JP2007164072A - Colored composition, forming method of dark colored separating image wall, color filter and its manufacturing method and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition by which occurrence of image unevenness and variation of contrast due to time elapse after image formation can be suppressed; a forming method of a dark colored separating image wall by which the dark colored separating image wall, where occurrence of display unevenness and variation of display contrast due to time elapse can be suppressed and an image of high contrast can be stably displayed, can be manufactured; a color filter by which occurrence of display unevenness and variation of display contrast due to time elapse can be suppressed and the image of high contrast can be stably displayed; and further its manufacturing method and a liquid crystal display device. <P>SOLUTION: The colored composition contains metallic particles or metal-containing particles and residual voltage is 200 mV or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coloring composition suitable for producing a color filter constituting a liquid crystal display device, a method for forming a dark color separation wall using the same, a color filter and a method for producing the same, and a liquid crystal display device.

  In recent years, in order to improve the contrast of a display image, a black matrix has been required to have a high optical density of 4.0 or more. On the other hand, since the surface smoothness of the color filter is impaired when the thickness of the black matrix is large, it is necessary to form a thin film.

  Conventionally, a metal thin film has been used for producing a black matrix for a display device having a high light shielding property. This is after applying a photoresist on a metal thin film such as chromium formed by vapor deposition or sputtering, and then exposing and developing the photoresist using a photomask having a pattern for a light shielding film for a display device. This is due to a method in which the exposed metal thin film is etched and finally the photoresist remaining on the metal thin film is peeled and removed (see, for example, Non-Patent Document 1).

  Since this method uses a metal thin film, a high light-shielding effect can be obtained even if the film thickness is small, but 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 and the cost is increased. In addition, since it is a metal film, the reflectance is extremely high, and there is a problem that display contrast is lowered under strong external light. Corresponding to these, a method using a low-reflective chromium film (such as one composed of two layers of metal chromium and chromium oxide) has been proposed, but it cannot be denied that the cost is further increased. Furthermore, since the waste liquid containing metal ions is discharged in the etching process, there is a great disadvantage that the environmental load is large. In particular, chromium that is most frequently used is harmful and has a very large environmental impact.

  On the other hand, there is a technique using carbon black as one of techniques for obtaining a black matrix with a small environmental load (see, for example, Patent Document 1). In this method, a photosensitive resin composition containing carbon black is applied to a substrate, dried, and exposed and developed to form a black matrix.

  However, since carbon black has a low optical density per unit coating amount, it tends to have a large film thickness in order to ensure a high light-shielding property and optical density. For example, an optical density 4.0 equivalent to the above metal film is used. If it is going to ensure, film thickness will be 1.2-1.5 micrometers. Therefore, when red, blue, and green pixels are formed after the black matrix is formed, there is a drawback that the surface of the color filter becomes unsmooth due to the step of the pixel edge portion and the display quality deteriorates.

In addition to the above, as a method for obtaining a black matrix having a small environmental load and a high optical density with a thin film, a method using metal fine particles instead of carbon black is known (see, for example, Patent Documents 2 to 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 2004-240039 A JP 2005-17322 A "Color TFT liquid crystal display" p.218-p.220, published by Kyoritsu Shuppan Co., Ltd. (April 10, 1997)

  However, although the metal fine particles are useful in that the black matrix is surely configured to be a thin film with a high optical density, if the residual voltage exceeds 200 mV, the liquid crystal panel produced over time may have a failure such as display unevenness. Occurs, the display contrast of the image gradually decreases, and as a result, the effect of improving the display contrast due to the selection of the metal fine particles is greatly impaired.

  The present invention has been made in view of the above, and a colored composition in which occurrence of image unevenness and contrast variation with time after image formation is suppressed, and occurrence of display unevenness and display contrast variation over time. , A method of forming a dark color separation wall capable of producing a dark color separation wall capable of stably displaying a high-contrast image, generation of display unevenness over time, and variation in display contrast are suppressed, It is an object of the present invention to provide a color filter capable of stably displaying an image with high contrast, a method for manufacturing the same, and a liquid crystal display device, and to achieve the object.

Specific means for achieving the above object are as follows.
<1> A colored composition containing metal particles or metal particles and having a residual voltage of 200 mV or less.
<2> The colored composition according to <1>, wherein the colored composition is used for forming a dark color separation wall separating a colored pixel portion formed by applying a droplet.
<3> A dark particle having a step of exposing a layer containing metal particles or metal-containing particles and a resin or a precursor thereof and having a residual voltage of 200 mV or less in a pattern and developing to form a dark color separation wall. This is a method of forming a color separation wall.
<4> The method for forming a dark color separation wall according to <3>, wherein at least one of the particles is a particle having a silver-tin alloy part.
<5> The method for forming a dark color separation wall according to <3> or 4>, wherein the optical density of the dark color separation wall is 2.5 or more.

<6> A method for producing a color filter having a pixel group composed of a plurality of colored pixels of two or more colors and a dark color separation wall separating each colored pixel of the pixel group, wherein the particle includes metal particles or metal And a resin or a precursor thereof, a layer having a residual voltage of 200 mV or less is exposed in a pattern and developed to form a dark color separation wall, and a recess between the formed dark color separation walls And a step of applying a droplet of a colored liquid composition to form a plurality of colored pixels of two or more colors.
<7> A color filter produced by the method for producing a color filter according to <6>.
<8> A liquid crystal display device comprising the color filter according to <7>.

  According to the present invention, a colored composition in which the occurrence of image unevenness and contrast variation with time after image formation is suppressed, and the occurrence of display unevenness and display contrast variation over time can be suppressed, and an image with high contrast can be obtained. A method of forming a dark color separation wall that can produce a dark color separation wall capable of stable display, generation of display unevenness over time, and display contrast fluctuation can be suppressed, and stable display of high contrast images is possible. A color filter, a manufacturing method thereof, and a liquid crystal display device can be provided.

  Hereinafter, the colored composition of the present invention will be described in detail, and the details of the method for forming a dark color separation wall, the color filter and the manufacturing method thereof, and the liquid crystal display device of the present invention will be described through the description.

<Coloring composition>
The colored composition of the present invention includes at least one kind of metal particles and metal-containing particles, and is configured to have a residual voltage of 200 mV or less. Since it contains metal particles or metal-containing particles, a high color density can be obtained while forming a thin film. For example, it is suitable for production of dark color separation walls such as a black matrix, and the residual voltage is set to 200 mV or less. Since the occurrence of image unevenness and contrast fluctuations over time of the generated images are suppressed, for example, when a liquid crystal display device or the like is configured, display unevenness can occur over time or display contrast fluctuations can be suppressed. Thus, an image with high contrast can be displayed.

The residual voltage is measured as follows according to the method described in paragraphs [0078] to [0082] of JP-A-2003-26918.
5 V DC is applied between the liquid crystal cells at 23 ° C. for 30 minutes and left for 1 second. After 10 minutes, the residual voltage [V] remaining in the liquid crystal cell is measured. To do. In the liquid crystal cell, two black matrix substrates each having a black matrix formed on one side of the substrate are prepared, and a 6 μm spacer is spread on the black matrix forming surface of one black matrix substrate, and then the other black matrix substrate is overlapped. A liquid crystal (HA5073LA, manufactured by Chisso Petrochemical Co., Ltd.) injected between two substrates is used.

  The residual voltage is adjusted by adjusting the number of washings (centrifugation → supernatant removal → pure addition → dispersion) after preparation of the particles to be used (metal particles or metal-containing particles), the removal amount of the supernatant liquid to be removed, It can be performed by refining raw materials used for particle formation.

-Metal particles or particles having metal-
The colored composition of the present invention contains at least one of metal particles and metal-containing particles (hereinafter sometimes referred to as “metal-based fine particles according to the present invention”).
The metal in the metal particles and the metal-containing particles is not particularly limited, and any metal may be used. The metal particles may be used in combination of two or more metals, and may be used as an alloy. Alternatively, composite fine particles of a metal and a metal compound may be used.

  As a metal particle, what is formed from a metal or a metal and a metal compound is preferable, and what is formed from a metal is especially preferable.

  In particular, a metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is preferably included as a main component. Moreover, it is preferable to contain the metal chosen from the group which consists of 2-14 groups, 2nd group, 8th group, 9th group, 10th group, 11th group, 12th group, 13th group, and More preferably, a metal selected from the group consisting of Group 14 is included as a main component. Among these metals, the metal particles are metals in the fourth period, the fifth period, or the sixth period, and are of Group 2, Group 10, Group 11, Group 12, or Group 14. Metal particles are more preferred.

  Preferred examples of the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, The at least 1 sort (s) chosen from antimony, lead, and these alloys can be mentioned. More preferable metals are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, calcium, iridium, and alloys thereof, and more preferable metals are copper, silver, gold, platinum, palladium, tin, and calcium. And at least one selected from these alloys, and particularly preferred metals are at least one selected from copper, silver, gold, platinum, tin, and alloys thereof. In particular, silver is preferable (as colloidal silver is preferable as silver), and particles having a silver-tin alloy part are most preferable. The particle | grains which have a silver tin alloy part are mentioned later.

