JP2007304207A - Color filter and its manufacturing method, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter which is free from a defect such as surface roughness, has high contrast by using a black matrix having satisfactory accuracy and can be manufactured at low costs, to provide its manufacturing method, and to provide a liquid crystal display which has a constant cell gap and can perform high contrast display. <P>SOLUTION: The manufacturing method of the color filter having the black matrix and colored pixels formed in the region partitioned by the black matrix and having at least one color of R, G and B on a substrate includes a step for forming the black matrix by transfer on the substrate by using a transfer material having a transfer layer for shielding containing at least one of a resin and its precursor and metal particles or particles containing metal on a temporary supporting body, a step for applying and forming the colored pixels having at least the one color of R, G and B, and a step for forming a photo spacer using a photo curing resin composition for the photo spacer on the black matrix. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a color filter constituting a liquid crystal display device, a manufacturing method thereof, 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 black matrix is thick, it is required to be formed into a thin film.

  Conventionally, a metal thin film has been used to manufacture a black matrix for a display device having high light shielding properties. 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 the carbon black has a low optical density per unit coating amount, an attempt to ensure high light-shielding properties and optical density necessarily increases the film thickness. 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 is deteriorated. Further, when the concentration of the pigment is increased, there is a disadvantage that surface roughness or pinhole-like defects generated on the black matrix occur.

  In addition to the above, as a method for obtaining a black matrix having a small environmental load and a high optical density, 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.

On the other hand, examples of the method for forming a color filter include a dyeing method, a pigment dispersion method, and an electrodeposition method. Among them, a pigment dispersion method is a common method.
The pigment dispersion method includes a coating method and a transfer method, but the black matrix is transferred and the RGB pixels are coated and formed with a slit coater in terms of ease of pixel formation, black matrix manufacturing accuracy, and cost. It is advantageous and has become widespread as a general method for producing color filters.

  Liquid crystal display devices, which have become mainstream in recent years, are widely used for display devices that display high-quality images. In general, a liquid crystal display device has a liquid crystal layer disposed between a pair of substrates to enable image display with a predetermined orientation.

In a liquid crystal display device, the distance between the TFT substrate and the color filter, that is, the thickness of the liquid crystal layer (cell gap), in other words, the uniformity of what indicates the distance between two electrodes that apply an electric field to the liquid crystal in the display region It greatly affects the quality of images. Usually, in order to keep the cell gap constant, the thickness and height uniformity of the spacer, the black matrix, the colored layer (red, green, blue layer) and the like are necessary.
In order to keep the cell gap uniform, the height (thickness) uniformity of the spacer is particularly important among the above.

In the spacer, inorganic particles such as silica were initially used (for example, see Patent Document 4). However, this method has a problem that fine particles exist in the pixel and impair the image quality of the color filter. In recent years, a columnar product (hereinafter also referred to as “columnar spacer”) is formed by photolithography using a photosensitive resin. It has come to be formed (see, for example, Patent Document 5).
However, the thickness and height uniformity of the spacer, black matrix, colored layer, and the like in the color filter are not sufficient, and there is a problem as display unevenness when used as a liquid crystal display device, and improvement therefor is necessary.
JP-A-62-9301 JP 2004-240039 A JP 2005-17322 A JP-A-5-181144 JP 2000-056122 A “Color TFT LCD” p. 218-p. 220, issued by Kyoritsu Publishing Co., Ltd. (April 10, 1997)

The present invention provides a high-contrast color filter that is free from defects such as surface defects and that uses a highly accurate black matrix and can be manufactured at low cost, and a method for manufacturing the same.
The present invention also provides a liquid crystal display device having a constant cell gap and high contrast.

In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> In a method for manufacturing a color filter having a black matrix on a substrate and a colored pixel having at least one of R, G, and B formed in a region separated by the black matrix, a temporary support Using a transfer material having a shielding transfer layer containing at least one of a resin and a precursor thereof and metal particles or metal-containing particles to form a black matrix by transfer onto a substrate; and R , G, and B, applying a colored pixel having at least one color, and forming a photospacer on the black matrix using a photocurable resin composition for photospacer. A method for producing a color filter.

<2> The method for producing a color filter according to <1>, wherein the coating is performed by a slit coater.
<3> The step <1> or <1>, wherein the step of forming the photospacer is a step of using a transfer material having a photocurable resin composition layer for photospacers on a temporary support. 2> The manufacturing method of the color filter as described in 2>.

<4> Any one of the above <1> to <3>, wherein at least one of the metal particles or the metal-containing particles contained in the shielding transfer layer is a particle having a silver-tin alloy part A method for producing a color filter according to claim 1.
<5> The method for producing a color filter according to any one of <1> to <4>, wherein the shielding transfer layer further contains a pigment.

<6> The method for producing a color filter according to any one of <1> to <5>, wherein the shielding transfer layer is a single layer.
<7> The shielding transfer layer comprises at least two resin layers, at least one of the resin layers is a light reflecting layer, and at least one of the resin layers is a light absorbing layer. The method for producing a color filter according to any one of <1> to <5> above.

<8> A color filter produced by the production method according to any one of <1> to <7> above.
<9> A liquid crystal display device comprising the color filter according to <8>.

  According to the present invention, even a high-concentration black matrix is free from defects such as pinholes, and an accurate black matrix can be produced. Display unevenness due to unevenness in the thickness of colored pixels formed in a subsequent process, etc. It is possible to provide a liquid crystal display device that can maintain a constant cell gap with a color filter having no color and a photo spacer formed on the black matrix, and that has a high contrast and a good liquid crystal display quality at low cost. .

