JP2008248118A - Fine particle-containing composition, ink for forming colored film for display device, light-shielding material, light-shielding film for display device, substrate with light-shielding film, color filter, liquid crystal display element and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fine particle-containing composition providing a thin film which has a thin thickness and excellent light-shielding properties, and of which the change of color is suppressed when exposed to high-temperature environment, and to provide an ink for a colored film for a display device, a light-shielding film for the display device, a light-shielding material, a substrate with the light-shielding film, and a color filter, a liquid crystal display device and a liquid crystal display device capable of providing high-contrast clear image display. <P>SOLUTION: The fine particle-containing composition contains fine particles containing a metallic compound and a polymer compound having a repeating unit derived from an ethylenically unsaturated monomer containing at least one kind of a thioether structure on the side chain. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fine particle-containing composition suitable for producing a light-shielding film (light-shielding film) provided inside a display device such as a plasma display device, EL display device, or CRT display device, and the fine particle-containing composition. The present invention relates to a colored film forming ink for display device, a light shielding film for display device, a light shielding material, a substrate with a light shielding film, a color filter, a liquid crystal display element, and a liquid crystal display device.

  A light-shielding film for use in a display device has a black edge, a grid around a pixel, a stripe-like black edge (so-called black edge) inside a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or the like. Matrix), thin film transistors (TFTs), which are provided as dot-like or linear black patterns for light shielding.

For example, a black matrix is an example of a light shielding film that constitutes a liquid crystal display device or the like, and is provided so as to surround each colored pixel (red, green, blue) of a color filter provided inside the liquid crystal display device. This prevents a decrease in contrast due to light leakage between pixels. As another example, in a liquid crystal display element of an active matrix driving system using TFTs, there is a light shielding film provided on the TFTs in order to prevent image quality degradation due to TFT current leakage due to light.
These light-shielding films are generally required to have a light-shielding property having an optical density of 2 or more, and the color tone of the light-shielding film is preferably black from the viewpoint of display quality of the display device.

  In relation to the above, there is a disclosure relating to a method of producing a light shielding film using a dispersion of metal fine particles (see, for example, Patent Document 1). In this method, a widely known dispersant is used for dispersing the metal fine particles.

Moreover, there is an example in which a polymer compound having a thioether group is used together with silver halide grains as a protective colloid for silver halide grains (see, for example, Patent Documents 2 to 4).
Also disclosed are core-shell fine particles having a shell made of a metal compound on the surface and a core made of a metal inside, and a black matrix using the same (for example, see Patent Document 5).
Furthermore, a black matrix having a polymer binder, metal fine particles dispersed in the polymer binder, and a compound having at least one sulfur atom and / or nitrogen atom is disclosed (for example, see Patent Document 6). .
JP 2004-334182 A Japanese Patent Laid-Open No. 2-166442 JP-A-4-151140 US Pat. No. 3,615,624 JP 2006-18201 A JP-A-2005-250461

  However, in the above-described method for producing a light-shielding film, the dispersant used for dispersing the metal fine particles is usually widely used, and as a use for the light-shielding film for a display device, the light-shielding performance is satisfactory because the dispersion of the metal fine particles is insufficient. Cannot be obtained.

  In addition, when producing a light-shielding film for use in a display device, it may be exposed to a high temperature in the manufacturing process (for example, post-baking after development), but dispersion of metal fine particles using a conventionally well-known dispersant. In the system, there is a problem that the color of the film is likely to change at a high temperature, and the desired light shielding performance and display contrast cannot be obtained.

  The present invention has been made in view of the above, and a fine particle-containing composition capable of obtaining excellent light-shielding performance with a thin film and suppressing color change when exposed to a high-temperature environment, for forming a colored film for a display device An object of the present invention is to provide ink, a light shielding film for a display device, a light shielding material, a substrate with a light shielding film, a color filter capable of displaying a high-contrast and vivid image, a liquid crystal display element, and a liquid crystal display device. The goal is to achieve this.