<Metal compound particles>
The “metal compound” is a compound of the metal and an element other than the metal. Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles. Of these, sulfide particles are preferred because of their color tone and ease of fine particle formation.
Examples of metal compounds include copper oxide (II), iron sulfide, silver sulfide, copper sulfide (II), and titanium black. From the viewpoint of color tone, ease of fine particle formation and stability, silver sulfide is particularly preferable. preferable.

<Composite particle>
Composite particles are particles in which a metal and a metal compound are combined into one particle. For example, the inside of the particle and the surface are different in composition, and the two kinds of particles are combined. Further, each of the metal compound and the metal may be one type or two or more types.
Specific examples of the composite fine particles of the metal compound and the metal include preferably composite fine particles of silver and silver sulfide, and composite fine particles of silver and copper (II) oxide.

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

  Moreover, as a preferable core material, at least 1 sort (s) chosen from copper, silver, gold | metal | money, palladium, nickel, tin, bismuth, anmotine, lead, and these alloys can be mentioned.

There is no restriction | limiting in particular in the preparation methods of the composite particle which has a core shell structure, The following are mentioned as a typical method.
(1) A method of forming a metal compound shell on the surface of metal fine particles produced by a known method by oxidation, sulfurization, etc. For example, metal fine particles are dispersed in a dispersion medium such as water, and sodium sulfide or This is a method of adding a sulfide such as ammonium sulfide. By this method, the surface of the particles can be sulfided to form core / shell particles.
In this case, the metal particles to be used can be produced by a known method such as a gas phase method or a liquid phase method. The method for producing metal particles is described in, for example, “Latest Trend II in Technology and Application of Ultrafine Particles” (Sumibe Techno Research Co., Ltd., issued in 2002).
(2) A method of continuously forming a metal compound shell on the surface in the process of producing metal particles. For example, a reducing agent is added to a metal salt solution to reduce a part of metal ions to form metal fine particles. And then adding a sulfide to form a metal sulfide around the produced metal fine particles.

As the metal particles, commercially available ones can be used, and the metal particles can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
Rod-shaped silver fine particles are obtained by adding spherical silver fine particles as seed particles, then adding a silver salt, and using a reducing agent with relatively weak reducing power such as ascorbic acid in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide). By using it, a silver bar or a wire can be obtained. This is described in Advanced Materials 2002, 14, 80-82. Similar descriptions are made in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189.

Further, as a method using electrolysis, Materials Letters 2001, 49, 91-95 and a method of generating a silver bar by irradiating microwaves are described in Journal of Materials Research 2004, 19, 469-473. . Journal of Physical Chemistry B 2003, 107, 3679-3683 is an example in which reverse micelles and ultrasonic waves are used in combination.
Similarly, gold is also described in Journal of Physical Chemistry B 1999, 103, 3073-3077 and Langmuir 1999, 15, 701-709, Journal of American Chemical Society 2002, 124, 14316-143.
The method for forming the rod-like particles can be prepared by improving the method described above (adjusting the addition amount and controlling the pH).

  The metal particles in the present invention can be obtained by combining various types of particles in order to approximate an achromatic color. By changing the particles from a spherical shape or a cubic shape to a flat plate shape (hexagonal shape, triangular shape) or a rod shape, a higher transmission density can be obtained, and according to this, a thin film can be achieved when the light shielding layer is formed.

  The particles having a silver-tin alloy part include those made of a silver-tin alloy part, those made of a silver-tin alloy part and another metal part, and those made of a silver-tin alloy part and another alloy part.

  In the particles having a silver-tin alloy part, at least a part of the particles is composed of a silver-tin alloy. For example, HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X) manufactured by Noran. And a spectrum measurement of the center 15 nm □ area of each particle with an acceleration voltage of 200 kV.

  Particles having a silver-tin alloy part have a high black density, can exhibit excellent light-shielding performance in a small amount or in a thin film, and have high thermal stability, so that the black density is not impaired and high temperature (for example, 200 degrees or more) Heat treatment can be performed, and a high light-shielding property can be secured stably. For example, it is suitable for a color filter light-shielding film (so-called black matrix) that requires a high degree of light-shielding properties and is generally subjected to a baking process.

  The particles having a silver-tin alloy part are preferably obtained by combining (for example, alloying) Ag and tin (Sn) with a silver (Ag) ratio of 30 to 80 mol%. By setting the Ag ratio in the above-described range, it is possible to obtain a high black density with high thermal stability at a high temperature range and low light reflectance. In particular, particles having an Ag ratio of 75 mol%, that is, AgSn alloy particles are easy to produce, and the obtained particles are also stable and preferable.

  Particles having a silver-tin alloy part can be formed by alloying by a general method such as heating, melting and mixing in a crucible or the like, but the melting point of Ag is around 900 ° C. Since the melting point of Sn is around 200 ° C. and there is a large difference between the melting points of the two, and an extra fine particle forming step after compounding (for example, alloying) is required, it is preferable to use the particle reduction method. . That is, the Ag compound and the Sn compound are mixed and reduced, and the metal Ag and the metal Sn are simultaneously precipitated at a position close to each other, thereby achieving composite (for example, alloying) and micronization at the same time. It is. Since Ag tends to be reduced and tends to precipitate before Sn, it is preferable to control the precipitation timing by making Ag and / or Sn a complex salt.

Preferred examples of the Ag compound include silver nitrate (AgNO ₃ ), silver acetate (Ag (CH ₃ COO)), silver perchlorate (AgClO ₄ · H ₂ O), and the like. Of these, silver acetate is particularly preferred. Preferred examples of the Sn compound include stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), stannous acetate (Ag (CH ₃ COO) ₂ ), and the like. Of these, stannous acetate is particularly preferable.

  As the reduction, a method using a reducing agent, a method of reducing by electrolysis, and the like can be mentioned as preferable reduction methods. Among these, the former method using a reducing agent is preferable in that fine particles can be obtained. Examples of the reducing agent include hydroquinone, catechol, paraaminophenol, paraphenylenediamine, and hydroxyacetone. Among these, hydroxyacetone is particularly preferable because it is easily volatilized and does not adversely affect the display device.

As the particle size distribution of the metal fine particles, it is preferable that the particle distribution is approximated by a normal distribution, and the particle size distribution width D ⁹⁰ / D ^{10 of the} number average particle diameter is 1.2 or more and less than 20. Here, the particle diameter is the major axis length L as the particle diameter, D ⁹⁰ is the particle diameter at which 90% of the particles close to the average particle diameter are found, and D ¹⁰ is the particle diameter close to the average particle diameter. 10% is the particle diameter found. From the viewpoint of color tone, the particle size distribution width is preferably 2 or more and 15 or less, more preferably 4 or more and 10 or less. If the distribution width is less than 1.2, the color tone may be close to a single color, and if it is 20 or more, turbidity may occur due to scattering by coarse particles.

In addition, the measurement of the particle size distribution width D ⁹⁰ / D ¹⁰ is specifically performed by measuring 100 metal particles in the film at random by the method of measuring the triaxial diameter, and determining the major axis length L. and particle diameter, and normal distribution approximating the particle size distribution, the particle diameter by the number of close to the average particle diameter of the particles becomes 90% of the range as D ^90, the particle diameter in the range a few 10% from the average particle size with D ^10, it is possible to calculate the ^D 90 ^/ D ^10.

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

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

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

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

Measurement of length L, width b, and thickness t Measurement of length L, width b, and thickness t can be made with a surface observation diagram (× 500000) by an electron microscope and an atomic force microscope (AFM). The average value of the values measured for 100 rod-shaped metal fine particles. The atomic force microscope (AFM) has several operation modes, which are selectively used depending on the application.
Broadly divided into the following three.
(1) Contact method: A method in which the probe is brought into contact with the sample surface and the surface shape is measured from the displacement of the cantilever. (3) Non-contact method: A method for measuring the surface shape from changes in the cantilever vibration frequency without contacting the probe with the sample surface.

On the other hand, the non-contact method needs to detect extremely weak attractive force with high sensitivity. Therefore, it is difficult to detect the static force by directly measuring the displacement of the cantilever, and the mechanical resonance of the cantilever is applied.
The above three methods can be mentioned, and any method can be selected according to the sample.

  In the present invention, the electron microscope can be measured at an acceleration voltage of 200 kV using an electron microscope JEM2010 manufactured by JEOL. Moreover, the atomic force microscope (AFM) includes SPA-400 manufactured by Seiko Instruments Inc. In the measurement with an atomic force microscope (AFM), the measurement is facilitated by inserting polystyrene beads in the comparison.

  In the present invention, the metal particles or the metal-containing particles are preferably metal particles or metal-containing metal compound particles, more preferably silver particles or silver-containing silver compound particles, and particles containing a silver-tin alloy part. Most preferred.

<Pigments and other>
In the present invention, other fine particles such as a pigment may be used in addition to the metal fine particles or together with the metal fine particles. When a pigment is used, the hue can be made closer to black.

