JP2008249967A - Metal fine particle dispersion, transfer material, substrate with light shielding image, color filter, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate with a light shielding image which has a shelding image low in reflectance. <P>SOLUTION: The substrate with the light shielding image has the light shielding image including at least metal fine particles, and is characterized in that the metal fine particles include amorphous flat plate metal fine particles. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a metal fine particle dispersion, a transfer material, a substrate with a light-shielding image, a color filter, and a display device.

Colored compositions using fine metal particles include printing inks, inkjet inks, etching resists, solder resists, plasma display panel (PDP) partition walls, dielectric patterns, electrode (conductor circuit) patterns, electronic component wiring patterns, and conductive pastes. Widely used for light-shielded images such as conductive films and black matrices. Among the colored compositions, the colored composition for the black material is a black edge or red, blue, or the like provided in the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, or a CRT display device. In addition to a so-called black matrix (hereinafter also referred to as “BM”), such as a grid-like or stripe-like black portion between green pixels, and a dot-like or linear black pattern for light-shielding a TFT, various light-shielded images It is expected to be used in
BM 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), in order to prevent deterioration in image quality due to current leakage due to light, and has high light shielding properties ( The optical density OD is 3 or more).

  On the other hand, in recent years, liquid crystal display devices have been applied to TVs. However, in TVs, high luminance is obtained using a color filter with low transmittance and high color purity, so that the luminance of the backlight is low. The BM is required to have a high light-shielding property in order to prevent a decrease in contrast and transparency 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. BM is required to have a high light-shielding property also in the sense that it is high and (2) the white color of the liquid crystal under external light becomes inconspicuous.

  As a method for forming a BM using a metal film such as chromium as a light shielding layer, for example, a metal thin film is prepared by vapor deposition or sputtering, a photoresist is applied on the metal thin film, and then a photo having a BM pattern is formed. There is a method of forming a BM by exposing and developing the photoresist layer using a mask, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film (see, for example, Non-Patent Document 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 one made of two layers of metal chromium and chromium oxide), but it cannot be denied that the cost is further increased.
And since the waste liquid containing a metal ion is discharged | emitted in an etching process, it also has the big fault that an environmental impact is large. There is a concern that chromium, which is most often used, is harmful and has a large environmental impact.
In recent years, as represented by the EU ELV and RoHS directives, there has been an increasing social interest in reducing environmental burdens, and proposals have been made for materials that replace chromium.

As another BM 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. A self-aligned BM formation method in which the entire surface is exposed from the side is known (see, for example, Patent Document 1).
Although the manufacturing cost is lower than the method by etching the metal film, the method has a problem that the film thickness is increased in order to obtain sufficient light shielding properties. As a result, an overlap (step) between the BM and the R, G, and B pixels occurs, the flatness of the color filter deteriorates, and the cell gap unevenness of the liquid crystal display element occurs, leading to display defects such as display unevenness. Become.

In addition to the above, as a method for obtaining a black matrix with a small environmental load and a high optical density, a method using a flat plate as the particle shape of metal fine particles is known (see, for example, Patent Documents 2 and 3). According to this method, it is said that a black matrix having a small optical load and a high optical density can be obtained.
JP-A-62-9301 JP 2004-334180 A JP 2005-17322 A Published by Kyoritsu Shuppan Co., Ltd. “Color TFT LCD”, pp. 218-220 (April 10, 1997)

However, it is not always possible to keep the reflectance of a light-shielded image low by using only a technique using a flat plate as the particle shape of the metal fine particles.
This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a substrate with a light-shielding image having a light-shielding image having a low reflectance.
Another object of the present invention is to use a metal fine particle dispersion and a transfer material, which can form a light-shielded image with low reflectance and high optical density, and can suppress the occurrence of display unevenness when used in a display device. It is an object of the present invention to provide a substrate with a light-shielding image, a color filter using the light-shielding image substrate, and a display device having excellent display quality in which occurrence of display unevenness is suppressed.

The present inventors have obtained the knowledge that, by using flat metal fine particles having an irregular main plane among flat metal fine particles, a light-shielded image having a low reflectance can be obtained, and based on such knowledge The present invention has been completed.
That is, specific means for solving the above-described problems are as follows.

<1> A substrate with a light-shielding image having a light-shielding image containing at least metal fine particles, wherein the metal fine particles include irregular-shaped flat metal fine particles.
<2> The light-shielding image-carrying substrate according to <1>, wherein 25% or more of the metal fine particles are amorphous plate metal fine particles with respect to the total number of metal fine particles having a particle diameter of 10 nm or more.
<3> The <1> or <2>, wherein the metal fine particles contain one or more metals selected from the group consisting of groups 2 to 14 of the periodic table It is a board | substrate with a light-shielding image.

<4> The substrate with a light-shielding image according to any one of <1> to <3>, wherein the metal fine particles are silver fine particles or silver-containing alloy fine particles.
<5> The substrate with a light-shielding image according to any one of <1> to <4>, wherein an average irregularity of the irregular shaped flat metal fine particles is 1.3 or more.
<6> The substrate with a light-shielding image according to any one of <1> to <5>, wherein the amorphous flat metal fine particles have an average aspect ratio of 3.0 or more.

<7> The substrate with a light-shielding image according to any one of <1> to <6>, wherein the number-average particle diameter of the irregular shaped flat metal fine particles is 5 to 50 nm.
<8> Dispersion containing at least metal fine particles, wherein the metal fine particles include irregular flat metal fine particles, and contain 10% or less of water with respect to the total mass of the metal fine particles. It is a dispersion.
<9> The metal fine particle dispersion according to <8>, wherein 25% or more of the metal fine particles are amorphous flat metal fine particles based on the total number of metal fine particles having a particle diameter of 10 nm or more.

<10> The metal fine particle dispersion according to <8> or <9>, further comprising a dispersion polymer having at least one sulfur atom and / or nitrogen atom.
<11> The fine metal particle dispersion according to <10>, wherein the dispersion polymer having at least one sulfur atom and / or nitrogen atom has alkali solubility.
<12> A transfer material comprising a light shielding layer formed using the metal fine particle dispersion according to any one of <8> to <11> on a temporary support.

<13> A substrate with a light-shielding image formed using the transfer material according to <12>.
<14> A color filter comprising the substrate with a light-shielding image according to any one of <1> to <7> and <13>.
<15> A display device comprising the color filter according to <14>.

ADVANTAGE OF THE INVENTION According to this invention, the board | substrate with a light-shielding image which has a light-shielding image with a low reflectance can be provided.
In addition, according to the present invention, it is possible to form a light-shielded image having a low reflectance and a high optical density, and a metal fine particle dispersion and a transfer material that can suppress the occurrence of display unevenness when used in a display device. It is possible to provide a substrate with a light-shielding image, a color filter using the light-shielding image substrate, and a display device having excellent display quality in which occurrence of display unevenness is suppressed.

  Hereinafter, the metal fine particles in the present invention will be described, and subsequently, the metal fine particle dispersion, the transfer material, the substrate with a light-shielding image, the color filter, and the display device of the present invention will be described in detail.

≪Metallic fine particles≫
The metal fine particle dispersion of the present invention and the light-shielded image in the substrate with a light-shielded image of the present invention contain at least one metal fine particle.
The metal fine particles include irregular flat metal fine particles.
Here, the irregular shaped flat metal fine particles refer to flat metal fine particles having an irregularity of 1.2 or more. As a method for identifying the irregular shaped flat metal fine particles from the entire group of metal fine particles having various shapes, for example, first, the flat metal fine particles are identified from the group of the metal fine particles, and then, among the identified flat metal fine particles. From the above, a method for specifying flat metal fine particles having an irregularity of 1.2 or more can be mentioned.
Hereinafter, the definition of the size of the metal fine particles, the flat metal fine particles, the irregular flat metal fine particles, the number average particle diameter of the metal fine particles, and the composition of the metal fine particles will be described in detail.