  Hereinafter, the transfer layer for shielding the transfer material and the colored pixels in the present invention will be described in detail, and the color filter of the present invention, the manufacturing method thereof, and the liquid crystal display device will be described in detail through the description.

<Shielding transfer layer>
The transfer layer for shielding in the present invention is a layer containing at least one kind of resin and its precursor and metal particles or particles containing metal (hereinafter also referred to as “metal fine particles”), and the resin and its precursor. It is formed using a coloring composition containing at least one kind of body and metal particles or metal-containing particles.
Since the shielding transfer layer contains metal particles or metal-containing particles, a high optical density can be obtained while forming a thin film. The shielding transfer layer is suitable for producing a black matrix, for example, and when a liquid crystal display device or the like is configured, an image having a high contrast can be stably displayed.
The shielding transfer layer may be a single layer or a multilayer composed of two or more layers, but a single layer is preferred from the viewpoint of simplicity of the process. As an example of a multilayer, the structure which consists of a light reflection layer and a light absorption layer as described in Paragraph Nos. [0042]-[0073] of Unexamined-Japanese-Patent No. 2006-11180 is mentioned.

-Metal particles or particles containing metal-
The colored composition in the present invention contains at least one of metal particles and metal-containing particles (hereinafter also referred to as “metal-based fine particles”).
The metal in the metal particle or the metal-containing particle 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.

<Metal particles>
As a metal particle, the particle | grains (composite metal particle) formed from a metal or a metal and a metal compound are preferable, and the particle | grains (metal particle) formed from a metal are especially preferable.

  In particular, it is preferable that 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 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.

Examples of metals preferable as the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, Examples thereof include at least one selected from bismuth, antimony, lead, and alloys thereof.
More preferable metal is at least one selected from 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, calcium, and alloys thereof, and particularly preferred metals are at least one selected from copper, silver, gold, platinum, tin, and alloys thereof.
In particular, silver and a silver tin alloy are preferable (colloidal silver is preferable as silver), and a silver tin alloy is most preferable.
As the metal particles, particles having a silver-tin alloy 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.
Specific examples of the metal compound 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 used. Particularly preferred.

<Composite metal particles>
Composite metal particles refer to 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 metal particles of metal compound and metal include composite particles of silver and silver sulfide, composite particles of silver and copper (II) oxide, and the like.

  The metal-based fine particles in 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, and specific examples thereof include paragraph numbers [0024] to [0027] of JP-A-2006-18210. And core-shell fine particles described in the above.

<Particles having a silver-tin alloy part>
The particles having a silver-tin alloy part include those composed of a silver-tin alloy part, those composed of a silver-tin alloy part and another metal part, and those composed of a silver-tin alloy part and another alloy part.

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

  The particles having the silver-tin alloy portion have a high black density, can exhibit excellent light shielding (shielding) performance in a small amount or in a thin film, and have high thermal stability, so that the black density is not impaired. Heat treatment at 200 ° C. or higher), and a high degree of 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 the silver-tin alloy part are preferably obtained by combining (for example, alloying) Ag and tin (Sn) with a silver (Ag) ratio in the silver-tin alloy part 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.

  The particles having the 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 900 ° C. In the vicinity, the melting point of Sn is around 200 ° C., and there is a large difference between the melting points of both, and an extra step of micronization after compounding (for example, alloying) is required. preferable. 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 (Sn (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.

The metal-based fine particles in the present invention can be commercially available, and can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
For example, rod-like or wire-like silver fine particles are obtained by using spherical silver fine particles as seed particles, then adding a silver salt, and relatively reducing power such as ascorbic acid in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide). Can be obtained by using a weak reducing agent. 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-based fine 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.

As the particle size distribution of the metal-based 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.

The particle size distribution width D ⁹⁰ / D ¹⁰ is measured specifically by measuring 100 metal fine particles in the film at random by the method of measuring the triaxial diameter, and the long axis length L It was the particle diameter, and the normal distribution approximates the particle size distribution, and the number of particles diameter is 90% of the particles close to the average particle diameter and D ^90, the particle diameter in the range number of 10% from the mean particle size By setting D to D ¹⁰ , D ⁹⁰ / D ¹⁰ can be calculated.

《Triaxial diameter》
The metal-based fine particles in 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, metal-based fine particles are placed on a flat surface so that the center of gravity is the lowest and remains stable. Next, the metal-based 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 long 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-shaped metal-based fine particles, is defined as the average value of values measured for 100 rod-shaped metal fine particles. The ratio (b / t) between the width b and the thickness t of the rod-like metal-based fine particles is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.3 or less. preferable. 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-based fine particles are preferably metal particles or metal compound particles containing metal, more preferably silver particles or silver compound particles containing silver, and most preferably particles containing a silver-tin alloy part.

<Pigments and other>
In the present invention, other fine particles such as pigments can be used together with the above-mentioned metal-based fine particles. When a pigment is used, the hue can be made closer to black.

  In general, the pigment is roughly classified into an organic pigment and an inorganic pigment. In the present invention, a pigment dispersed with the same dispersant as the metal-based fine particles 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, yellow, orange, red, violet, blue, green, brown or black.

As said black pigment, carbon black, titanium black, or graphite is mentioned as a suitable thing from a viewpoint of color.
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.
If the average particle size of titanium black is less than 40 nm, problems such as aggregation tend to occur, and if it exceeds 100 nm, a preferred color may not be obtained.
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.