Suitable examples of the pigment include carbon black, titanium black, and graphite.
As an example of carbon black, Pigment Black 7 (carbon black CI No. 77266) is preferable. Examples of commercially available products include Mitsubishi Carbon Black MA100 (manufactured by Mitsubishi Chemical Corporation) and Mitsubishi Carbon Black # 5 (manufactured by Mitsubishi Chemical Corporation).
As an example of titanium black, TiO ₂ , TiO, TiN and a mixture thereof are preferable. Examples of commercially available products include (trade names) 12S and 13M manufactured by Mitsubishi Materials Corporation. The average particle size of titanium black is preferably 40 to 100 nm.
As an example of graphite, a particle having a Stokes diameter of 3 μm or less is preferable. When graphite exceeding 3 μm is used, the contour shape of the light shielding pattern becomes non-uniform and sharpness may be deteriorated. Further, most of the particle diameter is desirably 0.1 μm or less.

  Known pigments other than the pigments can also be used. In general, the pigment is roughly classified into an organic pigment and an inorganic pigment. In the present invention, the organic pigment is preferable. Examples of pigments that can be suitably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The hue of the organic pigment is preferably, for example, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, or a black pigment.

Hereinafter, fine particles (coloring agents) such as pigments that can be used in the coloring composition are listed. However, the present invention is not limited to these.
Specific examples of the fine particles include the color materials described in JP-A-2005-17716 [0038] to [0040], the pigments described in JP-A-2005-361447 [0068] to [0072], and the like. The colorants described in Kaikai 2005-17521 [0080] to [0088] can be preferably used.

  In addition, it can also be used as appropriate by referring to those described in “Handbook of Pigment, Japan Pigment Technology Association, Seibundo Shinkosha, 1989”, “COLOUR INDEX, THE SOCIETY OF DYES & COLORIST, THIRD EDITION, 1987”. .

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

  The sphere equivalent diameter of the pigment is preferably 5 nm to 5 μm, particularly preferably 10 nm to 1 μm, and more preferably 20 nm to 0.5 μm for color filters.

--- Dispersion of metal fine particles-
The fine particles in the present invention are preferably present in a stable dispersed state, for example, more preferably in a colloidal state. In the colloidal state, for example, it is preferable that the metal fine particles are substantially dispersed in the fine particle state.

  As a dispersant for dispersion, polymers such as thiol group-containing compounds, amino acids or derivatives thereof, peptide compounds, polysaccharides and natural polymers derived from polysaccharides, synthetic polymers, and gels derived therefrom are used. be able to.

The kind of the thiol group-containing compound is not particularly limited, and any compound having one or more thiol groups may be used. Examples of the thiol group-containing compound include alkyl thiols (eg, methyl mercaptan, ethyl mercaptan, etc.), aryl thiols (eg, thiophenol, thionaphthol, benzyl mercaptan, etc.), and the like.
Examples of the amino acid or derivative thereof include cysteine and glutathione. Examples of the peptide compound include dipeptide compounds, tripeptide compounds, tetrapeptide compounds containing cysteine residues, and five or more amino acid residues. Examples of the dispersant include proteins (eg, globular proteins having metallothionein or cysteine residues arranged on the surface). However, the present invention is not limited to these.

Examples of the polymers include protective colloidal polymers such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkyleneamine, polyalkyl acid partial alkyl ester, polyvinyl pyrrolidone (PVP), and polyvinyl pyrrolidone copolymer. Etc.
For the polymer that can be used as the dispersant, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.

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

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

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

-Resin or its precursor-
The colored composition of the present invention can be suitably configured using at least one of a resin and its precursor. Here, the resin is a polymer component as a binder, and the precursor of the resin is a component that constitutes the resin when polymerized, and includes so-called monomers and oligomer components.

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

  The resin is preferably selected to have an acid value in the range of 30 to 400 mg KOH / g and a weight average molecular weight in the range of 1,000 to 300,000.

  In addition to the above, for the purpose of improving various performances, for example, the strength of the cured film, an alcohol-soluble polymer may be added within a range that does not adversely affect developability and the like. Examples of the alcohol-soluble polymer include alcohol-soluble nylon and epoxy resin.

  Examples of the “resin precursor” include a monomer that becomes a resin by being cured. These will be described later.

<Dark color separation wall preparation composition>
The coloring composition of this invention can be used suitably for preparation of a deep color separation wall. Hereinafter, a coloring composition suitable for preparation of a dark color separation wall (hereinafter, also referred to as “dark color separation wall preparation composition” and “light-shielding coloring composition”) will be described in detail.

  When the light-shielding layer (the layer before patterning) is formed using the light-shielding coloring composition of the present invention, the optical density per layer thickness of 1 μm of the formed light-shielding layer is preferably 1 or more.

  In addition, the content of the metal-based fine particles (and pigments and other if necessary) in the light-shielding coloring composition is, for example, metal fine particles (and, if necessary, pigments and other during post-baking, such as during the production of a color filter). In consideration of preventing fusion), it is preferable to adjust so as to be about 10 to 90% by mass, preferably 10 to 80% by mass with respect to the mass of the formed light shielding layer. In addition, the content of the metal-based fine particles (and pigments and the like as necessary) is preferably determined in consideration of the change in optical density due to the average particle diameter. The same applies to the content of metal-based fine particles (and pigments, etc., if necessary) contained in the composition for preparing a dark color separation wall having photosensitivity described later.

  The “dark color separation wall” referred to in the present invention is used to include a black matrix. “Black matrix” means a black edge provided around the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or a grid between red, blue and green pixels. And stripe-like black portions, and further, dot-like and linear black patterns for TFT light shielding, etc. The definition of this black matrix is, for example, “Liquid Crystal Display Manufacturing Device Dictionary” (2nd edition, Tadasu Kanno, p. 64, Nikkan Kogyo Shimbun, 1996). Examples of the dark color separation wall include an organic EL display (for example, Japanese Patent Application Laid-Open No. 2004-103507), a front panel of a PDP (for example, Japanese Patent Application Laid-Open No. 2003-51261), and a light shielding of a backlight in PALC.

  The black matrix improves the display contrast, and in the case of an active matrix drive type liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, The optical density OD is 3 or more).

<Coloring composition for preparing photosensitive dark color separation wall>
It is more preferable that the coloring composition for producing a dark color separation wall has photosensitivity.
Specifically, photosensitivity can be imparted by using a photosensitive resin composition. The photosensitive resin composition may be a polymer that serves as a binder, a photopolymerization initiator, and a monomer that has an ethylenically unsaturated double bond and undergoes addition polymerization upon irradiation with light (hereinafter, referred to as “photopolymerizable monomer”). Etc.) is preferable.

The photosensitive resin composition includes those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent. From the viewpoint of safety and the cost of the developer, those that can be developed with an aqueous alkaline solution are preferable, and from this point, it is preferable to use an alkali-soluble polymer as a polymer that serves as a binder.
The photosensitive resin composition may be a negative type in which a part that receives radiation such as light and electron beam as described above is cured, or may be a positive type in which a radiation non-receiving part is cured.

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

  The negative photosensitive resin composition includes a photosensitive resin (photopolymerizable composition) composed of a negative diazo resin and a binder, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin. Examples thereof include compositions. Particularly preferred among these is a photopolymerizable composition containing a photopolymerization initiator, a photopolymerizable monomer, and a binder as basic constituent elements.

  As the photopolymerizable composition, “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” and other components described in JP-A-11-133600 are used. be able to. For example, it is a negative type photosensitive resin composition that can be developed with an alkaline aqueous solution, and contains a carboxylic acid group-containing binder (alkali-soluble binder), a photopolymerization initiator, and a photopolymerizable monomer as main components. A photosensitive resin composition is mentioned. As the alkali-soluble binder, the resins listed in the above-mentioned <Resin or its precursor> section can be preferably used.

  As content of the said alkali-soluble binder, 10-95 mass% is preferable normally with respect to the total solid of the photosensitive coloring composition for dark-colored image separation wall preparation, Furthermore, 20-90 mass% is more preferable. In the range of 10 to 95% by mass, the adhesiveness of the photosensitive resin layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.

Examples of the photopolymerization initiator include a vicinal polyketaldonyl compound described in US Pat. No. 2,367,660, an acyloin ether compound described in US Pat. No. 2,448,828, and described in US Pat. No. 2,722,512. An aromatic acyloin compound substituted with an α-hydrocarbon, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, and a triarylimidazole dimer described in US Pat. No. 3,549,367 Benzothiazole compound and trihalomethyl-s-triazine compound described in JP-B-51-48516, trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, US Trihalomethyl described in Japanese Patent No. 4221976 Oxadiazole compounds, and the like. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer.
In addition to the above, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.

  The above photopolymerization initiator or photopolymerization initiator system may be used by mixing two or more kinds in addition to being used alone, and two or more kinds are particularly preferably used. Moreover, 0.5-20 mass% is common and, as for content of the photoinitiator with respect to the total solid of the photosensitive resin composition, 1-15 mass% is preferable.