<Dimensions of fine metal particles>
In the present invention, each dimension of the metal fine particles is defined in a state where one metal fine particle is contained in a cuboid having a triaxial diameter.
In other words, a box (cuboid) in which one metal fine particle can be exactly (contained) is considered, and the length L, width a, height or thickness b of the box is defined as the dimension of the metal fine particle. . There are several ways to store the metal fine particles in the box. In the present invention, the following method is adopted.
First, the metal fine particles are placed on a horizontal plane so that the center of gravity is the lowest and stably remains. Next, the metal fine particles are sandwiched between two parallel plates standing at right angles to the horizontal plane, and the plate interval at the position where the plate interval is the shortest is defined as “width a”. Next, metal fine particles are sandwiched between two parallel plates perpendicular to the two plates that determine the width a and also perpendicular to the horizontal plane, and the distance between the two plates is defined as “length L”. To do. Finally, the top plate is placed so as to be parallel to the horizontal plane so as to come into contact with the highest position of the metal fine particles. The distance between the top plate and the horizontal plane at this time is defined as “thickness b” (a rectangular parallelepiped defined by the horizontal plane, the four plates, and the top plate is formed by this method). That is, each dimension has a relationship of L ≧ a ≧ b.

<Flat metal particles>
The “plate metal fine particles” refer to metal fine particles having two opposing maximum outer surfaces (hereinafter also referred to as “main planes”) and an aspect ratio of 2.0 or more.
The main plane may be any plane, but is preferably a plane substantially parallel to a plane stretched by the directional axis of the length L and the directional axis of the width a, and is a (111) plane. Preferably there is.
The aspect ratio is a value obtained by dividing the diameter of a circle having the same area as the projected area of the main plane by the average value of the thickness b of the particles. The larger the aspect ratio, the flatter and the more prominent flat plate shape.
Hereinafter, a surface connecting two opposing substantially parallel main planes may be referred to as a “side surface” of the flat metal fine particles.

(Aspect ratio measurement method)
The aspect ratio of the metal fine particles in the metal fine particle dispersion may be measured by any method, and can be measured, for example, as follows.
First, a metal fine particle dispersion is coated on a substrate such as a glass substrate to form a coating film, a cross section of the coating film is observed with a transmission electron microscope, and the side surface is projected on the transmission electron microscope photograph. That is, 100 metal fine particles having a thickness b appear are selected, and the thickness b of each metal fine particle is measured. The average value of the 100 measured values obtained is taken as the average thickness of the group of metal fine particles.
Next, in the same manner as described above, observation is performed with a transmission electron microscope, and 100 metal fine particles on which the main plane is projected are selected on the transmission electron microscope photograph, and each metal fine particle has the same area as the projected area of the main plane. Find the diameter of the circle.
By dividing the diameter of the circle for each obtained metal fine particle by the above-mentioned average thickness, the aspect ratio of each metal fine particle can be obtained individually.
In the above, as a method of determining whether the side surface is projected or the main plane is projected, the particles that appear black on the transmission electron micrograph are regarded as the particles on which the side surfaces are projected, and are transparent and thin. Particles that appear in color can be regarded as particles on which the principal plane is projected.

  The aspect ratio of the metal fine particles in the substrate with the light-shielding image can also be measured by the same method as the aspect ratio of the metal fine particles in the metal fine particle dispersion. That is, it can be measured by observing the cross section of the light-shielded image with a transmission electron microscope.

  The metal fine particles having an individual aspect ratio of 2.0 or more determined as described above are “flat metal fine particles” referred to in the present invention.

(Flatification rate)
In the present invention, the ratio of the number of the flat metal fine particles to the total number of the metal fine particles is referred to as “flattening rate” (%).
Here, the total number of metal fine particles is the number of metal fine particles having a particle diameter of 10 nm or more on a transmission electron micrograph. Here, the “particle diameter” refers to the diameter of a circle having the same area as the projected area of each metal fine particle.
The flattening rate is preferably 25% or more, more preferably 35% or more, and particularly preferably 50% or more from the viewpoint of increasing the optical density of the light-shielded image.

<Amorphous flat metal particles>
The irregular shaped flat metal fine particles in the present invention refer to flat metal fine particles having an irregularity of 1.2 or more among the above-mentioned flat metal fine particles.

(Deformation degree)
The irregularity refers to the minimum value among the values represented by (1) to (3) below.
(1) The value obtained by dividing the area Sc of the smallest circle inscribed by the projection surface of the main plane of the metal fine particle by the projection area of the main plane of the metal fine particle. A value obtained by dividing the area Sh of the hexagon by the projected area of the main plane of the metal fine particles (3) The area St of the smallest triangle inscribed by the projection plane of the main plane of the metal fine particles is the projected area of the main plane of the metal fine particles Divided value

Since the irregular shaped flat metal fine particles of the present invention have a degree of irregularity of 1.2 or more, for example, flat metal fine particles having a main plane projection plane of a circle, hexagon, or triangle are referred to as “undefined”. It is not included in “Sized Flat Metal Fine Particles”.
When flat metal fine particles having an irregularity of less than 1.2 (for example, flat metal fine particles having a main plane projection surface of a circle, hexagon, or triangle) are used for a light-shielded image, the light-shielded image has a high reflectance.

(Measuring method of irregularity)
The degree of irregularity of the flat metal fine particles in the metal fine particle dispersion may be measured in any way, and can be measured, for example, as follows.
First, the aspect ratio is individually determined for each metal fine particle photographed on a transmission electron micrograph by the method described in “(Aspect ratio measurement method)” above, and the aspect ratio is 2.0 or more. Are selected as “flat metal particles”.
By calculating the values represented by the above (1) to (3) and obtaining the minimum value for each of the selected flat metal fine particles, the degree of irregularity of each flat metal fine particle can be determined individually.

  The irregularity of the flat metal fine particles on the substrate with the light-shielding image can also be measured by the same method as the irregularity of the flat metal fine particles in the metal fine particle dispersion. That is, it can be measured by observing the cross section of the light-shielded image with a transmission electron microscope.

  The flat metal fine particles having an individual degree of irregularity of 1.2 or more determined as described above are “indeterminate flat metal fine particles” referred to in the present invention.

(Amorphous flattening rate)
In the present invention, of the total number of fine metal particles, the ratio of the number of the irregular flat metal fine particles is referred to as “amorphous flattening ratio” (%).
Here, the total number of metal fine particles is the number of metal fine particles having a particle diameter of 10 nm or more on a transmission electron micrograph. In the present invention, “particle size” refers to the diameter of a circle having the same area as the projected area of each metal fine particle.
The amorphous flattening rate is preferably 25% or more, more preferably 35% or more, and particularly preferably 50% or more from the viewpoint of increasing the optical density of the dark shading image and suppressing the reflectance.

(Preferred irregularity of irregular shaped flat metal fine particles)
The irregularity of the irregular shaped flat metal fine particles in the present invention is not particularly limited as long as it is 1.2 or more. If the irregularity is less than 1.2, the reflectance is high.
From the viewpoint of further low reflectivity, it is preferable to include amorphous flat metal fine particles having an irregularity of 1.3 or more, more preferably to include amorphous flat metal fine particles having a profile of 1.4 or more. It is particularly preferable that the above-mentioned amorphous flat metal fine particles are included.

From the viewpoint of low reflectivity, the average value of the irregularity is also important.
In the present invention, from the viewpoint of low reflectivity, it is preferable that the average value of the irregularities of the 100 irregular flat metal fine particles (hereinafter also referred to as “average irregularity”) is 1.2 or more. It is more preferably 3 or more, and particularly preferably 1.4 or more.
Here, the average degree of irregularity is obtained by selecting 100 irregular-shaped flat metal fine particles from a transmission electron micrograph obtained by photographing metal fine particles, and obtaining individual irregularities for the selected irregular-shaped flat metal fine particles. It can be obtained by dividing the sum of the deformed degrees by 100.

(Preferred aspect ratio of irregular shaped flat metal fine particles)
The aspect ratio of the irregular shaped flat metal fine particles in the present invention is not particularly limited as long as it is 2.0 or more. However, in order to absorb light having a wavelength in the entire visible light range, the aspect ratio is 2.0 to 4.0. It is preferable to include amorphous flat metal fine particles, more preferably 2.5 to 4.0 amorphous flat metal fine particles, and still more preferably 3.0 to 4.0 amorphous flat metal fine particles. It is particularly preferable to contain amorphous flat metal fine particles of 3.5 to 4.0. The metal fine particle dispersion of the present invention preferably contains metal fine particles having different aspect ratios.

From the viewpoint of absorbing light having a wavelength in the entire visible light range, the average value of the aspect ratio is also important.
In the present invention, from the viewpoint of absorbing light having a wavelength in the entire visible light range, the average value of the aspect ratios of the 100 amorphous flat metal fine particles (hereinafter also referred to as “average aspect ratio”) is 2.5 or more. It is preferable that it is 3.0 or more.
Here, the average aspect ratio is obtained by selecting 100 amorphous plate metal fine particles from a transmission electron micrograph taken of metal fine particles, and obtaining individual aspect ratios for each of the selected amorphous plate metal fine particles. It can be obtained by dividing the sum of the obtained aspect ratios by 100.