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.
As specific examples of the fine particles, the coloring materials described in JP-A-2005-17716 [0038] to [0040], the pigments described in JP-A-2005-361447 [0068] to [0072], Colorants described in JP-A-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.
In the present invention, in the black matrix, the mass ratio B / A of the addition amount A of the metal-based fine particles and the addition amount B of the pigment is 0.2 or more and 10 or less, preferably 0.3 or more and 6.0 or less. More preferably, it is 0.8 or more and 5.0 or less. When the mass ratio B / A exceeds 10, the number of metal-based fine particles in the black matrix decreases, the transmission optical density decreases, and the black matrix needs to be thickened to maintain a predetermined transmission optical density. As a result, an overlap (step) between the black matrix and each of the R, G, and B pixels occurs, the flatness of the color filter deteriorates, and unevenness occurs in the cell gap of the liquid crystal display device. It tends to lead to defects.

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

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

  Examples of the dispersant for dispersion and the additive that may be added to the dispersion in the present invention include the dispersants and additives described in paragraphs [0027] to [0031] of JP-A-2005-17322. However, it is mentioned as a suitable thing also in this invention.

<Resin or its precursor>
The colored composition in 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. It can be preferably used.

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.
The resin preferably has an acid value in the range of 50 to 300 mg KOH / g and a weight average molecular weight in the range of 7000 to 100,000, and an acid value in the range of 60 to 200 mg KOH / g and a weight average in the range of 10,000 to 70000. Those having a molecular weight are particularly preferred.

  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.
As the monomer, monomers described in paragraphs [0010] to [0021] of JP-A-2006-23696 can be preferably used in the present invention.
The monomers may be used alone or in combination of two or more.
As for content with respect to the total solid of a coloring composition of a monomer, 5-50 mass% is common, and 10-40 mass% is preferable. When the content is within the above range, the photosensitivity and the image strength are not decreased, and the tackiness of the colored composition layer is not excessive.

  When the shielding transfer layer (the layer before patterning) is formed using the coloring composition of the present invention, the optical density per 1 μm layer thickness of the formed shielding transfer layer is preferably 1 or more. Is 1 or more and 20 or less, more preferably 2 or more and 15 or less, and particularly preferably 3 or more and 10 or less.

In addition, the content of the metal-based fine particles (and pigments and the like if necessary) in the coloring composition may be metal fine particles (and pigments and the like, if necessary) during post-baking, for example, when producing a color filter. In consideration of preventing fusion, the content of the metallic fine particles based on the total solid content of the coloring composition may be adjusted to be about 10 to 90% by mass, preferably 10 to 80% by mass. preferable.
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 photosensitive coloring composition described below.

  The “black matrix” referred to in the present invention is a black edge provided at the periphery of a liquid crystal display device, a black portion in a lattice shape or a stripe shape between red, blue, and green pixels, and further for light shielding a TFT. The definition of this black matrix is, for example, “Liquid Crystal Display Manufacturing Dictionary” (2nd edition, written by Taihei Kanno, p. 64, Nikkan Kogyo Shimbun, (1996).

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

<Photosensitive coloring composition>
The colored composition for producing the black matrix more preferably 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.
As the components of the photosensitive resin composition, the components constituting the colored photosensitive resin composition described in paragraphs [0010] to [0021] of JP-A-2006-23696 are also suitable for the present invention. Can be mentioned.

  Further, when the metal-based fine particles are used as an aqueous dispersion like a metal colloid, it is necessary to use a water-based one as the coloring composition for preparing the black matrix. 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 a black matrix is produced using the colored composition for producing a black matrix (including a photosensitive material) in the present invention, a black matrix having a high optical density can be produced with a thin film.

  The coloring composition in the present invention is suitable for forming a black matrix that separates the colored pixel portions.

<Photosensitive transfer material>
The photosensitive transfer material (hereinafter, also simply referred to as “transfer material”) is a temporary support provided with a shielding transfer layer formed using a coloring composition for producing a black matrix having at least photosensitivity, If necessary, a thermoplastic resin layer, an intermediate layer, a protective layer, and the like can be provided.

-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.

-Transfer layer for shielding-
The shielding transfer layer is a layer formed using the colored composition for producing the black matrix.
The thickness of the shielding transfer layer is preferably about 0.2 to 2.0 μm, and 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. For example, when a liquid crystal display device or the like is configured. Thus, fluctuations 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 black matrix is preferably 2.5 or more and 10.0 or less, more preferably 3.0 or more and 6.0 or less, and particularly preferably 3.5 or more and 5.5 or less. When the optical density is within the above range, light shielding properties can be imparted.

  The black matrix is formed by transferring a shielding transfer layer using a coloring composition for producing a black matrix containing the metal-based fine particles (metal particles or metal-containing particles), a resin, and a precursor thereof. Accordingly, there is no particular limitation as long as it is a method of patterning exposure and development (patterning).

  Examples of the layers other than the shielding transfer layer constituting the transfer material in the present invention include the thermoplastic resin layers, intermediate layers, and protective films described in paragraphs [0023] to [0066] of JP-A-2005-3861. It is mentioned as a suitable thing.

-Production of photosensitive transfer material-
Preparation of the photosensitive transfer material is carried out by applying a photosensitive black matrix preparation composition on a temporary support, for example, as described in paragraphs [0023] to [0066] of JP-A-2005-3861. Although it can carry out by using a coating device etc., in this invention, it is preferable to carry out by the coating device (slit coater) using a slit-shaped nozzle as follows.
The same can be done when the thermoplastic resin layer and the intermediate layer are provided.