  As an example in which good display characteristics can be obtained by increasing the exposure sensitivity without coloring such as yellowing, a combination of a diazole photopolymerization initiator and a triazine photopolymerization initiator can be mentioned. Methyl-5- (p-styrylstyryl) -1,3,4-oxadiazole and 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl)- A combination with 3′-bromophenyl] -s-triazine is most preferred. The ratio of these photoinitiators is a diazole / triazine mass ratio, preferably 95/5 to 20/80, more preferably 90/10 to 30/70, most preferably 80 / 20-60 / 40. These photopolymerization initiators are described in JP-A-1-152449, JP-A-1-254918, and JP-A-2-153353. Furthermore, a benzophenone series is also mentioned as a suitable example.

When the photosensitive coloring composition for dark color separation wall preparation is comprised using a pigment, the ratio of the pigment to the whole solid content of this coloring composition for dark color separation wall preparation is 15-25 mass% In the vicinity, the photopolymerization initiator can be mixed with a coumarin-based compound so that yellowing or the like is not colored and the sensitivity can be increased. As the coumarin compound, 7- [2- [4- (3-hydroxymethylbiperidino) -6-diethylamino] triazinylamino] -3-phenylcoumarin is most preferable. In this case, the ratio between the photopolymerization initiator and the coumarin compound is a mass ratio of photopolymerization initiator / coumarin compound, preferably 20/80 to 80/20, more preferably 30/70 to 70 /. 30 and most preferably 40/60 to 60/40.
However, the photopolymerizable composition that can be used in the present invention is not limited to these, and can be appropriately selected from known ones.

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

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

  Further, urethane acrylates described in JP-B-48-41708, JP-A-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, and 52- Polyfunctional acrylates and methacrylates such as polyester acrylates described in each publication of No. 30490, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

The photopolymerizable monomer may be used alone or in combination of two or more.
The content of the photopolymerizable monomer with respect to the total solid content of the photosensitive coloring composition for producing a dark color separation wall is generally 5 to 50% by mass, and preferably 10 to 40% by mass. When the content is within the above range, neither the photosensitivity nor the image strength is lowered, and the adhesiveness of the photosensitive light-shielding layer is not excessive.

  In addition to the above components, it is preferable to add a thermal polymerization inhibitor to the colored composition for producing a dark color separation wall. Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pt-butylcatechol, 2,6-di-t-butyl-p-cresol, β-naphthol, pyrogallol and other aromatic hydroxy compounds, benzoquinone Quinones such as p-toluquinone, amines such as naphthylamine, pyridine, p-toluidine, phenothiazine, aluminum salt or ammonium salt of N-nitrosophenylhydroxylamine, chloranil, nitrobenzene, 4,4′-thiobis (3-methyl) -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like.

  As a coloring composition for producing a dark color separation wall, if necessary, known additives such as plasticizers, surfactants, adhesion promoters, dispersants, anti-sagging agents, leveling agents, antifoaming agents, Flame retardants, brighteners, solvents and the like can be added.

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

  In addition, when the metal-based fine particles are used as an aqueous dispersion like silver colloid, it is necessary to use an aqueous one as a coloring composition for producing a dark color separation wall. Examples of such a photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and commercially available products such as “SPP-” manufactured by Toyo Gosei Kogyo Co., Ltd. M20 "and the like.

  When producing a dark color separation wall (including a black matrix) using the colored composition for producing a dark color separation wall (including a photosensitive material) of the present invention, it is a thin film and has a high optical density. A dark-colored separation wall (including a so-called black matrix) can be produced.

  The colored composition of the present invention is particularly suitable for forming a dark color separation wall that separates colored pixel portions formed by applying droplets. A method for forming a dark color separation wall that applies droplets to separate the colored pixel portions will be described later.

<Method of forming dark color separation wall>
In the method for forming a dark color separation wall according to the present invention, a layer containing at least one kind of metal particles and metal-containing particles and at least one kind of resin and its precursor and having a residual voltage of 200 mV or less is exposed in a pattern. And a step of developing to form a dark color separation wall (hereinafter, also referred to as “partition wall forming step”), and other steps may be provided as necessary.

The thickness of the layer having a residual voltage of 200 mV or less is preferably about 0.2 to 2.0 μm, more preferably 0.2 to 0.9 μm. Since the layer is obtained by dispersing metal particles or metal-containing particles, a high optical density (2.5 or more) can be obtained with a thin film as described above, and the residual voltage is 200 mV or less. For example, when a liquid crystal display device or the like is configured, display unevenness can occur over time, variation in display contrast can be suppressed, and an image with high contrast can be stably displayed.
In particular, it is effective to use particles having a silver-tin alloy part as metal particles or metal-containing particles.

  The optical density of the dark color separation wall is preferably from 2.5 to 10.0, more preferably from 3.0 to 6.0. When the optical density is within the above range, light shielding properties can be imparted.

The formation of the dark color separation wall in the partition wall forming step is a layer containing metal particles or metal-containing particles, a resin and a precursor thereof, and a residual voltage of 200 mV or less, preferably the dark color separation of the present invention described above. There is no particular limitation as long as it is a method of exposing (developing) (patterning) a layer formed using a coloring composition for producing a painting wall in a pattern.
Hereinafter, a method for producing a dark color separation wall for a display device will be described by taking a method for producing a black matrix pattern as an example.

  In the first method, first, the coloring composition for producing a dark color separation wall according to the present invention, which contains metal particles and at least one of a resin and a precursor thereof and has photosensitivity, is applied to a substrate, The contained photosensitive light shielding layer is formed. Thereafter, pattern formation is performed by removing the light shielding layer other than the pattern by pattern exposure and development to obtain a black matrix (dark color separation image wall). In addition, a layer having the same composition as the intermediate layer described above can be formed on the photosensitive light-shielding layer to form a protective layer. In this case, the coating liquid can be applied using the coating machine listed in the following section--Production of transfer material--. Of these, the spin coating method is preferred.

  In the second method, first, a metal particle containing at least one of a metal particle, a resin, and a precursor thereof, and a non-photosensitive coloring composition for producing a dark color separation wall according to the present invention is applied to a substrate to form a metal particle. A light shielding layer containing is formed. Thereafter, a photosensitive resist solution is applied on the light shielding layer to form a resist layer. Next, after exposing and developing the resist layer by exposure to form a pattern in the resist layer, the non-patterned portion (exposed portion) of the light shielding layer is dissolved in accordance with this pattern, and a pattern is formed in the light shielding layer. Finally, the resist layer is removed to obtain a black matrix (dark color separation wall).

  In the third method, a coating layer is previously formed on a portion other than the pattern on the substrate, and contains metal particles, a resin, and at least one of its precursors. A light-shielding layer containing fine particles is formed by applying a coloring composition for preparing a dark color separation wall. Next, the first formed coating layer is removed together with the upper light shielding layer to obtain a black matrix (dark color separation wall).

The fourth method is a method of producing a dark color separation image wall using a photosensitive transfer material, and the photosensitive transfer material is disposed on a light-transmitting substrate so that the photosensitive light-shielding layer is in contact with the photosensitive material. And then laminating the temporary support from the laminate of the photosensitive transfer material and the light-transmitting substrate, exposing the photosensitive light-shielding layer, and developing to obtain a black matrix (dark color separation wall) It is. This method does not require a cumbersome process and can be performed at low cost.
The photosensitive transfer material will be described later.

Next, exposure and development will be described.
A predetermined mask is arranged above the light shielding layer formed on the substrate, the light shielding layer is exposed through the mask from above the mask, and then developed with a developer to form a pattern image. A dark color separation wall can be produced by performing a washing process. In addition to the method of performing exposure by arranging a mask as described above, it is also possible to obtain a pattern image by directly scanning light based on image data directly without using a mask.

As the light source used for the exposure, any light source capable of irradiating light in a wavelength region capable of curing the photosensitive light-shielding layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an LD, an ultrahigh pressure mercury lamp, a YAG-SHG solid laser, a KrF laser, and a solid laser.
As an exposure amount, it is about 5-300 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.
The exposure machine used at this time is not particularly limited, but in addition to the proximity exposure machine that exposes through a mask, a scattered light exposure machine, a parallel light exposure machine, a stepper, a laser exposure, and the like are used. Can do.

There is no restriction | limiting in particular as a developing solution used for image development, Well-known developing solutions, such as what is described in Unexamined-Japanese-Patent No. 5-72724, can be used, Especially the dilute aqueous solution of an alkaline substance is used preferably. Specifically, the developer preferably has a developing behavior in which the photosensitive resin layer is dissolved. A small amount of an organic solvent miscible with water may be added.
Moreover, it is preferable to spray the pure water with a shower nozzle or the like before the development so that the surface of the photosensitive light-shielding layer is uniformly moistened.

  In the formation method by application of a dark color separation wall and the formation method using a photosensitive transfer material, the alkaline substance used for development includes alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal Carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicate Salts (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxide), trisodium phosphate, and the like. . The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

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

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

--Photosensitive transfer material--
The photosensitive transfer material is provided with a photosensitive light-shielding layer formed using a black composition for producing a dark color separation image wall having at least photosensitivity on a temporary support, and a thermoplastic resin layer as necessary. An intermediate layer, a protective layer, and the like can be provided.
The film thickness of the photosensitive light-shielding layer is preferably about 0.2 to 2.0 μm, more preferably 0.2 to 0.9 μm.