(Preferred thickness of irregular shaped flat metal fine particles)
Further, from the viewpoint of increasing the aspect ratio, increasing the optical density, and the like, the thickness b of the amorphous flat metal fine particles is also important.
In the present invention, from the above viewpoint, it is preferable to include amorphous flat metal fine particles having a thickness b of 1 nm to 50 nm, more preferably including irregular flat metal particles having a thickness b of 3 nm to 40 nm. It is particularly preferable to include amorphous flat metal fine particles having a thickness b of 7 nm to 25 nm.
Moreover, as average thickness (100 average value) of an amorphous flat metal fine particle, 1 nm-50 nm are preferable, 3 nm-40 nm are more preferable, and 7 nm-25 nm are especially preferable.

<Number average particle diameter of metal fine particles>
The number average particle diameter of the metal fine particles in the present invention is not particularly limited as long as it does not exceed the film thickness to be formed, but is preferably in the range of 5 nm to 1000 nm, more preferably in the range of 10 nm to 200 nm, and further in the range of 30 nm to 100 nm. preferable.
When the number average particle diameter of the metal fine particles in the present invention is in the range of 5 nm to 1000 nm, it is easy to produce, and the color filter produced using the tabular grains having the number average particle diameter range is visually in view of its characteristics. It is preferable in that it looks black (not brown), and it is preferable because the stability of the dispersion in which the particles are dispersed is improved and good light-shielding properties are exhibited.
Further, the metal fine particles in the present invention are not particularly limited with respect to the particle size distribution.

(Number average particle size of irregular shaped flat metal fine particles)
As described above, the number average particle size of the irregular shaped flat metal fine particles in the present invention is as follows from the viewpoint of ease of production, the point that looks more black visually, the viewpoint of dispersion stability, and the good light shielding property. The range of 2 nm to 100 nm is preferable, the range of 3 nm to 80 nm is more preferable, and the range of 5 nm to 50 nm is particularly preferable.

(Measurement method of number average particle diameter)
The number average particle diameter of the metal fine particles in the metal fine particle dispersion is observed with a transmission electron microscope, for example, in the same manner as described in the above (Method for measuring aspect ratio), and on the transmission electron micrograph. 100 particles are selected at random, and the diameter of a circle having the same area as the projected area of each particle is obtained. Let the diameter of the obtained circle be the particle diameter of each metal fine particle.
By dividing the total of the obtained particle diameters by 100, the number average particle diameter of the metal fine particles in the metal fine particle dispersion is obtained.

  The number average particle diameter of the metal fine particles in the substrate with the light-shielding image can also be measured by the same method as the number average particle diameter of the metal fine particles in the metal fine particle dispersion. That is, it can be measured by observing the cross section of the light-shielded image with a transmission electron microscope.

When measuring the number average particle diameter of the irregular flat metal fine particles, first, 100 irregular flat metal fine particles are selected from the metal fine particles on the transmission electron micrograph by the method described above.
The number average particle size of the irregular shaped flat metal fine particles can be measured for 100 selected irregular shaped flat metal fine particles by the same method as the method for measuring the number average particle size of the metal fine particles.

<Composition of metal fine particles>
The metal of the metal fine particles in the present invention is not particularly limited, and any metal may be used. In addition, as the metal fine particles in the present invention, two or more kinds of metals may be used in combination, or may be used as an alloy.
Among them, the metal fine particles in the present invention are preferably metal or composite fine particles of a metal and a metal compound, and those formed from a metal are particularly preferable.
In particular, as the types of metal fine particles preferably used in the present invention, the metal fine particles described in paragraph numbers [0038] to [0039] of JP-A-2006-251237 can be suitably used in the present invention.

  Among these, a preferable metal is at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or an alloy thereof, and more preferable metals are copper, silver, gold, platinum. , Tin and alloys thereof, and more preferably silver or an alloy containing silver.

The amorphous flat metal fine particles in the present invention can be obtained by reducing metal ions in the presence of a dispersion polymer described later.
Specifically, it is obtained by adding a metal salt-containing solution containing a metal and a reducing agent in the presence of a dispersion polymer, mixing them, and reducing metal ions.
The metal salt can be used without particular limitation, and examples thereof include metal salts such as chlorides, nitrates, nitrites, sulfates, ammonium salts, acetates, etc. Among these, the process of forming irregular tabular grains Nitrate, nitrite and acetate are preferable, nitrate and acetate are more preferable, and nitrate is particularly preferable.

  The reducing agent is not particularly limited as long as it is usually used. For example, borohydride metal salts such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum hydride, magnesium magnesium hydride, calcium aluminum hydride, etc. Aluminum hydride salt; sodium sulfite, hydrazine compound, dextrin, hydroquinone, hydroxylamine, citric acid and its salt, succinic acid and its salt, ascorbic acid and its salt, etc .; diethylaminoethanol, ethanolamine, propanolamine, triethanolamine, Alkanolamines such as dimethylaminopropanol; propylamine, butylamine, dipropyleneamine, ethylenediamine, triethylenepentamine Any aliphatic amine; heterocyclic amines such as piperidine, pyrrolidine, N-methylpyrrolidine, morpholine; aromatic amines such as aniline, N-methylaniline, toluidine, anisidine, phenetidine; benzylamine, xylenediamine, N- Aralkylamine such as methylbenzylamine; etc., and from the viewpoint of shape control of the metal fine particles, among these, it is preferable to use one or more selected from sodium sulfite, hydroquinone, ascorbic acid or a salt thereof, A combination of sodium sulfite and hydroquinone, a combination of sodium sulfite and ascorbic acid, or a combination of sodium sulfite and ascorbic acid is more preferable, and a combination of sodium sulfite and hydroquinone is more preferable.

  The metal salt / reducing agent equivalent ratio is preferably 0.2 to 5, more preferably 0.5 to 2, and particularly preferably 0.8 to 1.5.

In the method for producing fine metal particles of the present invention, the addition method of metal salt and reducing agent, the reaction temperature and the like are not particularly limited, and can be appropriately adjusted according to the intended fine metal particle composition to be prepared.
From the viewpoint of controlling the shape of the fine metal particles, the temperature during the reaction is preferably 60 ° C. or less, and more preferably 50 ° C. or less. The addition method is not particularly limited, but it is preferable to start the addition of metal ions earlier than the reducing agent. And it is preferable to stir from a viewpoint of forming a uniform system at the time of particle | grain formation, 200 rpm or more is preferable and the rotation speed is more preferable 400 rpm or more. Although there is no restriction | limiting in particular in pH at the time of particle | grain formation, It is preferable that pH before metal salt addition is 10 or more from a viewpoint of reducing a metal salt via a hydroxide.

-Composite fine particles-
The above-mentioned “composite fine particles of a metal compound and a metal” refers to particles obtained by combining a metal and a metal compound into one particle.
As the composite fine particles, metal compound fine particles, composite fine particles, and core shell type composite particles described in paragraphs [0040] to [0043] of JP-A-2006-251237 can be suitably used in the present invention. .

-Dispersion of fine metal particles-
In the present invention, the metal fine particles containing the irregular flat metal fine particles are preferably dispersed in the metal fine particle dispersion of the present invention described later. The presence state of the metal fine particles at the time of dispersion is not particularly limited, but the metal fine particles are preferably present in a stable dispersion state, for example, more preferably in a colloidal state.

The solvent used for dispersing the metal fine particles is not particularly limited, and among them, those having an SP value of 9.0 or more are preferable. The “SP value” is also called a solubility parameter, and is expressed by the square root of the cohesive energy density. In the present invention, the SP value means that described in page 838 of “Adhesion Handbook” (edited by the Japan Adhesive Society, published by Nikkan Kogyo Shimbun, first published in 1971).
For example, n-hexane / 7.3, toluene / 8.9, ethyl acetate / 9.1, methyl ethyl ketone / 9.3, acetone / 10.0, ethyl alcohol / 12.7, methyl alcohol / 14.5, water /23.4. Here, the unit of the SP value is “(cal / cm ³ ) ^1/2 ”.
When an SP value of 9.0 or more is used during redispersion in a solvent, the dispersibility is particularly good, and methyl ethyl ketone, 2-propanol, 1-propanol, 1-methoxy-2-propyl acetate, cyclohexanone, acetone , N-methylpyrrolidone, or a mixture thereof.
It is preferable that the content of the dispersion polymer described later is 70 to 99% by mass because the dispersion is sufficiently performed and aggregation is not caused, and tabular growth is not inhibited.

