-SHG solid laser, a KrF laser, and a solid laser. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.
The exposure machine used at this time is not particularly limited, but in addition to the proximity exposure machine that exposes through the mask, a scattered light exposure machine, a parallel light exposure machine, a stepper, a laser exposure, etc. Can be used.

The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. Among them, a dilute aqueous solution of an alkaline substance is preferably used. Specifically, the developer preferably has a developing behavior in which the photosensitive resin layer is dissolved. Further, a small amount of an organic solvent miscible with water may be added.
Further, before the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive light-shielding layer.

  Examples of the alkaline substance in the formation method by applying the light-shielding image and the formation method using a photosensitive transfer material include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, Sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, metasilicate) Acid sodium, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the light shielding layer, methods such as rubbing with a rotating brush or wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time depends on the composition of the light-shielding layer, the alkalinity and temperature of the developing solution, and the type and concentration when an organic solvent is added, but is usually about 10 seconds to 2 minutes. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the light-shielded image shape suitable. In this development step, a light-shielded image is formed.

≪Substrate with shading image≫
The substrate with a light-shielding image of the present invention is produced by patterning a light-shielding layer formed from a black composition for producing a light-shielding image on a light-transmitting substrate as described above.
The film thickness of the light-shielded image on this light-shielded image-attached substrate (preferably a black matrix substrate) is preferably 0.2 to 2.0 μm, particularly preferably 0.2 to 0.9 μm. Since the light-shielding layer in the black matrix substrate is made by dispersing rod-shaped metal fine particles, a thin film such as that described above has a sufficient optical density.

  The board | substrate with a light-shielding image of this invention can be applied without a restriction | limiting in particular to uses, such as portable terminals, such as a television, a personal computer, a liquid crystal projector, a game machine, a mobile telephone, a digital camera, and a car navigation. Moreover, it can be used suitably also in preparation of the following color filter.

≪Color filter≫
The color filter of the present invention comprises two or more pixel groups that are formed of a colored layer and have different colors on a light-transmitting substrate, and each of the pixels constituting the pixel group is mutually shielded (hereinafter referred to as “black”). The black matrix is prepared using the black composition for light-shielding image preparation or the photosensitive transfer material of the present invention. The number of pixel groups may be two, three, or four or more. For example, in the case of three, three hues of red (R), green (G), and blue (B) are preferably used. When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable, and any arrangement may be used when four or more types of pixel groups are arranged.

As the light transmissive substrate, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.
To produce a color filter, after forming two or more pixel groups on a light-transmitting substrate by a conventional method, a black matrix may be formed as described above, or a black matrix is first formed. Thereafter, two or more pixel groups may be formed.
Since the color filter of the present invention is provided with a black matrix having a high density and a thin film as described above, it has high display contrast and excellent flatness.

≪Display element≫
The black composition for light-shielding image preparation 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. Particularly, when used for a liquid crystal display device, the effect of the black composition for producing a light-shielding image of the present invention is remarkably exhibited. Is done. For definitions of display elements and explanations of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Sumi Kogyo Kenkyukai 1990)”, “Display Device (written by Junyuki Ibuki, published in 1989 by Sangyo Tosho)” It is described in.

  The display device of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, in addition to the color filter. Generally composed of various members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. The light-shielded image in the present invention can be applied to a liquid crystal display element composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Omoyoshi) The type of LCD includes STN, TN, VA, IPS, OCS, R-OCB, and the like.

As one of the liquid crystal display elements, at least one is provided with a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of light-transmitting substrates. Can be mentioned.
As the color filter, a color filter having a plurality of pixel groups as described above, and each pixel constituting the pixel group being separated from each other by the light-shielded image according to the present invention can be preferably used. Since the color filter has high flatness, the liquid crystal display element including the color filter does not cause cell gap unevenness between the color filter and the substrate, and the occurrence of display defects such as color unevenness is improved.