-Application by slit nozzle-
The coating film is preferably formed by a slit-like nozzle having a slit-like hole in a portion discharged from the composition. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit coaters having slit-like nozzles described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

Slit coating has a slit (gap) having a width of several tens of microns at the tip, and a coating head having a length corresponding to the coating width of a rectangular substrate, and a clearance (gap) between the substrate of several tens to several hundreds of microns. In this coating method, the substrate and the coating head are held at a constant relative speed, and the coating liquid supplied from the slit is applied to the substrate with a predetermined discharge amount.
This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

<Method for forming black matrix>
The black matrix forming method in the present invention uses a transfer material having at least one shielding transfer layer containing at least one kind of metal particles and metal-containing particles and at least one kind of resin and a precursor thereof, It is a method having a step of transferring the shielding transfer layer onto a substrate to form a black matrix (black matrix forming step), and it is preferable to form a black matrix by exposing to a pattern and developing. Furthermore, another process can be provided and configured as necessary.

More specifically, the method for forming a black matrix according to the present invention comprises laminating a photosensitive transfer material on a light-transmitting substrate using the photosensitive transfer material so that the photosensitive light-shielding layer is in contact with the laminate ( A transfer step), and then peeling the temporary support from the laminate of the photosensitive transfer material and the light-transmitting substrate, exposing and developing the photosensitive light-shielding layer, and forming a black matrix. Is preferred.
This method does not require a cumbersome process and can be performed at low cost.
Next, the transfer process will be further described.

-Transfer process-
The transfer layer for shielding formed in the form of a film using the transfer material can be transferred and pasted onto the substrate by pressure bonding or heat pressure bonding with a heated and / or pressurized roller or flat plate.
Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575.

  The black matrix forming step in the present invention may include steps such as exposure, development, post-exposure, and heat treatment in addition to the transfer, and these steps are described in paragraph No. [0067] of JP-A-2005-3861. To the process described in [0074] can be preferably used.

<Coloring pixel and pixel forming method>
The colored pixel in the present invention is a colored pixel having at least one of R, G, and B formed in a region separated by a black matrix on the substrate.
In the pixel forming method according to the present invention, at least one of the R, G, and B coating liquids is applied by coating to a concave portion of a region separated by the black matrix formed in the black matrix forming step, and the colored pixel is formed. Is a method having a step of forming (hereinafter also referred to as a “pixel forming step”). The pixel formation step can be configured by providing other steps as necessary. The coating method is the same as the method described in the section of the photosensitive transfer material, and the coating method using a slit coater is particularly preferable.

  As a method of applying with a slit coater, the “application with a slit-like nozzle” described in the black matrix forming step can be mentioned as a preferred specific example.

  Preferred examples of the coating liquid used for forming the colored pixels include the colored photosensitive resin compositions described in paragraphs [0010] to [0021] of JP-A-2006-23696.

<Photospacer and formation method thereof>
The photospacer in the present invention is a spacer for maintaining the cell thickness between the substrates, and is a photocurable resin composition for photospacer (hereinafter also referred to as “photospacer composition”) on the black matrix. It is characterized in that it is obtained by a step of forming a photospacer by forming the composition layer using

As a method of forming the photospacer photocurable composition layer, a step of forming the photospacer after applying the photospacer composition to form the photospacer photocurable composition layer (coating method) Or a method of forming a photospacer by transferring onto a substrate using a transfer material having a layer made of a photocurable composition for photospacer using the photospacer composition (transfer method). It may be a method having
The step of forming the photo spacer is preferably a step of forming using a transfer material from the viewpoint of photo spacer shape uniformity and high positional accuracy.
In particular, a photospacer formed using a transfer material is effective for keeping the cell thickness of the liquid crystal cell uniform. Therefore, the photo-spacer can be suitably used for a liquid crystal display device application that easily causes display unevenness due to a variation in the cell thickness of the liquid crystal cell.
Next, the photosensitive resin composition for photospacers will be described.

-Photocurable resin composition for photo spacer-
The photo-curable resin composition for a photospacer in the present invention needs to have photosensitivity, and it is preferable to use a resin composition having photosensitivity and capable of alkali development.
Among them, it contains at least (A) a polymer substance, (B) a polymerizable monomer, and (C) a photopolymerization initiator, and if necessary, (D) a colorant or a surfactant is used as another component. Can be configured.
Examples of the photo-curable photosensitive resin composition for the photospacer include the components constituting the “photosensitive resin layer” described in paragraphs [0027] to [0054] of JP-A-2006-64921, and JP-A-2006. The components constituting the “negative photosensitive layer” described in paragraph Nos. [0050] to [0109] of JP-A-18222 are preferable examples.
Among the above, the component constituting the “photosensitive resin layer” described in paragraphs [0027] to [0054] of JP-A-2006-64921 is preferable from the viewpoint of high plastic deformation resistance.

The deformation recovery rate of the photospacer in the present invention is as follows: a 17 μmφ photospacer with a 50 μmφ frustum indenter, a load speed of 0.145 gf / second, a maximum load of 78 mN, a holding time of 5 seconds, and a measurement temperature of 23 ° C. The deformation recovery rate when performing a load-unloading test is preferably 70% or more, more preferably 80% or more, and still more preferably 85% or more.
When the deformation recovery rate is within the above range, the liquid crystal layer having a desired thickness can be obtained by resisting external compressive strength and preventing plastic deformation during panel formation.
As a result, display unevenness that may occur due to a thickness change is eliminated, and a high-quality image can be displayed, which is preferable.