<Temporary support>
As a temporary support, well-known base materials, such as polyester and polystyrene, can be used, for example. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability. The thickness of the temporary support is preferably about 15 to 200 μm, more preferably about 30 to 150 μm. When the thickness of the temporary support is within the above range, it is possible to effectively suppress generation of a wrinkle of a tin plate due to heat during the lamination process, which is advantageous in terms of cost.
The temporary support may be provided with a conductive layer described in JP-A-11-149008 as required.

<Thermoplastic resin layer>
It is preferable to provide an alkali-soluble thermoplastic resin layer between the temporary support and the photosensitive light-shielding layer, or between the temporary support and the intermediate layer.
The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness of the underlying surface (including unevenness due to images already formed, etc.), so it deforms according to the unevenness. It is preferable to have a property that can be obtained.

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

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

  Among these, methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159, JP-B-55-38961 and JP-A-5-241340 are particularly preferable. Examples thereof include styrene / (meth) acrylic acid copolymers described in the publication.

  In order to adjust the adhesive force between the thermoplastic resin layer and the temporary support, the thermoplastic resin layer is provided with various plasticizers, various polymers, supercooling substances, adhesion improvers, surfactants, or release agents. It is possible to add. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono ( Addition reaction product with (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of rate, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate. As for the quantity of the plasticizer in a thermoplastic resin layer, 200 mass% or less is common with respect to a thermoplastic resin, Preferably it is 20-100 mass%.

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

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

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

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

The thickness of the intermediate layer is preferably from 0.1 to 5 μm, and more preferably from 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, oxygen barrier properties can be provided, and an increase in the intermediate layer removal time during development can be prevented.
The coating solvent for the intermediate layer is not particularly limited as long as the resin dissolves, and water is particularly preferable, and a mixed solvent obtained by mixing water with the above-described water-miscible organic solvent is also preferable. Specific examples of preferable coating solvents include, for example, water, water / methanol = 90/10, water / methanol = 70/30, water / methanol = 55/45, water / ethanol = 70/30, water / 1-propanol. = 70/30, water / acetone = 90/10, water / methyl ethyl ketone = 95/5 (where the ratio represents a mass ratio) and the like.

<Preparation of photosensitive transfer material>
Preparation of the photosensitive transfer material, on the temporary support, for example, a solution of the composition for preparing a dark color separation wall having the above-described photosensitivity, for example, a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, This can be done by applying and drying using a coating machine such as a wire bar coater or extruder. The same process can be performed when a thermoplastic resin layer and an intermediate layer are provided.

<Color filter and manufacturing method thereof>
The color filter manufacturing method of the present invention is to produce a color filter having a pixel group composed of a plurality of colored pixels of two or more colors and a dark color separation wall that separates the colored pixels of the pixel group. Specifically, a step of exposing a layer containing metal particles or metal-containing particles and a resin or a precursor thereof and having a residual voltage of 200 mV or less in a pattern and developing to form a dark color separation wall ( A partition formation step) and a step of forming a plurality of colored pixels of two or more colors by applying droplets of the colored liquid composition to the recesses between the formed dark color separation walls (hereinafter referred to as “pixel formation step”). And can be configured by providing other processes as necessary.

  The partition wall forming step includes at least one kind of metal particles and metal-containing particles and at least one kind of resin and its precursor, and a layer having a residual voltage of 200 mV or less, preferably for producing the above-described dark-colored separation wall. Formation of partition walls in the above-described method for forming a dark color separation wall according to the present invention is suitable for exposing a layer formed using the colored composition of the present invention in a pattern and developing it to form a dark color separation wall. It can be performed in the same manner as the process.

  As described above, the layer is formed by dispersing metal particles or metal-containing particles, so that a high optical density (2.5 or more) can be obtained with a thin film as described above, and the residual voltage can be reduced. Since it is configured to be 200 mV or less, for example, when a liquid crystal display device or the like is configured, it is possible to suppress display unevenness and fluctuation of display contrast when an image is displayed over time, and stably have high contrast. An image can be displayed.

In the pixel forming step, a droplet of the colored liquid composition is applied to the recesses between the dark color separation walls formed in the partition forming step to form a plurality of colored pixels having two or more colors.
An ink jet method is suitable as a method for applying droplets of the colored liquid composition. As the ink jet method, known methods such as a method of thermally curing ink, a method of photocuring, and a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance can be used.

  As an ink jet method, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and a method in which ink is heated and ejected intermittently using its foaming Various methods can be employed.

  The ink can be either oily or water-based. Further, the coloring material contained in the ink can be used for both dyes and pigments, and the pigment is more preferable from the viewpoint of durability. Further, a coating-type colored ink (for example, a colored resin composition described in paragraphs [0034] to [0063] of JP-A No. 2005-3861) used for producing a known color filter, or JP-A-10- The inkjet composition described in paragraph Nos. [0009] to [0026] of 195358 can be used.

In addition, in consideration of after ink droplet application, a component that is cured by heating or energy rays such as ultraviolet rays can be added to the ink. Various thermosetting resins can be widely used as the component cured by heating, and for example, a component obtained by adding a photoinitiator to an acrylate derivative or a methacrylate derivative can be used as the component cured by energy rays. . In particular, in view of heat resistance, those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and even those that are sparingly soluble in water can be used after being emulsified. In this case, a photosensitive resin composition containing a colorant such as a pigment mentioned in the above-mentioned <Coloring composition> section can be used as a suitable one.
As the ink, a thermosetting ink for a color filter containing at least a binder and a bifunctional or trifunctional epoxy group-containing monomer is also suitable.

  The color filter of the present invention is preferably a color filter in which pixels are formed by an inkjet method, and it is preferable to form three color filters by spraying RGB three color inks.

Preferably, after each colored pixel is formed, a heating step of performing a heat treatment (so-called baking treatment) is provided. Specifically, it can be carried out by heating in an electric furnace, a dryer or the like, or irradiating with an infrared lamp.
The heating temperature and time depend on the composition of the coloring composition and the thickness of the formed layer, but generally from about 120 ° C. to about 250 ° C. from the viewpoint of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. It is preferable to heat at about 10 minutes to about 120 minutes.

  The color filter of the present invention is a dark filter that separates a pixel group composed of two or more colored pixels that are formed of a colored layer and have different colors on a light-transmitting substrate, and each pixel constituting the pixel group. A color separation wall (black matrix) is provided, and is produced by the above-described method for producing a color filter of the present invention.

  The pixel group may be a pixel group composed of two colored pixels or three color pixels that exhibit different colors, or a pixel group composed of four or more colored pixels that represent different colors. There may be. For example, in the case of three colors, three hues of red (R), green (G), and blue (B) are preferably used. When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable, and any arrangement may be used when four or more types of pixel groups are arranged.

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

  As described above, the color filter of the present invention is a thin film produced using the colored composition of the present invention and has a high-density dark color separation wall (particularly a black matrix). In this case, display unevenness can occur over time, and variations in display contrast can be suppressed, and an image with high contrast can be stably displayed.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the above-described color filter of the present invention. As described above, the color filter includes a metal particle or metal-containing particle and a resin or a precursor thereof, and a layer formed by exposing and developing a layer having a residual voltage of 200 mV or less in a pattern. Since it has a color separation wall, display unevenness can occur over time and fluctuations in display contrast can be suppressed, and an image with high contrast can be stably displayed.

  Explanations of liquid crystal display devices are described in, for example, “Electronic Display Devices” (Akio Sasaki, Sumi Industry Research Committee, published every 1990), “Display Devices” (written by Junyuki Ibuki, published in 1989 in the industry book) Has been.

  In addition to the color filter, the liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. Generally configured using. In the liquid crystal display device composed of these known members, the color filter of the present invention described above can be applied, and the liquid crystal display device of the present invention can be manufactured. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market” (Kentaro Shima, CMC Co., Ltd., published in 1994), “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Table Ryoyoshi, Fuji Chimera Research Institute, Ltd., 2003, etc.), and the types of LCD include STN, TN, VA, IPS, OCS, and R-OCB.

As one of liquid crystal display devices, a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) are provided between a pair of substrates, at least one of which is a light-transmitting substrate. Can be mentioned.
As the color filter, a color filter having a plurality of pixel groups and each pixel constituting the pixel group being separated from each other by the black matrix according to the present invention can be suitably used.

  In another aspect of the liquid crystal display device, at least one of a pair of substrates, each of which is a light transmissive substrate, includes at least a color filter, a liquid crystal layer, and a liquid crystal driving unit, and the liquid crystal driving unit is an active element (for example, a TFT). And a black matrix formed by using the coloring composition or transfer material of the present invention between the active elements.

  The liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology” (edited by Tatsuo Uchida, Side Industry Research Committee, published in 1994). In the present invention, applicable display devices (liquid crystal display elements) are not particularly limited, and can be applied to, for example, various types of liquid crystal display elements described in the “next-generation liquid crystal display technology”. Especially, it is effective for a color TFT type liquid crystal display element.

  The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display” (Kyoritsu Publishing Co., Ltd., issued in 1996). Furthermore, the present invention can be 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. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest trends in technology and market" (Toray Research Center, Research Division, issued in 2001).