≪Metal fine particle dispersion≫
The metal fine particle dispersion of the present invention is a dispersion containing at least the above-mentioned metal fine particles, wherein the metal fine particles include the irregular shaped flat metal fine particles, and 10% or less of water with respect to the total mass of the metal fine particles. It is characterized by containing.
Since the metal fine particle dispersion of the present invention has the above-described configuration, the reflectance of the light-shielded image when a light-shielded image is formed can be reduced.
If the water content exceeds 10%, the dispersion state of the metal fine particles may be deteriorated, or display defects such as display unevenness may occur.
Display unevenness is light unevenness observed when a gray test signal is input to the liquid crystal display device. It is said that when the black matrix substrate surface is not smooth, the orientation of the liquid crystal is disturbed, causing display unevenness. "Stripes" that appear to be relatively sharp and streaky are those that occur during the formation of alignment control protrusions such as thickness unevenness, exposure unevenness, development processing unevenness, heat treatment unevenness, etc. that occur during the formation of the photosensitive resin layer. In addition, when functioning as a liquid crystal display device, there may be unevenness caused by the interaction between the alignment control protrusion and the liquid crystal, but the mechanism is not clear.

Among these, from the viewpoint of more effectively achieving the effects of the present invention, the viewpoint of improving the optical density of the light-shielded image when a light-shielded image is formed, and the viewpoint of suppressing reflectance, the metal contained in the metal fine particle dispersion Of the total number of fine metal particles having a particle diameter of 10 nm or more, 25% or more are preferably amorphous flat metal fine particles.
The preferred forms of the irregular flat metal fine particles and metal fine particles are as described above.
Furthermore, the metal fine particle dispersion of the present invention may contain a dispersion polymer having at least one sulfur atom and / or nitrogen atom as an optional component.
Hereinafter, the dispersion polymer having one or more sulfur atoms and / or nitrogen atoms will be described. Furthermore, the coloring composition which is a preferable usage form of a metal fine particle dispersion is also demonstrated.

<Dispersion polymer having one or more sulfur atoms and / or nitrogen atoms>
Next, a dispersion polymer having at least one sulfur atom and / or nitrogen atom in the present invention (hereinafter also referred to as “dispersion polymer”) will be described.
The metal fine particle dispersion of the present invention can further improve the dispersion stability of the metal fine particles by containing a dispersion polymer.
Moreover, the metal fine particle dispersion of the present invention can be made into a dispersion excellent in dispersion stability of metal fine particles by preparing metal fine particles in the presence of a dispersion polymer.

The dispersion polymer in the present invention may be a polymer containing both a sulfur atom and a nitrogen atom, or may be a polymer having either a sulfur atom or a nitrogen atom, both of which are the metal fine particles of the present invention. A dispersion stability effect can be obtained.
As the polymer having a sulfur atom, those having a thioether group, a mercapto group, a sulfide group or a thioxo group are preferable. As the polymer having a nitrogen atom, those having an amino group or an imino group or a nitrogen-containing heterocyclic compound can be used. preferable.

  Examples of the nitrogen-containing heterocyclic compound include 2-mercaptobenzimidazole, pyrrole, pyrrolidine, oxazole, thiazole, imidazole, pyrazole, pyridine, piperidine, pyridazine, pyrimidine, pyrazine, indole, quinoline, benzothiazole, and benzimidazole. These groups may be unsubstituted or substituted.

  The dispersion polymer in the present invention may have the above-described group containing a sulfur atom or nitrogen atom as a side chain terminal group of a polymer (including a copolymer) or a polymerizable compound described later, Although it may have other than that, what has as a side chain terminal group is preferable. Hereinafter, a polymer (including a copolymer) or a polymerizable compound is also simply referred to as a polymer.

The dispersion polymer in the present invention preferably has alkali solubility from the viewpoint of forming a pattern having no defect during pattern formation.
In the present invention, “alkali solubility” means a substance that is insoluble in distilled water (H ₂ O) and can be dissolved in an alkaline aqueous solution having a pH of 10 to 13. For example, the water-soluble polymer compound is soluble in an alkaline aqueous solution, but is similarly soluble in distilled water, and is excluded from the polymer in the present invention.

The determination of “alkali solubility” in the present invention can be determined, for example, by the following evaluation method.
First, 0.2 g of the compound to be evaluated is added to 20 ml of NaOH aqueous solution adjusted to pH 12.0, and vigorously stirred. Leave in a constant temperature layer at 25 ° C. for 6 hours to confirm solubility. At the same time, 0.2 g of the compound to be evaluated is added to 20 ml of distilled water and stirred vigorously. The solubility is confirmed after standing in a constant temperature layer at 25 ° C. for 6 hours. At this time, if white turbidity and sediment are confirmed, it is determined to be insoluble, and if no cloudiness and sediment are confirmed, it is determined to be soluble. By selecting a substance that is soluble in an aqueous NaOH solution adjusted to pH 12.0 and insoluble in distilled water by such an evaluation method, the “alkali solubility” in the present invention can be confirmed.

  As a dispersion polymer in this invention, what has an acidic group is mentioned suitably, for example. There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boronic acid, a phenol, and a sulfoamide. Among these, a carboxyl group is preferable. The introduction amount of the structural unit having an alkali-soluble group in the dispersion polymer in the present invention is such that the dispersion polymer in the present invention can be dissolved in an alkaline aqueous solution having a pH of 10 to 13 by the presence of the alkali-soluble group. There is no particular limitation.

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

  Examples of the polymer having a carboxyl group as the acidic group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, a modified epoxy resin, and the like. Among these, solubility in a coating solvent, A vinyl copolymer having a carboxyl group is preferred from the viewpoint of solubility in an alkali developer, suitability for synthesis, ease of adjustment of film properties, and the like. A copolymer containing at least one of styrene and a styrene derivative is also preferable.

The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group and (2) a monomer copolymerizable with the vinyl monomer of (1).
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like. In the present specification, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The monomer copolymerizable with the vinyl monomer (1) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, and vinyl esters. , Maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes (eg, styrene, styrene derivatives, etc.), (meth) acrylonitrile, vinyl groups Substituted heterocyclic rings (eg, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, phosphorus Acid mono (2-a Liloyloxyethyl ester), phosphoric acid mono (1-methyl-acryloyloxyethyl ester), vinyl monomers having a functional group (for example, urethane group, urea group, sulfonamide group, phenol group, imide group) Of these, styrenes are preferred.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-ethyl (meth) acrylate, tert-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl (meth ) Acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (Meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate and the like can be mentioned.

Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.
Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of the vinyl alcohol esters include vinyl versatoate, vinyl acetate, vinyl formate, vinyl propionate, and vinyl butyrate.
Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, tert-butyloxycarbonyl group), methyl vinylbenzoate, α-methylstyrene, and the like.

  The molecular weight of the dispersion polymer in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of the dispersion stability of the metal fine particles, for example, the weight average molecular weight is 2,000 to 300,000. Is preferable, 4,000 to 150,000 is more preferable, and 6,000 to 100,000 is particularly preferable.

Further, the organic / inorganic ratio (I / O value) of the dispersion polymer in the present invention is preferably 0.44 or more and 1.65 or less, and more preferably 0.5 or more and 0.6 or less. When the I / O value is 0.44 or more, the solubility in water can be further reduced, and when the I / O value is 1.65 or less, the solubility in an alkaline aqueous solution is further improved. Can be improved.
The organic / inorganic ratio (I / O value) can be obtained by referring to “Organic Conceptual Diagram” issued by Sankyo Publishing Co., Ltd.
When the dispersion polymer in this invention has a sulfur atom, 0.5 mass%-20 mass% are preferable from a viewpoint of the dispersion stability of a metal microparticle, and, as for content of the sulfur atom in a polymer, 1.0 mass%- 10.0 mass% is still more preferable.
Moreover, when the dispersion polymer in this invention has a nitrogen atom, 0.5 mass%-20 mass% are preferable from a viewpoint of the dispersion stability of a metal microparticle, and the content of the nitrogen atom in a polymer is 1.0 mass. % To 10.0% by mass is more preferable.
Furthermore, when the dispersion polymer in this invention has both a sulfur atom and a nitrogen atom, mass ratio (s / n) of a sulfur atom (s) and a nitrogen atom (n) is from a viewpoint of the dispersion stability of a metal microparticle. 0.01 to 200 is preferable, and 0.1 to 20 is more preferable.