In the present invention, the photospacer needs to be provided on the black matrix.
By providing the photo spacer on the black matrix, light leakage due to the photo spacer can be prevented, and display quality can be improved. Further, it may be provided on a portion where the black matrix and the colored layer overlap each other, and in this case, a sufficient cell gap can be maintained even with a photo spacer having a low height.

Furthermore, since the black matrix in the present invention has the configuration using the shielding transfer layer, the black matrix can be formed with high accuracy, and the photo spacer in the present invention is a photocuring for photo spacer having the above configuration. Since the film thickness variation is small because the conductive resin composition is used, the cell thickness variation defined by the light-shielding film and the photo spacer can be reduced. As a result, liquid crystal using these The display quality of the display device is improved.
In particular, in the case of a thin film configuration having a cell thickness of 2 to 4 μm, display unevenness in an image displayed by the liquid crystal display device can be effectively prevented.

The photospacer in the present invention can be produced by a production method similar to the production method described in the above black matrix section.
When forming the photocurable resin layer for a photospacer, the layer thickness is preferably 0.5 to 10.0 μm, and more preferably 1 to 6 μm. It is preferable for the layer thickness to be in the above-mentioned range since the occurrence of pinholes during coating formation during production is prevented, and development and removal of unexposed portions can be performed without requiring a long time.

<Color filter and manufacturing method thereof>
The color filter manufacturing method of the present invention includes the black matrix on a substrate, and a colored pixel having at least one of R, G, and B formed in a region separated by the black matrix. In a method for producing a color filter, transfer onto a substrate using a transfer material having a shielding transfer layer containing at least one of a resin and its precursor and a metal particle or a metal-containing particle on a temporary support. A step of forming a black matrix, a step of applying and forming a colored pixel having at least one of R, G, and B, and a photocurable resin composition for a photospacer on the black matrix. It has the process of forming a photo spacer.
The coating is preferably performed by a slit coater as described above, and the forming method in each step is as described above.
The color filter in the present invention is produced by the method for producing a color filter of the present invention.
The color filter manufactured in this way can be free from defects such as surface irregularities and unevenness in the thickness of colored pixels formed in a subsequent process even if it is a high-density black matrix.
Further, when a color filter is used in a liquid crystal display device, it becomes possible to maintain a constant cell gap by the photo spacer formed on the black matrix, and the liquid crystal display device can be obtained with high contrast and low cost. it can.

-Board-
As the substrate for forming the color filter, 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 prepared using the colored composition of the present invention and has a high-concentration black matrix. Can be suppressed and fluctuations 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, this color filter is a highly accurate black formed by exposing and developing the shielding transfer layer containing metal particles or metal-containing particles and a resin or a precursor thereof in a pattern. Since it has a matrix, display unevenness can occur over time, and variations 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 liquid crystal driving means, and the liquid crystal driving means is an active element (for example, a TFT). And a black matrix produced using the colored composition or transfer material according to the present invention is formed 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
<Preparation of a dispersion of particles having a silver-tin alloy part (dispersion A1)>
In 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 is subdivided into a volume of 150 ml, and the rotational speed is 2,000 r.m. using a desktop centrifuge H-103n [manufactured by Kokusan Co., Ltd.]. p. m. For 30 minutes. 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 composition shown in Table 1 below was mixed to prepare a photosensitive coating solution A1 for BM.

* Surfactant 1 used was a fluorosurfactant F-780-F, manufactured by Dainippon Ink & Chemicals, Inc.
* As the binder A, a styrene / acrylic acid copolymer (molar ratio = 56/44, weight average molecular weight 30,000) was used.
* The composition of the DPHA solution is as follows.
・ Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.… 76 parts ・ Propylene glycol monomethyl ether acetate… 24 parts

<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 BM photosensitive coating solution A1 prepared above was applied onto 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 film composed of a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film laminated structure by pressure-bonding a protective film (polypropylene film having a thickness of 12 μm) to the surface of the photosensitive resin layer. A resin transfer material was prepared. Hereinafter, this is referred to as BM photosensitive transfer material K1.

--- Formulation H-- for 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・ Fluorosurfactant 1 0.54 parts

--Prescription P1 of intermediate layer coating solution P1--
PVA-205 32.2 parts [manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550; polyvinyl alcohol]
・ Polyvinylpyrrolidone: 14.9 parts (manufactured by ASP 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, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) 12 times with pure water (1 part by mass of T-PD2 and pure water) The mixture was mixed at a ratio of 11 parts by mass (30 ° C.) and subjected to shower development with a flat nozzle at a pressure of 0.04 MPa for 50 seconds to remove the thermoplastic resin layer and the intermediate layer. 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>
-Preparation of colored photosensitive resin composition-
Colored photosensitive resin compositions R1, G1, and B1 having the compositions shown in Table 2 below were prepared.

-Formation of red (R) pixels-
The film thickness is 1 using a glass substrate coater MH-1600 (manufactured by FAS Asia) provided with a slit nozzle on the BM forming surface side of the glass substrate on which the black matrix (BM) is formed. The colored photosensitive resin composition R1 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 process). Next, using a slit-like nozzle on this photosensitive layer, the intermediate layer coating solution obtained above was applied to a dry film thickness of 1.5 μm to form a protective layer, and dried at 100 ° C. for 5 minutes. A protective layer was formed to produce an R pixel photosensitive material.