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass. In the present embodiment, a case where a black matrix (hereinafter sometimes abbreviated as “BM”) is formed as an example of a dark color separation wall is shown.

(Example 1): Coating method <Preparation of dispersion of particles having silver-tin alloy part (dispersion A1)>
To 1000 ml of pure water, 23.1 g of silver (I) acetate, 65.1 g of tin (II) acetate, 54 g of gluconic acid, 45 g of sodium pyrophosphate, 2 g of polyethylene glycol (molecular weight 3,000), and E735 (IS Japan ( Co., Ltd .; vinyl pyrrolidone / vinyl acetate copolymer) 5 g was dissolved to obtain solution 1.
Separately, 36.1 g of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.

  While the solution 1 obtained above was vigorously stirred while maintaining at 25 ° C., the above solution 2 was added thereto over 2 minutes, and the stirring was continued gently for 6 hours. Then, the liquid mixture turned black, and particles having a silver-tin alloy part (hereinafter sometimes referred to as “silver-tin alloy part-containing particles”) were obtained. Next, the following operation (A) was repeated three times to remove the water-soluble substances and to disperse the silver-tin alloy part-containing particles.

-Operation (A)-
The liquid containing the silver-tin alloy part-containing particles was centrifuged to precipitate the silver-tin alloy part-containing particles. Centrifugation was carried out for 30 minutes at a rotational speed of 2,000 rpm by using a table centrifuge H-103n (manufactured by Kokusan Co., Ltd.) in a small volume of 150 ml. Then, the supernatant was discarded, the total liquid volume was made 150 ml, 1350 ml of pure water was added thereto, and the mixture was stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again.

  Thereafter, the liquid was further centrifuged to precipitate silver tin alloy part-containing particles again. Centrifugation was performed under the same conditions as described above. After centrifuging, the supernatant was discarded as described above, the total liquid volume was made 150 ml, 850 ml of pure water and 500 ml of acetone were added thereto, and the mixture was further stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again.

Centrifugation was performed again in the same manner as described above to precipitate the silver-tin alloy part-containing particles. Then, the supernatant was discarded as described above to a liquid volume of 150 ml, and 150 ml of pure water and 1200 ml of acetone were added thereto, and the mixture was further stirred for 15 minutes. Then, the silver tin alloy part-containing particles were dispersed again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. Thereafter, the supernatant was discarded to make the total liquid volume 70 ml, and 30 ml of acetone was added thereto. This was dispersed for 6 hours using an Eiger mill (Eiger mill M-50 type (media: diameter 0.65 mm zirconia beads 130 g, manufactured by Eiger Japan Co., Ltd.)), and a dispersion of silver-tin alloy part-containing particles (dispersion A1) Got.
It was confirmed by X-ray scattering that the silver-tin alloy part-containing particles were a composite composed of an AgSn alloy (2θ = 39.5 °) and a Sn metal (2θ = 30.5 °). Here, the numbers in parentheses are the scattering angles of the respective (III) planes. As a result of observing the fine particle dispersion with a transmission electron microscope, the dispersion average particle size was about 40 nm in terms of number average particle size.

The number average particle size was measured using a photograph obtained with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) as follows.
100 particles were selected, the diameter of a circle having the same area as each particle image was defined as the particle diameter, and the average of the particle diameters of 100 particles was defined as the number average particle size. At this time, a photograph taken at a magnification of 100,000 times and an acceleration voltage of 200 kV was used.

<Preparation of photosensitive coating liquid A1 for black matrix (BM)>
The following composition was mixed to prepare a photosensitive coating solution A1 for BM.
〔composition〕
-Dispersion of the silver-tin alloy part-containing particles (dispersion A1) ... 50.00 parts-Propylene glycol monomethyl ether acetate ... 28.6 parts-Methyl ethyl ketone ... 37.6 parts-Fluorine surfactant ... 0.2 parts (F-780-F, manufactured by Dainippon Ink & Chemicals, Inc.)
Hydroquinone monomethyl ether 0.001 part Styrene / acrylic acid copolymer 9.6 parts (molar ratio = 56/44, weight average molecular weight 30,000)
Dipentaerythritol hexaacrylate 9.6 parts (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
-Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.5 parts

<Preparation of coating solution for protective layer>
The following compositions were mixed to prepare a protective layer coating solution.
・ Polyvinyl alcohol: 3.0 parts (PVA-205, manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone: 1.3 parts (PVP-K30, manufactured by IS Japan Co., Ltd.)
・ Distilled water: 50.7 parts ・ Methyl alcohol: 45.0 parts

<Formation of black matrix (BM) by coating>
(1) 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 film thickness is 1 on the substrate using a glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) equipped with a slit-like nozzle. The photosensitive coating solution A1 for BM obtained above was applied so as to have a thickness of 2 μm, and dried at 100 ° C. for 5 minutes to form a photosensitive layer (application step). Next, the protective layer coating solution obtained above was applied on the photosensitive layer using a slit nozzle so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 5 minutes to form a protective layer. Thus, a photosensitive material for BM was produced.

(2) Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, a mask (quartz exposure mask having an image pattern) and the above-described light-sensitive film photosensitive material are vertically set up. In this state, the entire surface was exposed at an exposure amount of 70 mJ / cm ² with the distance between the mask surface and the surface of the photosensitive material for the light-shielding film in contact with the intermediate layer of the photosensitive layer being 200 μm (exposure process). Next, the light-sensitive material for the light-shielding film after exposure is developed using a development processing solution T-CD1 (produced by Fuji Photo Film Co., Ltd .; alkaline developer) diluted 5 times (pH in use is 10.2). Processing (33 ° C., 20 seconds; development step) was performed to form a black matrix (BM) on the glass substrate.
Next, the glass substrate on which the BM is formed is heated at 220 ° C. for 60 minutes by a substrate preheating device, and then further heated at 240 ° C. for 50 minutes and baked (baking process), and the opening in the pixel formation region is 86 μm. A black matrix having a line width of 24 μm was formed so as to be × 304 μm. Hereinafter, the glass substrate on which the black matrix is formed is referred to as a “black matrix substrate”.

<Production of color filter and liquid crystal display device>
-Preparation of colored photosensitive resin composition-
Colored photosensitive resin compositions R1, G1, and B1 having the compositions shown in Table 1 below were prepared.

-Formation of red (R) pixels-
Using the colored photosensitive resin composition R1 obtained above on the BM formation surface side of the glass substrate on which the black matrix (BM) is formed, the same process as the formation of the black matrix described above is performed, and heat treatment is performed. A finished R pixel was formed.

-Formation of green (G) pixels-
Using the colored photosensitive resin composition G1 obtained above on the surface of the glass substrate on which the black matrix and R pixels are formed, the same process as the formation of the black matrix described above is performed, and heat treatment is performed. A finished G pixel was formed.

-Formation of blue (B) pixels-
Using the colored photosensitive resin composition B1 obtained above on the surface of the glass substrate on which the black matrix, R pixel, and G pixel are formed, the same process as the formation of the black matrix described above is performed. Thus, a heat-treated B pixel was formed.
A color filter (hereinafter referred to as a color filter substrate) was produced as described above.

Here, preparation of the colored photosensitive resin compositions R1, G1, and B1 described in Table 1 will be described.
<Preparation of colored photosensitive resin composition R1>
Colored photosensitive resin composition R1 measures R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and mixes at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4 as shown in Table 1 above. -Oxadiazole, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine, and phenothiazine, Add in this order at a temperature of 24 ° C. (± 2 ° C.) and stir at 150 rpm for 30 minutes, then weigh out the amount of Surfactant 1 listed in Table 1 above to a temperature of 24 ° C. (± 2 ° C.). In and stirred for 5 minutes at 30r.p.m. added, it is obtained by filtering with a nylon mesh # 200.

In addition, the detail of each composition R1 in the composition of the said Table 1 is as follows.
* Composition of R pigment dispersion 1-C.I. I. Pigment Red 254 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 8.0 parts-Compound 1 (dispersing agent) below: 0.8 parts-Polymer (benzyl methacrylate / methacrylic acid) (= 72/28 [molar ratio]) random copolymer, molecular weight: 30,000) 8 parts propylene glycol monomethyl ether acetate 83 parts

* Composition of R pigment dispersion 2-C.I. I. Pigment Red 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals) ... 18 parts-Random copolymer (weight) of polymer [benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) Average molecular weight 37,000)] ... 12 parts Propylene glycol monomethyl ether acetate 70 parts * Binder 2 compositionRandom co-polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate (= 38/25/37 [molar ratio]) Polymer, molecular weight: 40,000) 27 parts Propylene glycol monomethyl ether acetate 73 parts * Composition of DPHA solution Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, trade name: KAYARAD DPHA, Japan) Drugs Ltd.) ... 76 parts Propylene glycol monomethyl ether A cetearyl - the amount ... 24 parts * Composition of the surfactant 1 shown below structure 1 ... 30 parts Methyl ethyl ketone 70 parts

<Preparation of colored photosensitive resin composition G1>
The colored photosensitive resin composition G1 measures the amount of G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and mixes at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3 shown in Table 1 above. , 4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethylamino) -3′-bromophenyl] -s-triazine, and phenothiazine And added in this order at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 30 minutes, and weighed out the surfactant 1 in the amount shown in Table 1 above. It was added in degrees 24 ℃ (± 2 ℃) and stirred for 5 minutes at 30 rpm, is obtained by filtering with a nylon mesh # 200.