  Specific examples of the case where the dispersion polymer in the invention contains a sulfur atom include a polymer compound having at least one repeating unit represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a sec butyl group, an isobutyl group, and a tert-butyl group. Groups are preferred.

In the general formula (1), R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms. The group, the aryl group, and the aralkyl group may each independently be unsubstituted or substituted, and may form a saturated or unsaturated cyclic structure. Saturated or unsaturated cyclic structures include 2-mercaptobenzimidazole, pyrrole, pyrrolidine, oxazole, thiazole, imidazole, pyrazole, pyridine, piperidine, pyridazine, pyrimidine, pyrazine, indole, quinoline, benzothiazole, benzimidazole. .

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

  Among the above, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, and a tert-butyl group are Particularly preferred.

The aryl group represented by R ² may be unsubstituted or substituted, and examples thereof include an aryl group such as a phenyl group, a toluyl group, a xylyl group, a naphthyl group, and an anthracenyl group. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.

  Among the above, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

The aralkyl group represented by R ² may be unsubstituted or substituted, and examples thereof include aralkyl groups such as a benzyl group, a phenethyl group, a naphthylmethyl group, and an anthracenylmethyl group. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
Among the above, an aralkyl group having 7 to 11 carbon atoms is preferable, and a benzyl group is particularly preferable.

In the general formula (1), Z represents —O— or —NH—. Y represents -O-, -CO-, -NR- (R is a hydrogen atom, an alkyl group or an aryl group), or a divalent linking group having 1 to 8 carbon atoms in total.
The divalent linking group having 1 to 8 carbon atoms represented by Y is an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group ( Examples, ethynylene, propynylene), arylene groups (eg, phenylene), divalent heterocyclic groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine 2,4-diyl group, quinoxaline) 2,3-diyl group, pyridazine-3,6-diyl), or a combination thereof (e.g., -NHCH ₂ CH ₂ NH -, - is preferably a NHCONH-, etc.).
Among the above, the alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent. Examples of the substituent are the same as those of the aryl group. Alkyl and aryl groups of R are the same as each of R ^2, and preferred examples are also the same.

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

  The dispersion polymer in the present invention may be a polymer compound containing two or more sulfur atoms by copolymerizing not only one type of repeating unit represented by the general formula (1) but also two or more types.

  The dispersion polymer in the present invention introduces a thioether structure into a desired polymer compound (preferably as a side chain), homopolymerizes a monomer having a thioether group (preferably in a side chain), or a thioether group. It can be obtained by copolymerizing a monomer (preferably in the side chain) with another monomer. Preferably, a thioether structure is introduced into the side chain of the ethylenically unsaturated monomer, or an ethylenically unsaturated monomer containing a thioether structure in the side chain is homopolymerized, or an ethylenic group containing a thioether structure in the side chain It can be obtained by copolymerizing an unsaturated monomer and another copolymer component.

  Specific examples of the repeating unit represented by the general formula (1) are shown below. However, the present invention is not limited to these.

Among the above, from the viewpoint of excellent binding to fine particles when combined with metal fine particles, R ¹ is particularly a hydrogen atom or a methyl group, and R ² is a methyl group, an ethyl group, a normal propyl group, or a normal butyl group. , A tert-butyl group and a phenyl group, wherein Z is —O— and Y is an ethylene group, are preferred.

  Specific examples of the case where the dispersion polymer in the present invention contains a nitrogen atom include, for example, a polymer compound having at least one repeating unit represented by the following.

  Specific examples (example compounds PO-1 to PO-34) of the dispersion polymer containing a sulfur atom or a nitrogen atom in the present invention are listed below, but the invention is not limited thereto. The following exemplary compounds PO-1 to PO-34 are copolymers having repeating units represented by A, B, and C. Moreover, the quantitative ratio of the repeating units A, B, and C is expressed by the ratio of the respective mass%.

As content of the said dispersion polymer in the metal fine particle dispersion of this invention, 1-30 mass% is preferable with respect to the total solid, 3-20 mass% is more preferable, 5-15 mass% is especially preferable.
When the content of the dispersed polymer is within the above range, the resolution can be improved more effectively, aggregation can be prevented, and inhibition of plate growth due to polymer adsorption can be prevented.

  In addition, a surfactant, preservative, or dispersion stabilizer may be appropriately added to the metal fine particle dispersion of the present invention.

  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 is preferably 3 to 6 because the solvent of the coating solution is a nonpolar solvent.

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. Furthermore, surfactant compounds described in the aforementioned “Surfactant Handbook” can also be used.

  As the dispersion stabilizer, for example, those described in “Pigment Dispersion Technology (issued by Technical Information Association, Inc. 1999)” can be used.

<Coloring composition>
The metal fine particle dispersion of the present invention is preferably used in the form of a colored composition by further adding other components.
That is, the colored composition contains the metal fine particle dispersion of the present invention, and if necessary, at least one kind of resin or its precursor, pigment fine particles, a polymer serving as a binder, a monomer, an initiator, a solvent, and the like. You may contain.
The coloring composition includes printing ink, inkjet ink, photomask preparation material, printing proof preparation material, etching resist, solder resist, plasma display panel (PDP) partition, dielectric pattern, and electrode (conductor circuit). It can be used for shading images such as patterns, wiring patterns of electronic components, conductive pastes, conductive films, and black matrices.
For example, in order to improve the display characteristics of a color filter used in a color liquid crystal display device or the like, it is preferably used to provide a light-shielded image in the color pattern interval portion, the peripheral portion, the outside light side of the TFT, and the like.
In addition, black edges provided in the periphery of display devices such as liquid crystal display devices, plasma display devices, EL display devices, and CRT display devices, and black or black stripes or stripes between red, blue, and green pixels This portion is more preferably used as a black matrix such as a dot-like or linear black pattern for shielding a TFT.

  Moreover, it is preferable that the said coloring composition is a black black composition. Here, “black” refers to a color in which the deviation of chromaticity from the achromatic color point (x = 0.333, y = 0.333, Y = 0) is ΔE within 100.

The “black composition” means the absorbance at wavelengths of 450 nm and 550 nm when the total metal atom concentration contained in the colored composition of the present invention is 4.0 × 10 ⁻⁴ mol / L. The ratio, that is, the blackness (k = Abs (450 nm) / Abs (550 nm)) means a composition having a range of 0.5 to 2.0. The absorption of the black composition can be measured using a Hitachi U-3410 type self-recording spectrophotometer.

  As components constituting the coloring composition other than the metal fine particle dispersion, components constituting the photosensitive resin composition described in paragraphs [0023] to [0075] of JP-A-2006-251095, The components constituting the photopolymerizable composition described in paragraph numbers [0077] to [0100] of 2006-251237 can be suitably used in the present invention.

  When a light-shielding layer (layer before patterning) is formed using the colored composition, the optical density per 1 μm thickness of the light-shielding layer is preferably 1 or more. For example, in consideration of preventing the metal fine particles from fusing during post-baking, such as when producing a color filter, the content of the metal fine particles in the light-shielding coloring composition is the total amount of the light-shielding layer to be formed. It is preferable to adjust so that it may become 10-90 mass% with respect to solid content, Preferably it is about 10-80 mass%. The content is preferably determined in consideration of optical density variation due to the number average particle diameter of the metal fine particles.

  By forming a light-shielding image using the colored composition, a light-shielding image having a thin film and a high optical density and a low reflectance can be produced.

In the present invention, the “light-shielded image” 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 shielding, etc. The definition of this black matrix is, for example, written by Taihei Kanno, “Liquid Crystal Display Device 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 the display contrast, and in the case of an active matrix driving type liquid crystal display device using thin film transistors (TFTs), in order to prevent image quality deterioration due to light current leakage, it has a high light shielding property (with an optical density OD). 3 or more) is required.

≪Transfer material≫
The transfer material of the present invention is provided with at least a light-shielding layer formed using the above-described metal fine particle dispersion of the present invention on a temporary support, and further, if necessary, a thermoplastic resin layer, an intermediate layer, etc. It is configured by providing other layers. By pressure-bonding the transfer material to a substrate such as glass, a light shielding layer can be formed on the substrate.
As a preferable form of the transfer material, for example, a photosensitive resin transfer material described in JP-A-5-72724, that is, an integrated film form is suitable. An example of the structure of the integral film is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / light-shielding layer / protective film is laminated in this order.
The temporary support, the thermoplastic resin layer, the intermediate layer, the protective film, and the method for producing the transfer material constituting the transfer material are described in paragraphs [0023] to [0066] of JP-A-2005-3861. Can be mentioned as suitable.