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, with the mask (quartz exposure mask having an image pattern) and the above-mentioned photosensitive material for R pixels standing vertically The entire surface was exposed with an exposure amount of 70 mJ / cm ² at a distance of 200 μm between the mask surface and the surface of the photosensitive material for the R pixel which is in contact with the protective layer (exposure step). Next, the photosensitive material for R pixel after exposure was developed using a developing 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, and R pixels were formed on the glass substrate on which the black matrix (BM) was formed.
Next, the glass substrate on which the R pixel 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 to be baked (baking process). 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 the R pixel are formed, the same process as the formation of the R pixel 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 R pixel described above is performed. Thus, a heat-treated B pixel was formed.
As described above, a color filter (hereinafter also referred to as “color filter substrate”) was produced.

In addition, the detail of each composition in composition R1 of the said Table 2 is as follows.
* Composition of R Pigment Dispersion 1 I. Pigment Red 254 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 8.0 parts, the following compound 1 (dispersant) ... 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 Co., Ltd.) ... 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 composition / Random 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

* DPHA solution and surfactant 1 are the same as those used for the coating solution for BM.

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-Polymer (benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]) random copolymer (weight average molecular weight 38,000)) ... 27 parts · Propylene glycol monomethyl ether acetate ... 73 parts

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

  A transparent electrode made of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above by sputtering.

<Formation of photo spacer>
-Production of photosensitive transfer material for photospacer formation-
In the production of the BM photosensitive transfer material K1, the photo spacer was prepared in the same manner as described above except that the BM photosensitive coating solution A1 used was changed to a photo spacer forming resin composition having the following composition. A forming photosensitive transfer material was prepared. The dry layer thickness of the photosensitive resin layer was 2.5 μm.

-Composition of photo spacer forming resin composition-
1-methoxy-2-propyl acetate 452 parts methyl ethyl ketone 327 parts methanol 0.035 parts binder 4 101 parts (methacrylic acid / allyl methacrylate copolymer (= 20/80 [molar ratio], weight average molecular weight 36000; Polymeric substances))
DPHA solution 99 parts 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine
2.5 parts ・ Hydroquinone monomethyl ether 0.039 parts ・ Surfactant 1 0.86 parts ・ Decolorizer 17 parts (Product name: Victoria Pure Blue BOH-M, manufactured by Hodogaya Chemical Co., Ltd.)

-Formation of photo spacer-
The protective (cover) film of the obtained photosensitive transfer material for forming the photospacer is peeled off, and the exposed surface of the photosensitive resin layer is placed on the ITO film of the color filter substrate on which the ITO film prepared above is sputtered. Lamination was performed using a laminator type Lamic II [manufactured by Hitachi Industries, Ltd.], and the film was bonded at a conveyance speed of 2 m / min under pressure and heating conditions of a linear pressure of 100 N / cm and 130 ° C. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (layer forming step).

Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 40 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed from the side with an exposure amount of 60 mJ / cm ² . Next, KOH developer (trade name: CDK-1, manufactured by FUJIFILM Electronics Materials Co., Ltd.) was sprayed from a flat nozzle for 80 seconds at 23 ° C. and a nozzle pressure of 0.04 MPa, and shower development was performed. Was removed by development to obtain a pattern (spacer pattern) (patterning step).

  The obtained spacer pattern was formed on the ITO film formed on the laminated portion of the black matrix and the red (R) pixel, and was a transparent column having a diameter of 16 μm and an average height of 2.0 μm.

  Next, the color filter substrate provided with the spacer pattern was heat-treated at 230 ° C. for 30 minutes (heat treatment step) to produce a photospacer.

<Production of liquid crystal display device>
Separately, a glass substrate was prepared as a counter substrate, and the PVA mode was patterned on the transparent electrode and the counter substrate of the color filter substrate obtained above, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method 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 and bonded to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, and DB1112H (as a blue (B) LED. A side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd. and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

(Examples 2 and 4)
In Example 1, the black matrix (BM) photosensitive coating liquid (dispersion A1) was used as the black matrix (BM) photosensitive coating liquid A2 (Example 2) and A3 (Example 4) described in Table 1 above. A black matrix substrate, a color filter, and a liquid crystal display device were produced in the same manner as in Example 1 except that the above was changed.

(Example 3)
In Example 1, the dispersion liquid A1 (dispersion liquid A1) of the silver-tin alloy part-containing particles was changed to the following silver fine particle dispersion liquid B1 (dispersion liquid B1), and further the BM photosensitive coating liquid A4 was used. In the same manner as in Example 1, a black matrix substrate, a color filter, and a liquid crystal display device were 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 three times to remove the soluble substance in the aqueous phase, thereby obtaining a silver fine particle dispersion B1 (dispersion B1).

<Preparation of photosensitive coating solution A4 for BM>
The following composition was mixed to prepare a photosensitive coating solution A4 for BM.
〔composition〕
-Silver fine particle dispersion B1 ... 60.00 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 5)
A black matrix substrate, a color filter, and a liquid crystal display device were produced in the same manner as in Example 1 except that the BM photosensitive coating solution A1 in Example 1 was changed to the BM photosensitive coating solution A5 prepared as follows. .