In another aspect of the liquid crystal display element, at least one of them is provided with a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is an active element ( For example, a black matrix produced using the black composition for producing a light-shielding image or the photosensitive transfer material of the present invention is formed between each active element.
The liquid crystal display element is described in, for example, “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Side Industry Research Committee, 1994)”. The display device (liquid crystal display element) of the present invention is not particularly limited, and can be applied to various types of liquid crystal display elements described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for color TFT type liquid crystal display elements.
The color TFT liquid crystal display element is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention can be applied to a liquid crystal display element with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  Examples of the liquid crystal that can be used for the liquid crystal display element include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, unless otherwise specified, “part” represents “part by mass” and “molecular weight” represents “mass average molecular weight”.

[Example 1]
<< Production of photosensitive material >>
<Preparation of rod-shaped silver fine particle dispersion>
73.5 g of rod-shaped silver fine particles (major axis length L: 400 nm, width b: 30 nm, thickness t: 25 nm, b / t = 1.2) and a dispersant (trade name: Solsperse 20000, manufactured by Avicia Co., Ltd.) ) 1.05 g and methyl ethyl ketone 16.4 g were mixed. This was dispersed using an ultrasonic disperser (trade name: Ultrasonic generator model US-6000 ccvp, manufactured by nissei) to obtain a rod-shaped silver fine particle dispersion.

In addition, the rod-shaped silver fine particles of various shapes in this example are obtained by changing the pH and reaction temperature during silver salt reduction by the fine particle preparation method described in Materials Chemistry and Physics 2004, 84, P197-204. The dispersion was prepared as a dispersion of rod-shaped silver fine particles having various shapes, and the obtained dispersion was centrifuged (10000 rpm, 20 minutes), and the supernatant was discarded and concentrated appropriately to obtain rod-shaped silver fine particles. Further, the major axis length L and b / t ratio of the rod-shaped metal fine particles were adjusted by adjusting the ratio of the seed particles to the metal salt.
The major axis length L, width b and thickness t, and particle size distribution D90 / D10 of the rod-shaped metal fine particles were measured by the method described above.

<Preparation of coating solution for photosensitive light shielding layer>
The following composition was mixed and the coating liquid for photosensitive light shielding layers was prepared.
〔composition〕
・ Bar-shaped silver fine particle dispersion 40.00 parts ・ Propylene glycol monomethyl ether acetate 28.6 parts ・ Methyl ethyl ketone 37.6 parts ・ Fluorosurfactant 0.2 parts (trade name: F176PF, Dainippon Ink & Chemicals, Inc.) Made)
Hydroquinone monomethyl ether 0.001 part benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, molecular weight 30000)
・ Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
Here, the addition amount of dipentaerythritol hexaacrylate is set to an amount that is 0.9 in terms of mass ratio when the amount of benzyl methacrylate / methacrylic acid copolymer in the coating solution is 1, and The volume ratio was set to 0.13.
-Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.1 part

<Preparation of coating solution for protective layer>
The following compositions were mixed to prepare a protective layer coating solution.
・ 3.0 parts of polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd.)
-Polyvinylpyrrolidone 1.3 parts (Brand name: PVP-K30, manufactured by IS Japan Co., Ltd.)
・ Distilled water 50.7 parts ・ Methyl alcohol 45.0 parts

<Production of photosensitive material>
The photosensitive light-shielding layer coating solution was applied onto a glass substrate using a spin coater so that the dry film thickness was 1.00 μm, and dried at 100 ° C. for 5 minutes to form a photosensitive light-shielding layer. Next, the coating solution for the protective layer is applied on this using a spin coater so that the dry film thickness is 1.5 μm, and dried at 100 ° C. for 5 minutes to form a protective layer. The material was made.

<Production of black matrix>
With a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and protective layer are The distance between the coated surfaces was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² . Next, development processing (33 ° C., 20 seconds) was performed using a development processing solution TCD (produced by Fuji Photo Film Co., Ltd., alkaline developer). A black matrix having a screen size of 10 inches, a number of pixels of 480 × 640, a black matrix width of 24 μm, and an opening of the pixel portion of 86 μm × 304 μm was obtained.

<Evaluation>
The obtained black matrix was evaluated as follows. The results are shown in Table 1 below.
-Optical density measurement-
The optical density of the film was measured by the following method.
First, the photosensitive light-shielding layer coated on the glass substrate before producing the black matrix was exposed to 500 mJ / cm ² from the coated surface side using the ultrahigh pressure mercury lamp. Next, the optical density (OD) was measured using a Macbeth densitometer (trade name: TD-904, manufactured by Macbeth), and further baked at 240 ° C. for 120 minutes, and then the optical density (OD). Was measured. Separately, the optical density (OD ₀ ) of the glass substrate was measured by the same method. D. OD ₀ was subtracted from this to obtain the optical density of the film before and after baking.