In addition, the detail of each composition in the composition G1 of the said Table 1 is as follows.
* G pigment dispersion 1
Product name: GT-2 (Fuji Film Electronics Materials Co., Ltd.)
* Y pigment dispersion 1
Product name: CF Yellow EX3393 (manufactured by Gokoku Color Co., Ltd.)
* Composition of binder 1-Random copolymer of polymer (benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]) (weight average molecular weight 38,000) ... 27 parts-Propylene glycol monomethyl ether acetate ... 73 parts

<Preparation of colored photosensitive resin composition B1>
Colored photosensitive resin composition B1 measures the amount of B pigment dispersion 1, B pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and mixes at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4 as shown in Table 1 above. -Oxadiazole and phenothiazine were weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. The amount of surfactant 1 listed in Table 1 was weighed out, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200. .

In addition, the detail of each composition in composition B1 of the said Table 1 is as follows.
* B Pigment dispersion 1
Product name: CF Blue EX3357 (Mikuni Dye Co., Ltd.)
* B Pigment dispersion 2
Product name: CF Blue EX3383 (manufactured by Gokoku Color Co., Ltd.)
* Composition of binder 3-Random copolymer of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate (= 36/22/42 [molar ratio]) (weight average molecular weight 38,000) ... 27 parts-Propylene glycol monomethyl ether acetate ... 73 parts

-Production of liquid crystal display device-
A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above. Separately, a glass substrate was prepared as a counter substrate, patterned on the transparent electrode of the color filter substrate and the counter substrate for the PVA mode, and an alignment film made of polyimide was further provided thereon.
Thereafter, an epoxy resin sealant is printed at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped to form 10 kg / cm ² with the counter substrate. After bonding with the pressure of, the bonded substrate was heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as a green (G) LED, and DB1112H (Stanley (as a blue (B) LED) A side-light type backlight was constructed using a chip type LED manufactured by Co., Ltd., and was placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

(Example 2): Coating method In Example 1, except that the operation (A) in the preparation of the dispersion liquid A1 of particles having a silver-tin alloy part was repeated twice. Thus, a dispersion of silver-tin alloy part-containing particles was obtained, a photosensitive coating solution for BM was prepared, a black matrix substrate was produced, and a liquid crystal display device was produced.

(Example 3): Coating method In Example 1, the silver-tin alloy part-containing particle dispersion A1 was replaced with the silver fine particle dispersion B1 prepared as follows, and a BM photosensitive coating liquid B1 was used. A black matrix substrate was produced in the same manner as in Example 1 except that a liquid crystal display device was produced.

<Preparation of silver fine particle dispersion B1>
73.5 g of silver fine particles having an average aspect ratio of 2.2, 1.05 g of a dispersant (trade name: Solsperse 20000, manufactured by Avicia Co., Ltd.), and 16.4 g of methyl ethyl ketone were mixed. This was dispersed using an ultrasonic disperser (trade name: Ultrasonic generator model US-6000 ccvp, manufactured by nissei) to obtain a dispersion of silver fine particles having an equivalent circle diameter of 100 nm. Next, silver fine particles were dispersed by the following operation (B).

-Operation (B)-
Centrifugation treatment (10,000 rpm, 20 minutes) was performed on the obtained dispersion of silver fine particles, and the supernatant was discarded and concentrated as appropriate. This operation was repeated 3 times to remove the soluble substance in the aqueous phase to obtain a silver fine particle dispersion B1.

<Preparation of photosensitive coating solution B1 for BM>
The following composition was mixed to prepare a photosensitive coating solution B1 for BM.
〔composition〕
-Silver fine particle dispersion B1 ... 40.00 parts-Propylene glycol monomethyl ether acetate ... 28.6 parts-Methyl ethyl ketone ... 37.6 parts-Surfactant 1 ... 0.2 parts-Hydroquinone monomethyl ether ... 0.001 parts Benzyl methacrylate / methacrylic acid copolymer 2.1 parts (molar ratio = 73/27, molecular weight 30,000)
・ Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.1 parts

  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 volume of the silver fine particles is further increased. The amount was such that the fraction was 0.13.

(Example 4): Coating method In Example 3, silver fine particle dispersion was carried out in the same manner as in Example 1 except that the operation (B) in preparing the silver fine particle dispersion B1 was repeated twice. While obtaining the liquid, a photosensitive coating liquid for BM was prepared, a black matrix substrate was produced, and a liquid crystal display device was produced.

Example 5: Transfer Method, Inkjet Method <Formation of Black Matrix (BM)>
-Production of photosensitive resin transfer material-
Using a slit-like nozzle on a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a thermoplastic resin layer coating solution having the following formulation H1 is applied and dried to form a thermoplastic resin layer. Formed. Next, an intermediate layer coating solution having the following formulation P1 was further applied onto the thermoplastic resin layer and dried to laminate the intermediate layer. Subsequently, the photosensitive coating solution A1 for BM prepared in Example 1 was applied on the intermediate layer and dried to further laminate a black photosensitive resin layer.

  As described above, a thermoplastic resin layer having a dry layer thickness of 14.6 μm, an intermediate layer having a dry layer thickness of 1.6 μm, and a photosensitive resin layer having a dry layer thickness of 1.2 μm are provided on the PET temporary support. A photosensitive transfer material having a laminated structure of a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer is prepared by pressure-bonding a protective film (polypropylene film having a thickness of 12 μm) to the surface of the photosensitive resin layer. Produced. Hereinafter, this is referred to as BM photosensitive transfer material K1.

<Prescription H1 of coating solution for thermoplastic resin layer>
-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 ... 5.83 parts (copolymerization) Ratio [molar ratio] = 55 / 11.7 / 4.5 / 28.8, molecular weight = 90,000, Tg≈70 ° C.)
Styrene / acrylic acid copolymer: 13.6 parts (copolymerization ratio [molar ratio] = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.)
・ 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .; compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate) 9.1 parts・ Surfactant 1: 0.54 parts

<Prescription P1 of coating solution for intermediate layer>
PVA-205 32.2 parts [manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550; polyvinyl alcohol]
・ Polyvinylpyrrolidone: 14.9 parts (APS Japan, K-30)
・ Distilled water: 524 parts ・ Methanol: 429 parts

-Formation of black matrix (BM)-
A non-alkali glass substrate (hereinafter referred to as a unit “glass substrate”) was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower, and after pure water shower washing, Silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution; trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower and washed with pure water. did. Then, this board | substrate was heated for 2 minutes at 100 degreeC with the board | substrate preheating apparatus, and it sent to the laminator.

The protective film is peeled off from the BM photosensitive transfer material K1 obtained above from the glass substrate after the silane coupling treatment, and the surface of the photosensitive resin layer exposed after the removal is overlapped with the surface of the glass substrate. In addition, lamination was performed using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) under the conditions of a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min.
Subsequently, the PET temporary support was peeled off at the interface with the thermoplastic resin layer, and the temporary support was removed. After peeling off the temporary support, use a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp to vertically stand the substrate and mask (quartz exposure mask with image pattern) In this state, the distance between the mask surface and the dark photosensitive layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

  Next, a triethanolamine developer (containing 30% by mass of triethanolamine, 0.1% by mass in total of polypropylene glycol, glycerol monostearate, polyoxyethylene sorbitan monostearate and stearyl ether, trade name: T -PD2, manufactured by Fuji Photo Film Co., Ltd.) with pure water diluted 12 times (1 part by mass of T-PD2 and 11 parts by mass of pure water) (30 ° C.) for 50 seconds. Then, shower development was performed with a flat nozzle at a pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed. Subsequently, air was blown onto the substrate to drain the liquid, and then pure water was sprayed for 10 seconds by a shower to perform pure water shower cleaning, and air was blown to reduce the liquid pool on the substrate.

  Subsequently, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and Stabilizer-containing; trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 5 times with pure water (29 ° C.) for 30 seconds, shower with cone type nozzle at pressure of 0.15 MPa Development was performed to develop and remove the photosensitive resin layer to obtain a pattern image.

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer; trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) was diluted 10 times with pure water. Using a liquid (33 ° C.) for 20 seconds, a cone type nozzle was used as a shower at a pressure of 0.02 MPa, and the residue was removed by rubbing the pattern image with a rotating brush having nylon bristles to obtain a black matrix. . Thereafter, the substrate on which the black matrix was formed was post-exposed with an ultrahigh pressure mercury lamp from both sides at an exposure amount of 500 mJ / cm ² and then heat-treated (baked) at 220 ° C. for 15 minutes (black matrix substrate).

<Production of color filter>
Next, a red (R) ink, a green (G) ink, and a blue color (G) having the following composition are selectively used by using an inkjet device in a concave portion surrounded by a pattern wall constituting the black matrix of the obtained black matrix substrate. B) Each ink was sprayed to form colored pixels.