<Preparation of carbon black dispersion>
With a motor mill M50 (manufactured by Eiger), a dispersion of carbon black having the following formulation was prepared using zirconia beads having a diameter of 0.65 mm.
-Normal propanol 69 parts-Methacrylic acid / allyl methacrylate copolymer (copolymerization ratio = 20:80) 10 parts-Solsperse 20000 (Zeneca Corporation) 1 part-Carbon black (carbon black MA100, Mitsubishi Chemical Corporation 20) Part

<Preparation of silver particle dispersion>
-Production of silver particles-
3488 g of distilled water was added to 112 g of gelatin, and the resulting mixture was heated to about 47 ° C. to dissolve the gelatin. To this was added 4.0 g calcium acetate and 2.0 g potassium borohydride. Immediately thereafter, 6.0 g of silver nitrate dissolved in 1.0 L of distilled water was added with rapid stirring. Further, distilled water was added to adjust the final mass to 5.0 kg. The product was then cooled to near the gel temperature and extruded through a small hole into chilled water, thereby creating a very fine noodle. These noodles were supplied as amplification catalysts for producing blue silver on site. For convenience and to prevent the noodles from forming a molten mass, the noodles were diluted with water to make water 1 to noodle 3.

  6.5 g of potassium hydroquinone monosulfonate and 0.29 g of KCl dissolved in 81 g of distilled water were added to 650 g of borohydride-reduced silver nuclei. The noodle slurry was cooled to about 6 ° C.

Moreover, the following two types of solutions (A) and (B) were prepared in separate containers.
(A): Sodium sulfite (anhydrous) 19.5 g, sodium bisulfite (anhydrous) 0.98 g, distilled water 122.0 g
(B) ... Silver nitrate 9.75 g, distilled aqueous solution 122.0 g

  The above solutions (A) and (B) were mixed and stirring was continued to form a white precipitate. Immediately, this mixture was then added to the noodle slurry with rapid stirring in a short time (within 5 minutes). The temperature was maintained at 10 ° C. and amplification was allowed to proceed for about 80 minutes until all soluble silver salt was reduced onto the nuclei. The resulting blue slurry particles were washed through the slurry in a nylon mesh bag through the slurry and washed for about 30 minutes with the wash water passing through the bag so that all the salt was washed away. The blue silver dispersed and washed in the gel slurry was drained until the product mass was 412 g so as to obtain a blue silver dispersion having a concentration of 1.5% by weight silver when melted. When measured by a transmission electron micrograph, it was shown that the silver was composed of particles having a particle diameter of 80 nm.

-Preparation of silver particle dispersion-
To 4000 g of the silver dispersion slurry obtained as described above, 6 g of a dispersant (“Lapizol B-90” manufactured by NOF Corporation) and 2000 g of papain 5% aqueous solution were added and stored at a temperature of 37 ° C. for 24 hours. . This liquid was centrifuged at 2000 rpm for 5 minutes to precipitate silver particles. After discarding the supernatant, it was washed with distilled water to remove the degradation product of gelatin decomposed by the enzyme. The silver particle sediment was then washed with methyl alcohol and dried. An aggregate of about 60 g of silver fine particles was obtained. 53 g of this agglomerate, 5 g of a dispersant (“Solsperse 20000” manufactured by Avicia Co., Ltd.), and 22 g of methyl ethyl ketone were mixed. This was mixed with 100 g of 2 mmφ glass beads and dispersed with a paint shaker over 3 hours to obtain the intended silver particle dispersion.

The following additives were added to the silver particle dispersion obtained above and mixed to obtain a silver particle-containing coating solution A1.
-40.0 g of the above silver particle dispersion
・ Propylene glycol monomethyl ether acetate 40.0g
・ Methyl ethyl ketone 37.6g
・ Surfactant 1 (F-780-F) 0.1 g
・ Hydroquinone monomethyl ether 0.001 g
・ Dipentaerythritol hexaacrylate 2.1g
-Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.1 g

<Preparation of photosensitive coating solution A5 for BM>
The carbon black dispersion obtained above and the silver particle-containing coating solution A1 obtained above were added and mixed to prepare a photosensitive coating solution A5 for BM. The BM photosensitive coating solution A5 was prepared such that the blend ratio of carbon black / silver particles was 2.64.

(Example 6)
In the same manner as in Example 5 except that the BM photosensitive coating solution A6 prepared so that the carbon black / silver particle blend ratio was 1.40 was used in the BM photosensitive coating solution A5 in Example 5. A black matrix substrate, a color filter, and a liquid crystal display device were produced.

(Example 7)
In Example 1, a black matrix substrate, a color filter, and a liquid crystal display device were produced in the same manner as in Example 1 except that the BM photosensitive transfer material K1 was changed to the following BM photosensitive transfer material K2.

-Photosensitive transfer material for BM K2-
On a temporary support of polyethylene terephthalate film having a thickness of 75 μm, using a slit nozzle, a coating solution for a thermoplastic resin layer composed of the above-mentioned formulation H1 is applied so that the dry thickness becomes 5 μm. Let dry for minutes.
Next, the intermediate layer coating solution composed of the above-mentioned formulation P1 was applied on the thermoplastic resin layer prepared above with a slit coater so as to have a dry thickness of 1.5 μm, and dried at 100 ° C. for 3 minutes.
Further, a coating solution for a light reflecting layer containing metal fine particles obtained from the following formulation A7 is applied on the intermediate layer prepared above using a slit coater so that the optical density is 3.4, Further, a light absorbing layer coating solution obtained from the following formulation A8 was applied thereon using a slit coater so that the optical density was 0.6, and dried at 100 ° C. for 3 minutes.
In this way, a film in which the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the light reflecting layer and the light absorbing layer are integrated on the temporary support is prepared, and a protective film (polypropylene film having a thickness of 12 μm) is formed thereon. The resultant was pressure-bonded to obtain a photosensitive transfer material K2 for BM.