-Black matrix quality-
Further, the quality (color) of the black matrix before and after the baking was visually confirmed and evaluated.

-Heat resistance evaluation-
The heat resistance was evaluated according to the following criteria based on the change in optical density before and after baking.
・ ○ OD change less than 0.5 ・ × OD change 0.5 or more and less than 1.0 ・ XX OD change 1.0 or more

(Creation of liquid crystal display device)
A liquid crystal display device was produced by using the substrate formed with the black matrix obtained above and using the method described in the first embodiment [0079] to [0082] of JP-A-11-242243. It was confirmed that it displayed without malfunction.

[Examples 2 and 3]
When preparing the rod-like silver fine particle dispersion liquid of Example 1, a black matrix was prepared in the same manner as in Example 1 except that the rod-like silver fine particles shown in Table 1 were used, and the same evaluation was performed. The results are shown in Table 1 below.

[Example 4]
<< Production of photosensitive transfer material >>
Using a glass substrate coater (manufactured by FS Japan Co., Ltd., trade name: MH-1600) having a slit-like nozzle on the biaxially stretched 75 μm-thick polyethylene terephthalate film support surface, The thermoplastic resin layer coating solution prepared in (1) was applied to a thickness of 15 μm and dried at 100 ° C. for 5 minutes to form a thermoplastic resin layer. Next, an intermediate layer coating solution having the same composition as that of the protective layer coating solution in Example 1 was applied thereon so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 5 minutes. Formed. Further thereon, a coating solution for photosensitive light-shielding layer prepared by replacing the rod-like silver fine particles used in the rod-like silver fine particle dispersion of Example 1 with the rod-like silver fine particles shown in Table 1, was obtained with a dry film thickness of 1.0 μm. And dried at 100 ° C. for 5 minutes to form a photosensitive light-shielding layer, and a photosensitive transfer material was produced.

<Preparation of coating solution for thermoplastic resin layer>
The following composition was mixed to prepare a coating solution for a thermoplastic resin layer.
Copolymer of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid (55 / 11.7 / 4.5 / 28.8) (molecular weight 80000) 58 parts Copolymer of styrene / acrylic acid = 63/37 Polymer (molecular weight 7000)
136 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylate) 90 parts · Fluorosurfactant 1 part (trade name: F780F, Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 541 parts ・ 1-methoxy-2-propanol 63 parts ・ Methyl alcohol 111 parts

<< Production of photosensitive material >>
The glass substrate and the photosensitive transfer material obtained above are overlapped so that the photosensitive light-shielding layer is in contact with the glass substrate, and both are used using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). Were pasted together. The lamination conditions were a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min. Thereafter, the support (polyethylene terephthalate film) was peeled from the photosensitive transfer material to produce a photosensitive material.

<Production of black matrix>
The exposure was performed using the same exposure machine and the same exposure conditions as in Example 1. Next, development processing in the following three steps was performed to obtain a black matrix.
[Development processing]
First step: Development processing was performed using a development processing solution (trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 30 ° C. for 40 seconds.
Second step: Development processing was performed using a developing solution (trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 33 ° C. for 20 seconds.
Third step: Development processing was performed using a developing solution (trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 33 ° C. for 20 seconds.

<Evaluation>
Evaluation similar to Example 1 was performed. The results are shown in Table 1 below.

[Examples 5 and 6]
A black matrix was prepared in the same manner as in Example 4 except that the rod-shaped silver fine particles shown in Table 1 were used in the rod-shaped silver fine particle dispersion of Example 4, and the same evaluation was performed. The results are shown in Table 1 below.