≪Substrate with shading image≫
The substrate with a light-shielding image of the present invention has a configuration in which a light-shielding image containing metal fine particles including the above-mentioned irregular flat metal fine particles is provided on a substrate such as a light-transmitting substrate.
Since the substrate with a light-shielding image of the present invention is configured as described above, the reflectance of the light-shielding image can be reduced.
Among them, from the viewpoint of more effectively achieving the effects of the present invention, 25% or more of the total number of metal fine particles included in the light-shielded image and having a particle diameter of 10 nm or more are amorphous plate metal fine particles. preferable.
The preferred forms of the irregular flat metal fine particles and metal fine particles are as described above.

The substrate with a light-shielding image of the present invention can be produced by forming a light-shielding image on the substrate.
A method for forming the light-shielding image on the substrate is not particularly limited, and a light-shielding layer forming step for forming a light-shielding layer containing metal fine particles including the irregular plate-like metal fine particles on the substrate, and a method of forming the light-shielding image on the substrate. A method comprising an exposure process for exposing the entire light shielding layer or exposing it in a pattern and a developing process for developing the exposed light shielding layer when exposed in a pattern is suitable. Furthermore, you may provide other processes, such as post-exposure and post-baking, as needed.

In the light shielding image forming step, the method for forming the light shielding layer on the substrate is not particularly limited.
For example, a method of transferring the light-shielding layer in the transfer material onto the substrate using the transfer material of the present invention described above (hereinafter also referred to as “transfer method”) can be mentioned. Moreover, the method of apply | coating the metal fine particle dispersion of this invention on the board | substrate or the coloring composition containing this metal fine particle dispersion by a well-known coating method (henceforth "coating method") is also mentioned. In any of the methods, since the metal fine particle dispersion of the present invention is used, the reflectance of the formed light-shielded image can be lowered and the optical density can be improved. When the light-shielded image is used in a display device, the display is performed. Unevenness can be suppressed.
Of the above methods, it is preferable to form the light shielding layer by the “transfer method” from the viewpoint of maintaining the uniformity of the thickness of the light shielding layer and the viewpoint of cost reduction.

  Regarding the steps such as exposure and development, the method described in paragraph Nos. [0096] to [0106] of JP-A-2006-251095 and the paragraph numbers [0116] to [0126] of JP-A-2006-251237 are disclosed. The method for forming a light-shielded image described in (1) can also be suitably used in the present invention.

  In addition to the light shielding layer, other layers such as an intermediate layer (oxygen barrier layer) may be formed on the substrate. In this case, the other layers may be removed in the development step. preferable.

The film thickness of the light-shielded image in the substrate with a light-shielded image (preferably a black matrix substrate) of the present invention is preferably 0.2 to 5.0 μm, particularly preferably 0.2 to 2.0 μm. Since the light shielding layer in the substrate with the light shielding image is obtained by dispersing the metal fine particles in the present invention, even a thin film as described above can have a sufficient optical density (for example, OD 3.5 or more).
The light-shielding layer in the substrate with a light-shielding image preferably has a reflectance of 7.0% or less, particularly 5.0%, as measured from the glass substrate side (the side opposite to the surface on which the coating film is formed) at a wavelength of 500 nm. The following is preferred.

  As a board | substrate in the board | substrate with a light-shielding image of this invention, a light transmissive board | substrate can be used, for example. 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.

  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 is produced using the substrate with a light-shielding image of the present invention.
More specifically, the color filter of the present invention has a pixel group consisting of a colored layer on a light-transmitting substrate and exhibiting two or more different colors, and each pixel constituting the pixel group is mutually It is preferable that the image is separated by a light-shielded image (black matrix).
The pixel group exhibiting two or more different colors may be two colors, three colors, or four colors or more. For example, in the case of three colors, three hues of red (R), green (G), and blue (B) are preferably used. When arranging pixel groups of three colors of red, green, and blue, the arrangement of a mosaic type or a triangle type is preferable, and any arrangement may be used when four or more types of pixel groups are arranged.

In order to produce the color filter of the present invention, a black matrix may be formed as described above after forming a pixel group of two or more colors on a light-transmitting substrate by a conventional method. A black matrix may be formed, and then a pixel group of two or more colors may be formed.
Since the color filter of the present invention includes the black matrix having a high density and a thin film as described above, the display has high display contrast and excellent flatness.

≪Display device≫
A display device according to the present invention includes the substrate with a light-shielding image according to the present invention.
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Applicable. 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)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The black matrix of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[Example 1]
<< Preparation of Silver Nanoparticle Dispersion A-1 >>
The exemplified compound PO-1 was added to 1000 mL of pure water so as to be 6.0 × 10 ⁻³ % (W / W), and 10 mL of 1.0 mol / L calcium nitrate aqueous solution was added and stirred. Thereafter, 50 mL of 1.0 mol / L silver nitrate aqueous solution was added over 30 seconds, and then 50 mL of 1.0 mol / L sodium sulfite aqueous solution and 25 mL of 1.0 mol / L hydroquinone aqueous solution were added over 30 seconds.
Nitric acid was added dropwise to the silver fine particle solution to adjust the pH to 4, and the silver fine particles were aggregated and settled.
The supernatant liquid of the aggregated silver fine particle liquid was removed, 750 mL of distilled water was added thereto, and the mixture was allowed to stand for 120 minutes to remove the supernatant again. This was repeated 4 times.

Methyl ethyl ketone was added to the above-mentioned aggregated silver fine particles so that the silver content was 8 mass%, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifer II type” ultrasonic homogenizer manufactured by Branson.
Subsequently, 40 nm ultrasonic waves were irradiated for 10 minutes with a “Model 2000bdc-h 40: 0.8 type ultrasonic homogenizer” manufactured by Branson to obtain a silver nanoparticle dispersion (metal fine particle dispersion).
During the ultrasonic irradiation, the liquid was cooled by COOLNICS CTW400 manufactured by Yamato Scientific Co., Ltd. so that the liquid was maintained at 25 ° C.
The water content in the silver nanoparticle dispersion obtained as described above was 0.3% by mass.

<Measurement of silver nanoparticles>
The following measurement was performed about the silver nanoparticle contained in the silver nanoparticle dispersion liquid obtained above. The measurement results are shown in Table 1 below.
First, the silver nanoparticle dispersion obtained above was applied to a glass substrate to form a coating film, and the cross section of the coating film was observed with a transmission electron microscope (magnification 100000 times).
From the group of silver nanoparticles on this transmission electron micrograph (magnification 100000 times), the main particle shape was determined, flat silver nanoparticles were selected, and the flattening rate was determined.
Furthermore, amorphous tabular silver nanoparticles were selected from the selected tabular silver nanoparticles, and the amorphous tabularization rate was determined.
The number average particle diameter, the average aspect ratio, and the average degree of irregularity were determined for the selected amorphous tabular silver nanoparticles.
Hereinafter, each selection method and each measurement method will be described.

-Main particle shapes-
The particle shape was observed on a transmission electron micrograph, and the most common shape among 100 particles was defined as the main particle shape.

-Selection of flat silver nanoparticles-
On the transmission electron micrograph, 100 silver nanoparticles whose side surfaces were projected were selected, and the thickness b of each silver nanoparticle was measured. The average value of the 100 measured values obtained was defined as the average thickness of the group of silver nanoparticles.
Next, on the transmission electron micrograph, 100 silver nanoparticles on which the main plane is projected are selected, and for each silver nanoparticle, the diameter of the circle having the same area as the projected area of the main plane, that is, the particle diameter is set. Asked.
The aspect ratio of each silver nanoparticle on which the main plane was projected was determined individually by dividing the particle diameter of each silver nanoparticle on which the main plane was projected by the average thickness described above.
Here, as a method of determining whether the side surface is projected or the main plane is projected, on the transmission electron micrograph, the particles that appear black are regarded as the particles on which the side surfaces are projected, and the color is transparent. The visible particles were considered as particles on which the main plane was projected. Those that could not be discriminated were not measured.
Silver nanoparticles having an aspect ratio of 2.0 or more obtained as described above were selected as “tabular silver nanoparticles”.

-Flattening rate-
On the transmission electron micrograph, the ratio of the number of tabular silver nanoparticles to the number of all silver nanoparticles having a particle diameter of 10 nm or more was determined and used as the tabularization rate (%).