(Coating solution formulation for light reflecting layer: A7)
-Liquid A * 10 parts-Dipentaerythritol hexaacrylate (KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 76% propylene glycol monomethyl ether acetate solution) 0.19 parts-Bis [4- [N- [4- (4 6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate (0.2% dilute toluene) 0.1 part • 0.14 parts of the surfactant 1 • benzyl methacrylate / methacrylic acid (Molar ratio = 60/40, number average molecular weight 35000, 2.5% MEK diluted solution) 0.4 parts

  * Solution A is a heptane dispersion containing 30% of silver particles and obtained by thermally reducing silver stearate (average particle size 30 nm, distribution 5 nm to 50 nm, NAG- manufactured by Daiken Chemical Co., Ltd.) 09), 4 times the amount of toluene was added and stirred for 30 minutes. At this time, the volume (rate) of the metallic silver with respect to the solid content of the formulation A7 of the light reflecting layer coating solution is 60%.

(Coating liquid formulation for light absorbing layer: A8)
Benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, viscosity = 0.12, weight average molecular weight 38000) 37.9 parts dipentaerythritol hexaacrylate 29.1 parts bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 1.7 parts carbon black (black, NIPX35, manufactured by Degussa) 30.1 parts methyl cellosolve 560 parts of acetate / 280 parts of methyl ethyl ketone

(Comparative Examples 1-3)
In Example 1, except that the photosensitive coating liquid A1 for BM was changed to the photosensitive coating liquids K1 to K3 for black matrix (BM) shown in Table 3 below, a black matrix substrate and a color were prepared in the same manner as in Example 1. A filter was produced to produce a liquid crystal display device.

* Carbon Black Dispersion / Carbon Black (Nipex 35, manufactured by Degussa) ... 13.1 parts-Compound 1 (dispersing agent) ... 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 4)
In Example 1, the black matrix substrate was formed in the same manner as in Example 1 except that the BM photosensitive coating solution A1 was used to form a black matrix by the same coating method as the RGB pixel forming method of Example 1. A color filter and a liquid crystal display device were produced.

[Evaluation]
(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.

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

(Black matrix height uniformity)
The film thickness of the black matrix after baking is measured using a contact surface roughness meter (trade name: P-10, manufactured by TENCOR), and the standard deviation σ at 100 measurement points is calculated. Evaluation based on the criteria.
<Evaluation criteria>
◎: Standard deviation σ is less than 0.15 ○: Standard deviation σ is 0.15 or more and less than 0.2 ×: Standard deviation σ is 0.2 or more

(Spacer height uniformity)
Using the contact type surface roughness meter (trade name: P-10, manufactured by Tencor Corporation) as the layer thickness, the height of the highest part of the spacer from the color filter substrate surface on which the ITO is formed is used. Measurement was performed, a standard deviation σ at 100 measurement points was calculated, and evaluated according to the following criteria.
<Evaluation criteria>
◎: Standard deviation σ is less than 0.15 ○: Standard deviation σ is 0.15 or more and less than 0.2 ×: Standard deviation σ is 0.2 or more and less than 0.25 XX: Standard deviation σ is 0.25 or more

(Display unevenness)
For each of the liquid crystal display devices obtained above, the gray display when a gray test signal was input was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Display unevenness was not recognized at all.
○: Display unevenness was slightly recognized.
X: Some display unevenness was recognized.
XX: Display unevenness was recognized remarkably.

As is apparent from Table 4, in the example, a thin film and high-definition and high-density black matrix can be obtained, and the height uniformity of the spacer is good, so that the display is affected by the spacer, BM, and colored pixels. It can be seen that the unevenness is good.
On the other hand, in the comparative example, the BM is slightly thick, and it can be seen that the display unevenness affected by the spacer, the BM, and the colored pixels is extremely inferior.

Claims (9)

In a method for manufacturing a color filter having a black matrix on a substrate and a colored pixel having at least one of R, G, and B formed in a region separated by the black matrix, a resin is provided on the temporary support. And a transfer material having a shielding transfer layer containing at least one of its precursors and metal particles or metal-containing particles, and transferring to a substrate to form a black matrix; R, G, A step of applying and forming a colored pixel having at least one color of B, and a step of forming a photospacer on the black matrix using a photocurable resin composition for a photospacer. A method for producing a color filter. The method for producing a color filter according to claim 1, wherein the coating is performed by a slit coater. 3. The color according to claim 1, wherein the step of forming the photospacer is a step of forming using a transfer material having a photocurable resin composition layer for photospacers on a temporary support. A method for manufacturing a filter. The metal particle contained in the said transfer layer for shielding or at least 1 type of the particle | grains containing a metal is a particle | grain which has a silver tin alloy part, The any one of Claims 1-3 characterized by the above-mentioned. A method for producing a color filter. The method for producing a color filter according to claim 1, wherein the shielding transfer layer further contains a pigment. The method for producing a color filter according to claim 1, wherein the shielding transfer layer is a single layer. The shielding transfer layer includes at least two resin layers, at least one of the resin layers is a light reflecting layer, and at least one of the resin layers is a light absorbing layer. Item 6. The method for producing a color filter according to any one of Items 1 to 5. A color filter produced by the production method according to claim 1. A liquid crystal display device comprising the color filter according to claim 8.