[Example 7]
In the same manner as in Example 1, rod-shaped silver fine particles were prepared, and 200 parts of the silver fine particles were dispersed in an acetone dispersion (major axis length L: 150 nm, width b: 40 nm, thickness t: 30 nm, concentration 2.5% by mass). 0.95 part of P-1 (vinyl pyrrolidone / vinyl acetate = 60/40 (mass ratio) copolymer, molecular weight 5000) was added and stirred for 30 minutes.
Next, with stirring, an aqueous sodium sulfide solution having a concentration of 7.2% by mass was added so that the sulfidation rate of the metal was 10%.

The “sulfidation rate” referred to here is the proportion of metal fine particles that are sulfided, 0% sulfide is not sulfided at all, and 100% is a state in which the entire particle is completely sulfided. To express. The liquid temperature when the aqueous sodium sulfide solution was added was 23 ° C.
After addition of the aqueous sodium sulfide solution, stirring was continued for 30 minutes.
Silver / silver sulfide core-shell fine particles having a silver sulfide shell were produced by the above process.

The mass ratio of shells in the particles was 0.11. This mass ratio was calculated from the number of moles of silver and sulfur in the particles. The number of moles of both was determined by fluorescent X-ray analysis using a fluorescent X-ray analyzer Type 3370E (manufactured by Rigaku Corporation) on a sample obtained by spin-coating a particle dispersion on a polyethylene terephthalate support. Sulfur and silver moles each m _s, When m _A, the number of moles of Ag ₂ S shells m _s, the number of moles of the core of Ag becomes m _A -2m _s.
Therefore, the mass ratio of shell to core is
(M _s /247.8):(m _A -2 m _s /107.9)
become.

  Using the silver / silver sulfide core-shell fine particles prepared above, metal fine particles having the shape shown in Table 1 were prepared by the same method as in Example 1, and using the metal fine particles, a black matrix was obtained as in Example 4. The same evaluation was performed. The results are shown in Table 1 below.

[Example 8]
In Example 1, when preparing the coating solution for the photosensitive light-shielding layer, instead of the rod-shaped silver fine particle dispersion, rod-shaped gold fine particles and carbon black (trade name: CFP-FF-949K, Fuji Film Electronics Materials Co., Ltd.) ) And a black matrix as in Example 1 except that the addition amount of carbon black was changed to the addition amount of rod-shaped gold fine particles: carbon black = 95: 5 (mass ratio) with respect to the addition amount of the rod-shaped gold fine particle dispersion. The same evaluation was performed. The results are shown in Table 1 below.

[Example 9]
<Preparation of AgSn alloy fine particle dispersion>
In 1000 ml of pure water, 61.2 g of silver perchlorate (I), 35.8 g of tin acetate (II), 45 g of sodium pyrophosphate, 5 g of polyethylene glycol (molecular weight 3,000), and AGRIMER AL-10LC (IS Japan) A solution 1 was obtained by dissolving 5 g of a vinyl pyrrolidone / vinyl acetate copolymer (manufactured by Co., Ltd.).
Separately, 36.1 g of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.

While the solution 1 obtained above was vigorously stirred while maintaining at 25 ° C., the solution 2 was added thereto over 7 minutes, and the stirring was continued gently for 6 hours. Then, the liquid mixture turned black, and silver tin (AgSn) alloy fine particles were obtained. Subsequently, this liquid was centrifuged to precipitate AgSn alloy fine particles. Centrifugation is subdivided into a volume of 150 ml, and a rotational speed of 2,000 r.m. using a desktop centrifuge H-103n (manufactured by Kokusan Co., Ltd.). p. m. For 30 minutes. The supernatant was discarded and the total liquid volume was made 150 ml. To this, 150 ml of acetone was added and stirred for 5 minutes, and then 300 ml of acetone was further added and stirred for 5 minutes. Furthermore, 900 ml of acetone was added and stirred for 30 minutes. The obtained liquid was concentrated using an ultrafiltration module (manufactured by Sartorius Co., Ltd.) and Zaltoconmini (fractionated molecular weight 10,000) until the liquid volume became 100 ml. The filtration rate was 3.0 l / h (filtration area 0.1 m ² ).

  A black matrix was produced in the same manner as in Example 4 using the AgSn alloy fine particle dispersion prepared above instead of the rod-shaped silver fine particle dispersion used in Example 4, and the same evaluation was performed. The results are shown in Table 1 below.