-Selection of irregular shaped flat silver nanoparticles-
For each of the tabular silver nanoparticles selected above, the values represented by the following (1) to (3) are calculated, and the minimum value of (1) to (3) is determined as the degree of irregularity of each tabular silver nanoparticle. did.
(1) The value obtained by dividing the area Sc of the smallest circle inscribed by the projection surface of the main plane of the metal fine particle by the projection area of the main plane of the metal fine particle. A value obtained by dividing the area Sh of the hexagon by the projected area of the main plane of the metal fine particles (3) The area St of the smallest triangle inscribed by the projection plane of the main plane of the metal fine particles is the projected area of the main plane of the metal fine particles Divided values Tabular silver nanoparticles having an irregularity of 1.2 or more were selected as “indeterminate tabular silver nanoparticles”.

-Amorphous flattening rate-
On the transmission electron micrograph, the ratio of the number of amorphous tabular silver nanoparticles to the number of all silver nanoparticles having a particle diameter of 10 nm or more was determined and used as the amorphous tabularization rate (%).

-Number average particle diameter of irregular shaped tabular silver nanoparticles-
About each of the irregular-shaped tabular silver nanoparticle selected above, the diameter when it was made into the circle of the same area was calculated | required, and this average value of 100 pieces was made into the number average particle diameter of an irregular-shaped tabular silver nanoparticle.

-Average aspect ratio of amorphous silver nanoparticles-
The aspect ratio was determined for each of the amorphous tabular silver nanoparticles selected above by the same method as described above in “-Selection of tabular silver nanoparticles—”, and the average value of 100 values was determined to be amorphous. The average aspect ratio of the flat silver nanoparticles was taken.

-Average irregularity of irregular shaped flat silver nanoparticles-
The degree of irregularity was determined by the above-mentioned method for each of the amorphous tabular silver nanoparticles selected above by the same method as described above in “-Selection of amorphous tabular silver nanoparticles”. The average value was taken as the average degree of irregularity of the irregular shaped tabular silver nanoparticles.

≪Production of substrate with black matrix (shading image) ≫
<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〕
・ Metal fine particle dispersion A-1 ・ ・ ・ 40.00 parts ・ Propylene glycol monomethyl ether acetate ・ ・ ・ 28.6 parts ・ Methyl ethyl ketone ・ ・ ・ 37.6 parts ・ Fluorosurfactant (trade name: F780F, large (Made by Nippon Ink Chemical Co., Ltd.)
・ ・ ・ 0.2 part ・ Hydroquinone monomethyl ether ・ 0.001 part ・ Benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, molecular weight 30000) ・ ・ ・ 2.1 parts ・ Dipentaerythritol hexa Acrylate (KAYARAD DPHA (Nippon Kayaku Co., Ltd.))
Here, the amount of dipentaerythritol hexaacrylate added is such that the mass ratio is 0.9 when the amount of benzyl methacrylate / methacrylic acid copolymer in the coating solution is 1, and the above-mentioned metal fine particle dispersion liquid The amount was such that the volume fraction of A-1 was 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.
・ Polyvinyl alcohol (trade name: PVA205, manufactured by Kuraray Co., Ltd.) 3.0 parts ・ Polyvinylpyrrolidone (trade name: PVP-K30, manufactured by IS Japan Co., Ltd.)
・ ・ ・ 1.3 parts ・ Distilled water ・ ・ ・ 50.7 parts ・ Methyl alcohol ・ ・ ・ 45.0 parts

<Production of photosensitive material by coating method>
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. Thereafter, this substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
Subsequently, after cooling the substrate and adjusting the temperature to 23 ° C., the dry film thickness was adjusted on the substrate using a glass substrate coater MH-1600 (manufactured by FAS Asia) equipped with a slit-like nozzle. The photosensitive light-shielding layer coating solution was applied to a thickness of 1.00 μm and dried at 100 ° C. for 5 minutes to form a photosensitive composition layer (application process). Next, using the slit-shaped nozzle on this photosensitive composition layer, the protective layer coating solution obtained above was applied to a dry film thickness of 1.5 μm, and dried at 100 ° C. for 5 minutes for protection. A layer was formed to prepare a photosensitive material.

<Formation of black matrix>
In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the photosensitive material and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface The distance between the protective layer application surfaces was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² . Next, development processing (33 ° C., 20 seconds) was performed using a development processing solution T-CD1 (produced by Fuji Photo Film Co., Ltd .; alkaline developer) diluted 5 times (pH in use: 10.2). went. A black matrix having a screen size of 10 inches, a pixel count of 480 × 640, a black matrix width of 24 μm, and an aperture of the pixel portion of 86 μm × 304 μm was obtained.
As described above, a substrate with a black matrix (light-shielded image) was obtained.

≪Evaluation≫
The following evaluation was performed about the board | substrate with a black matrix obtained above. The evaluation results are shown in Table 2 below.
<Reflectance measurement>
Using an absolute reflectance measuring device ARV-474 manufactured by JASCO Corporation in combination with a spectrophotometer V-560 manufactured by JASCO Corporation. Absolute reflectance was measured. The measurement angle is 5 degrees and the wavelength is 500 nm.

<Quality (color) evaluation>
The photosensitive light-shielding layer before and after the baking was visually observed to evaluate its quality (color).

[Example 2]
In Example 1, silver nanoparticle dispersion liquid A-1 was prepared in the same manner as in Example 1 except that Exemplified Compound PO-2 was used instead of Exemplified Compound PO-1 to prepare a silver nanoparticle dispersion A-1. A particle dispersion A-2 was prepared. About the prepared silver nanoparticle dispersion liquid A-2, it carried out similarly to Example 1, and measured the silver nanoparticle. The measurement results are shown in Table 1 below.
Further, in Example 1, “Preparation of substrate with black matrix” in Example 1 except that silver nanoparticle dispersion liquid A-1 was changed to silver nanoparticle dispersion liquid A-2. Was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

[Example 3]
In Example 1, in the preparation of the silver nanoparticle dispersion A-1, Example 1 was used except that an aqueous ascorbic acid solution was used instead of the hydroquinone aqueous solution and that the pH was adjusted to 7 instead of adjusting to pH 4. Similarly, a silver nanoparticle dispersion liquid A-3 was prepared. The silver particles had the same color as that immediately after the formation of the particles. About the prepared silver nanoparticle dispersion liquid A-3, it carried out similarly to Example 1, and measured the silver nanoparticle. The measurement results are shown in Table 1 below.
Further, in Example 1, “Preparation of substrate with black matrix” in Example 1 except that the silver nanoparticle dispersion liquid A-1 was changed to the silver nanoparticle dispersion liquid A-3. Was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

[Example 4]
In Example 1, except for the following operations, a substrate with a black matrix was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2 below.

<Production of transfer material>
A thermoplastic resin layer coating solution composed of the following formulation H1 is applied on a 75 μm thick polyethylene terephthalate film temporary support using a slit-like nozzle so that the dry thickness is 5 μm, and is heated at 100 ° C. for 3 minutes. Dried.
Next, an intermediate layer coating solution having the same composition as that of the protective layer coating solution in Example 1 was applied onto the thermoplastic resin layer so that the dry film thickness was 1.5 μm, and further at 100 ° C. for 5 minutes. Dried to form an intermediate layer. Further, the photosensitive light-shielding layer coating solution in Example 1 was applied onto the intermediate layer so that the dry film thickness was 0.6 μm, thereby forming a photosensitive light-shielding layer. Further, a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded on the photosensitive light-shielding layer.
As described above, a transfer material having a configuration in which the temporary support / thermoplastic resin layer / intermediate layer / photosensitive light-shielding layer / protective film was laminated in this order was obtained.

Coating liquid for thermoplastic resin layer: Formulation H1
Methanol: 11.1 parts Propylene glycol monomethyl ether acetate: 6.36 parts Methyl ethyl ketone: 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (co-polymer) Polymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 90,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer ( Copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 80,000, Tg≈100 ° C.) 13.6 parts. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・ ・ ・ 9.1 parts ・ Surfactant 1 (Megafac F780F, Dainippon Ink & Chemicals, Inc.) Business Co., Ltd.)
... 0.54 parts

<< Production of photosensitive material by transfer method >>
After peeling off the protective film of the transfer material obtained above, the transfer material is overlaid on the glass substrate so that the light-shielding layer of the transfer material is in contact with the glass substrate (thickness 1.1 mm), and a laminator (manufactured by Hitachi Industries, Ltd.) (Lamic type II) was used to bond at a pressure of 0.8 Pa and a temperature of 130 ° C.
Subsequently, the polyethylene terephthalate temporary support was peeled off to obtain a photosensitive material.