The R ink is a C.I. I. Pigment Red 254, Solsperse 24000, and ethyl 3-ethoxypropionate were mixed, and a pigment dispersion was prepared using a three-roll and bead mill. The remaining amount of the pigment dispersion was stirred while thoroughly stirring with a dissolver or the like. R ink was prepared by adding other components little by little.
<R ink composition>
・ C. I. Pigment Red 254 (pigment) 5 parts Solsperse 24000 (manufactured by AVECIA; polymer dispersant) 1 part Glycidyl methacrylate-styrene copolymer (binder) 3 parts First epoxy resin 2 parts (Novolac Type epoxy resin, Epicoat 154 manufactured by Yuka Shell
・ Second epoxy resin: 5 parts (Neopentyl glycol diglycidyl ether)
・ Trimellitic acid (curing agent) 4 parts ・ Ethyl 3-ethoxypropionate (solvent) 80 parts

  Next, C.I. I. Pigment Red 254 with C.I. I. G ink was prepared in the same manner as R ink except that the same amount was used instead of Pigment Green 36. In addition, C.I. I. Pigment Red 254 with C.I. I. B ink was prepared in the same manner as R ink except that the same amount was used instead of CI Pigment Blue 15: 6.

  Then, the colored pixels and the black matrix were further baked in an oven at 230 ° C. for 30 minutes to further cure the colored pixels and the black matrix, thereby obtaining a color filter.

  When the obtained color filter was evaluated by an optical microscope from the pixel formation side in the thickness direction of the substrate for the presence of the ink of each color applied by the ink jet in the thickness direction of the substrate, the ink of each color was exactly in the recess between the black matrix walls. There was no defect due to color mixing between adjacent pixels.

(Comparative Example 1)
In Example 1, except that the dispersion A1 of the silver-tin alloy part-containing particles was replaced with the carbon black dispersion prepared as described below, and a BM photosensitive resin composition K1 having the following formulation was used. In the same manner as described above, a black matrix substrate was manufactured and a liquid crystal display device was manufactured.

<Prescription of photosensitive resin composition K1 for BM>
The following carbon black dispersion (carbon black particle size 20 nm) 23 parts Propylene glycol monomethyl ether acetate 8.0 parts Methyl ethyl ketone 53 parts Binder 2 9.1 parts Hydroquinone monomethyl ether 0.002 Part · DPHA solution ... 4.5 parts · 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine ... 0.16 part ・ Surfactant 1... 0.055 part

* Carbon black dispersion ・ Carbon black (Nipex 35, manufactured by Degussa) ... 13.1 parts ・ Compound 1 (dispersant) ... 0.80 parts ・ Polymer [benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) ) Random copolymer, molecular weight 37,000) ... 6.72 parts · Propylene glycol monomethyl ether acetate ... 79.38 parts

(Comparative Example 2)
In Example 1, except that the dispersion A1 of the silver-tin alloy part-containing particles was replaced with the carbon black dispersion prepared as follows, and the photosensitive resin composition K2 for BM having the following formulation was used. In the same manner as described above, a black matrix substrate was manufactured and a liquid crystal display device was manufactured.

<Prescription of BM photosensitive resin composition K2>
・ Carbon black dispersion (carbon black particle size 20 nm) 44 parts ・ Propylene glycol monomethyl ether acetate 18 parts ・ Methyl ethyl ketone 35 parts ・ 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane (new 0.98 parts ・ Hydroquinone monomethyl ether 0.002 parts ・ DPHA solution 1.6 parts ・ 2,4-bis (trichloromethyl) -6- [4 ′-(N , N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine ... 0.064 parts-Shigenox 102 (manufactured by Hackol Chemical Co.) ... 0.018 parts-TAZ-204 (manufactured by Midori Chemical Co., Ltd.) ... 0.064 parts ・ Surfactant 1 ... 0.043 parts

(Comparative Example 3)
A black matrix substrate was produced in the same manner as in Comparative Example 1 except that the thickness of the black matrix was changed from 1.2 μm to 1.6 μm in Comparative Example 1, and a liquid crystal display device was produced.

(Comparative Example 4)
In Example 1, a silver-tin alloy was obtained in the same manner as in Example 1 except that the operation (A) repeated three times during the preparation of the dispersion A1 of the silver-tin alloy part-containing particles was changed to one. While obtaining the dispersion liquid of part containing particle | grains, the photosensitive coating liquid for BM was prepared, the black matrix substrate was produced, and the liquid crystal display device was produced.

(Comparative Example 5)
In Example 3, a silver fine particle dispersion was obtained in the same manner as in Example 3 except that the operation (B) repeated three times during the preparation of the silver fine particle dispersion B1 was changed to one time. A photosensitive coating solution for BM was prepared, a black matrix substrate was produced, and a liquid crystal display device was produced.

(Evaluation)
Each of the black matrix substrate and the liquid crystal display device produced in the above-described Examples and Comparative Examples was measured and evaluated according to the following method. The results of measurement and evaluation are shown in Table 2 below.

-1. Residual voltage-
It carried out according to the method as described in Unexamined-Japanese-Patent No. 2003-26918 (paragraph numbers [0078]-[0082]). Specifically, a “dielectric absorption method” in which 5V DC is applied between the liquid crystal cells at 23 ° C. for 30 minutes and left for 1 second, and then the residual voltage [V] remaining in the liquid crystal cell is measured after 10 minutes have elapsed. The residual voltage was measured. In the liquid crystal cell, two black matrix substrates prepared in each example and comparative example were prepared, and 6 μm spacers were spread on the black matrix forming surface and then overlapped, and a liquid crystal (HA5073LA) was placed between the two substrates. , Manufactured by Chisso Petrochemical Co., Ltd.).

-2. Contrast
Each liquid crystal display device fabricated as described above was energized and allowed to stand for 1000 hours, and then the contrast was measured and evaluated by the following method. The evaluation results are shown in Table 2 below.
When the luminance meter BM-5 manufactured by TOPCON CORPORATION JAPAN is installed at a distance of 50 cm in the normal direction of the panel surface of each liquid crystal display device, and when the liquid crystal display device displays black and white The difference from the brightness was measured. The measurement was performed in a dark room.

-3. Optical density
The optical density of the black matrix after baking was measured by the following method.
Using a spectrophotometer UV-2100 (manufactured by Shimadzu Corporation), the transmission optical density (OD) of the black matrix substrate was measured at a wavelength of 555 nm, and the transmission optical density of the glass substrate used for each black matrix substrate ( OD ⁰ ) was measured by the same method. Then, a value obtained by subtracting OD ⁰ from OD (transmission OD; = OD−OD ⁰ ) was defined as the transmission optical density.

-4. Film thickness
The thickness of the black matrix after baking was measured using a contact type surface roughness meter P-10 (manufactured by TENCOR).

-5. Display unevenness after storage over time
Each liquid crystal display device manufactured as described above was energized and left for 1000 hours, and then the display unevenness was measured and evaluated by the following method.
First, a gray test signal was input to each liquid crystal display device and observed visually and with a magnifying glass to evaluate the occurrence of unevenness. The evaluation was “5” when no unevenness was observed visually or with a loupe, “4” when unevenness was observed only with the loupe, and “3” where slight unevenness was visually observed. The case where unevenness was observed visually was designated as “2”, and the case where unevenness was noticeable visually was designated as “1”.

-6. Development latitude
In the development process for producing a black mat risk, the range of development time in which a pattern can be formed is 20 seconds or more, “◯” is 10 seconds or more and less than 20 seconds, and “△” is less than 10 seconds. The thing was made into "x".

  As shown in Table 2, in the example, the occurrence of display unevenness with time and the change in display contrast were suppressed, and an image with high contrast could be stably displayed. Also, the development latitude during development was good. On the other hand, in the comparative example, display unevenness occurred over time, and the display contrast variation could not be suppressed.

Claims (8)

  A coloring composition containing metal particles or metal-containing particles and having a residual voltage of 200 mV or less.   The colored composition according to claim 1, wherein the colored composition is used for forming a dark color separation wall that separates colored pixel portions formed by applying droplets.   Dark color separation having a step of forming a dark color separation wall by exposing a pattern containing a metal particle or a metal-containing particle and a resin or a precursor thereof and having a residual voltage of 200 mV or less in a pattern. Wall formation method.   The method for forming a dark color separation wall according to claim 3, wherein at least one of the particles is a particle having a silver-tin alloy part.   5. The method of forming a dark color separation wall according to claim 3, wherein the optical density of the dark color separation wall is 2.5 or more. A method for producing a color filter having a pixel group composed of a plurality of colored pixels of two or more colors and a dark color separation wall separating the colored pixels of the pixel group,
A step of exposing a layer containing metal particles or metal-containing particles and a resin or a precursor thereof and having a residual voltage of 200 mV or less in a pattern and developing to form a dark color separation wall;
Forming a plurality of colored pixels of two or more colors by applying a droplet of the colored liquid composition to the recesses between the formed dark color separation walls; and
The manufacturing method of the color filter which has this.   A color filter produced by the method for producing a color filter according to claim 6.   A liquid crystal display device comprising the color filter according to claim 7.