[Example 10]
A black matrix was prepared in the same manner as in Example 9 except that the AgSn alloy particle dispersion used in Example 9 was changed to the shape shown in Table 1, and the same evaluation was performed. The results are shown in Table 1 below.

[Example 11]
A black matrix was produced in the same manner as in Example 1 except that the rod-shaped silver particle dispersion used in Example 1 was changed to the shape shown in Table 1, and the same evaluation was performed. The results are shown in Table 1 below.

[Comparative Examples 1 and 2]
A black matrix was prepared in the same manner as in Example 1 except that the rod-shaped silver fine particle dispersion used in Example 1 was changed to the shape shown in Table 1, and the same evaluation was performed. The results are shown in Table 1 below.

From Table 1, all of the black matrices of the examples have a small OD decrease due to baking, and after baking, all have a high OD of 3.5 or more, and the color remains black. The quality of was high.
On the other hand, the black matrix of Comparative Example 1 had an OD after baking of 3.1, but the color changed from brown to yellow brown by baking (the color became lighter), and the quality as a black matrix Was not preferred. Furthermore, the OD of the black matrix of Comparative Example 2 was greatly reduced by baking and the OD after baking was 2.5, and the color changed from brown to yellow brown by baking as in Comparative Example 1 (color). However, it was not possible to demonstrate satisfactory performance as a black matrix.

Claims (14)

A black composition comprising black rod-shaped fine metal particles, at least one of a resin or a precursor thereof, a monomer and an initiator. The metal particles include metals, metal compounds, are formed from one of the composite fine particles of the metal compound and a metal, the elemental silver or Kanemoto element.   2. The black composition according to claim 1, wherein the metal fine particles are silver fine particles, gold fine particles, fine particles having a silver sulfide shell in the core of silver fine particles, or silver tin alloy fine particles. The major axis length (L), the width (b), and the thickness (t) of the rod-shaped metal fine particles satisfy the following conditions (1) to (3). Black composition.
(1) The major axis length (L) is 10 nm or more and 1000 nm or less.
(2) Long axis length (L)> Width (b) ≧ Thickness (t)
(3) The ratio (b / t) of the width (b) to the thickness (t) is 2.0 or less.   The particle size distribution of the rod-shaped metal fine particles is 1.2 or more and less than 20 in the particle size distribution width (D90 / D10) of the number average particle diameter obtained by approximating the particle distribution to a normal distribution. The black composition of any one of 1-3.   Furthermore, a pigment is included, The black composition as described in any one of Claims 1-4 characterized by the above-mentioned.   The black composition according to claim 5, wherein the pigment is at least one selected from carbon black, titanium black, and graphite.   The black composition according to claim 1, wherein the black composition is used for production of a light-shielded image.   A photosensitive transfer material comprising at least a photosensitive light-shielding layer on a support, wherein the photosensitive light-shielding layer is formed of the black composition according to claim 7.   A substrate with a light-shielding image, comprising a light-shielding image produced using the black composition according to claim 7.   A substrate with a light-shielding image, comprising a light-shielding image produced using the photosensitive transfer material according to claim 8.   In the color filter which has two or more pixel groups which consist of a colored layer on a light-transmitting substrate and which exhibit mutually different colors, and each pixel which constitutes the pixel group is separated from each other by a light-shielding image, A color filter, wherein a light-shielded image is produced using the black composition according to claim 7 or the photosensitive transfer material according to claim 8.   12. A liquid crystal display device comprising at least a color filter, a liquid crystal layer, and a liquid crystal driving means between a pair of substrates that are at least one of light transmissive, wherein the color filter is the color filter according to claim 11. A characteristic liquid crystal display element.   A process for producing a light-shielding image, comprising: forming a light-shielding layer on the light-transmitting substrate using the black composition according to claim 7; and exposing and developing the light-shielding layer. Method.   The photosensitive transfer material according to claim 8, wherein at least a photosensitive light-shielding layer is provided on a support, and the photosensitive transfer material is laminated on a light-transmitting substrate so that the photosensitive light-shielding layer is in contact therewith. A light-shielded image comprising: a step; a step of peeling the support from a laminate of the photosensitive transfer material and the light-transmitting substrate; and a step of exposing and developing the photosensitive light-shielding layer. Production method.