≪Preparation of black matrix≫
In Example 1, the black matrix was prepared in the same manner as in Example 1 except that the photosensitive material produced by the coating method used for producing the black matrix was changed to the photosensitive material produced by the transfer method prepared above. An attached substrate was produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

[Comparative Example 1]
In Example 1, in the preparation of the silver nanoparticle dispersion A-1, the silver nanoparticle dispersion S-1 was prepared in the same manner as in Example 1 except that silver nitrate, sodium sulfite and hydroquinone were added simultaneously over 30 minutes. Prepared. With respect to the prepared silver nanoparticle dispersion liquid S-1, silver nanoparticles were measured in the same manner as in Example 1. The measurement results are shown in Table 1 below.
Further, in Example 1, “Preparation of substrate with black matrix” in Example 1 except that silver nanoparticle dispersion liquid A-1 was changed to silver nanoparticle dispersion liquid S-1, and the substrate with black matrix was changed. Was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

[Comparative Example 2]
In Example 3, in the preparation of the silver nanoparticle dispersion A-3, except that 50 mL of 1.0 mol / L hydroquinone aqueous solution was added and 50 mL of 1.0 mol / L sodium sulfite aqueous solution was not used. In the same manner as in Example 3, a silver nanoparticle dispersion liquid S-2 was prepared. About the prepared silver nanoparticle dispersion liquid S-2, it carried out similarly to Example 1, and measured the silver nanoparticle. The measurement results are shown in Table 1 below.
Further, in Example 1, “Preparation of substrate with black matrix” in Example 1 except that the silver nanoparticle dispersion liquid A-1 was changed to silver nanoparticle dispersion liquid S-2. Was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

  As shown in Table 2, the black matrices of Examples 1 to 4 including irregular flat metal fine particles showed low reflectance. On the other hand, the black matrixes of Comparative Examples 1 and 2 that did not contain amorphous flat metal fine particles had high reflectance.

[Comparative Example 3]
In Example 1, in “Preparation of substrate with black matrix”, silver nanoparticle dispersion liquid A-1 was changed to silver nanoparticle dispersion liquid S-3 prepared by the following method in the same manner as in Example 1. A substrate with a black matrix was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4 below.

<< Preparation of silver nanoparticle dispersion S-3 >>
The exemplified compound PO-1 was added to 4000 mL of pure water so as to be 6.0 × 10 ⁻³ % (W / W), and 40 mL of 1.0 mol / L calcium nitrate aqueous solution was added and stirred. Then, 200 mL of 1.0 mol / L silver nitrate aqueous solution was added over 30 seconds, and then 200 mL of 1.0 mol / L sodium sulfite aqueous solution and 100 mL of 1.0 mol / L hydroquinone aqueous solution were added over 30 seconds. An ultrafiltration module SIP1013 (manufactured by Asahi Kasei Co., Ltd .; molecular weight cut off 6000), a magnet pump, and a stainless steel cup were connected with a silicon tube to obtain an ultrafiltration device. The silver fine particle dispersion (aqueous solution) was put into a stainless steel cup, and ultrafiltration was performed by operating a pump. When the filtrate from the module reached 2.5 liters, 2.5 liters of distilled water was added to the stainless steel cup for washing. After the above washing was repeated 10 times, concentration was performed until the amount of the mother liquor was 50 ml. Methyl ethyl ketone was added to the above-mentioned aggregated silver fine particles so that the silver content was 8 mass%, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifer II type” ultrasonic homogenizer manufactured by Branson.
Then, 40 nm ultrasonic wave was irradiated for 10 minutes with “Model 2000bdc-h 40: 0.8 type ultrasonic homogenizer” manufactured by Branson, and silver nanoparticle dispersion S-3 (metal fine particle dispersion) was applied. Obtained.
During the ultrasonic irradiation, the liquid was cooled by COOLNICS CTW400 manufactured by Yamato Scientific Co., Ltd. so that the liquid was maintained at 25 ° C.
The content of water in the silver nanoparticle dispersion liquid S-3 obtained as described above was 19.1% by mass. About the silver nanoparticle in this silver nanoparticle dispersion liquid S-3, the same measurement as Example 1 was performed. The measurement results are shown in Table 3 below.

<< Measurement of optical density >>
About the board | substrate with a black matrix (light-shielding image) produced in Examples 1-4 and Comparative Example 3, the optical density was measured as follows. The measurement results are shown in Table 4 below. First, using a material in which a black matrix is formed, a thin film layer having an OD of 3.0 or less is formed on a transparent substrate, and each of the examples is not exposed in a pattern. A sample for measurement (film-like) was obtained through the same steps. This transmission optical density was measured at 555 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100) (OD). Separately, the transmission optical density of the glass substrate was measured by the same method (OD ₀ ).
The value obtained by subtracting OD ₀ from OD was taken as the transmission optical density of the black matrix. Using a contact-type surface roughness meter P-10 (manufactured by KLA-Tencor Corporation), the film thickness of the measurement sample is measured, and from the relationship between the transmission optical density and the film thickness of the measurement results, Examples 1-4 , And the optical density of the black matrix having a film thickness produced in Comparative Example 3 was calculated.

≪Preparation of color filter≫
Using the black matrix (light-shielding image) -provided substrates prepared in Examples 1 to 4 and Comparative Example 3, respectively, transfer-type photosensitive materials described in paragraph numbers [0158] to [0170] of JP-A-2006-251237. A color filter having a predetermined size and shape of red, green, and blue was formed by a color filter production method using a conductive resin film, and the color filters of Examples 1 to 4 and Comparative Example 3 were produced.

≪Production of liquid crystal display device≫
Using the color filter obtained above, the liquid crystal display devices of Examples 1 to 4 and Comparative Example 3 were manufactured by the method for manufacturing a liquid crystal display device described in paragraph [0171] of JP-A-2006-251237. Each was produced.

≪Evaluation of display unevenness≫
For the liquid crystal display devices of Examples 1 to 4 and Comparative Example 3, a gray test signal was input, and display unevenness was confirmed. The evaluation results are shown in Table 4 below.

  As shown in Table 4, the black matrices of Examples 1 to 4 showed high optical density, and no display unevenness was observed in the liquid crystal display devices of Examples 1 to 4. On the other hand, display unevenness occurred in the liquid crystal display device of Comparative Example 3.

Claims (15)

  A substrate with a light-shielding image having a light-shielding image containing at least metal fine particles, wherein the metal fine particles include amorphous flat-plate metal fine particles.   2. The substrate with a light-shielding image according to claim 1, wherein among the metal fine particles, 25% or more of the metal fine particles having a particle diameter of 10 nm or more are amorphous flat metal fine particles.   3. The substrate with a light-shielding image according to claim 1, wherein the metal fine particles contain one or more metals selected from the group consisting of groups 2 to 14 of the periodic table. .   The substrate with a light-shielding image according to any one of claims 1 to 3, wherein the metal fine particles are silver fine particles or alloy fine particles containing silver.   5. The substrate with a light-shielding image according to claim 1, wherein the irregular plate-like metal fine particles have an average degree of irregularity of 1.3 or more.   6. The substrate with a light-shielding image according to claim 1, wherein the amorphous flat metal fine particles have an average aspect ratio of 3.0 or more.   The substrate with a light-shielding image according to any one of claims 1 to 6, wherein the irregular-shaped flat metal fine particles have a number average particle diameter of 5 to 50 nm.   A dispersion containing at least metal fine particles, wherein the metal fine particles include irregular flat metal fine particles and contain 10% or less of water with respect to the total mass of the metal fine particles.   The metal fine particle dispersion according to claim 8, wherein 25% or more of the metal fine particles are amorphous flat metal fine particles with respect to the total number of metal fine particles having a particle diameter of 10 nm or more.   The metal fine particle dispersion according to claim 8 or 9, further comprising a dispersion polymer having at least one sulfur atom and / or nitrogen atom.   11. The metal fine particle dispersion according to claim 10, wherein the dispersion polymer having at least one sulfur atom and / or nitrogen atom has alkali solubility.   A transfer material comprising a light-shielding layer formed using the metal fine particle dispersion according to any one of claims 8 to 11 on a temporary support.   The board | substrate with a light-shielding image formed using the transfer material of Claim 12.   A color filter comprising the substrate with a light-shielding image according to any one of claims 1 to 7 and 13.   A display device comprising the color filter according to claim 14.