  In the present invention, use of a polymer having a thioether structure as a dispersing agent for fine particles of a metal compound is effective for dispersibility when dispersed, dispersion stability after dispersion, and suppression of color change in a high temperature environment. It has been achieved based on such knowledge. Specific means for achieving the above object are as follows.

<1> Fine particles containing a metal compound and a polymer compound having a repeating unit derived from an ethylenically unsaturated monomer having at least one thioether structure in the side chain Containing composition.
<2> The fine particle-containing composition according to <1>, wherein the metal compound is a metal sulfide.

<3> The fine particle-containing composition according to <1>, wherein the metal sulfide is silver sulfide.
<4> The fine particle-containing composition according to any one of <1> to <3>, wherein the polymer compound has at least a repeating unit represented by the following general formula (I).

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total, and R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms in total, an aryl group having 6 to 14 carbon atoms in total, or An aralkyl group having 7 to 16 carbon atoms in total is represented. Z represents —O— or —NH—, and Y represents a divalent linking group having 1 to 8 carbon atoms in total. ]

<5> The fine particle-containing composition according to any one of <1> to <4>, wherein the polymer compound further has an acid group.
<6> The fine particle-containing composition according to <5>, wherein the acid group is a carboxylic acid group.

<7> The fine particle-containing composition according to any one of <1> to <6>, further including a compound that is cured by heat or light.
<8> The fine particle-containing composition according to any one of <1> to <7>, further including a photopolymerization initiator.

<9> The fine particle-containing composition according to <8>, wherein the photopolymerization initiator includes one or more selected from aromatic ketones, hexaarylimidazole compounds, and ketoxime ester compounds.
<10> A colored film forming ink for a display device, comprising the fine particle-containing composition according to any one of the above items <1> to <9>.

<11> A light-shielding material used for forming a light-shielding film for a display device, comprising: a fine particle containing a metal compound and a polymer compound having a repeating unit represented by the following general formula (I) on a support; A light-shielding material comprising at least one fine particle-containing layer.

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total, and R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms in total, an aryl group having 6 to 14 carbon atoms in total, or An aralkyl group having 7 to 16 carbon atoms in total is represented. Z represents —O— or —NH—, and Y represents a divalent linking group having 1 to 8 carbon atoms in total. ]

<12> The light-shielding material according to <11>, wherein the fine particle-containing layer further contains a compound that is cured by heat or light.
<13> The light-shielding material according to <11> or <12>, further containing a photopolymerization initiator.

<14> The light-shielding material according to any one of <11> to <13>, wherein the fine particle-containing layer is a layer that can be transferred to a transfer target.
<15> The fine particle-containing composition according to any one of <1> to <9>, the colored film forming ink for display device according to <10>, or the above <11> to <14>. A light shielding film for a display device, comprising the light shielding material according to any one of the above items.

<16> A substrate with a light shielding film, comprising the light shielding film for a display device according to <15>.
<17> On a color filter having a pixel group including a plurality of pixels exhibiting different hues on a light-transmitting substrate and a light-shielding image separating each pixel constituting the pixel group, the light-shielding image is A color filter, which is the light shielding film for a display device according to <15>.

<18> A color filter comprising the substrate with a light-shielding film according to <16>.
<19> A liquid crystal display device comprising the substrate with a light-shielding film according to <16>.
<20> A liquid crystal display device comprising the liquid crystal display element according to <19>.

  ADVANTAGE OF THE INVENTION According to this invention, the fine particle containing composition excellent in the dispersion stability which can obtain the outstanding light-shielding performance with a thin film, and can suppress the color change when exposed to a high temperature environment, The coloring film forming ink for display apparatuses Further, it is possible to provide a light-shielding film for a display device, a light-shielding material, a substrate with a light-shielding film, a color filter capable of displaying a high-contrast and vivid image, a liquid crystal display element, and a liquid crystal display device.

  Hereinafter, the fine particle-containing composition of the present invention will be described in detail, and through the description, the colored film forming ink for display device, the light shielding film for display device, the light shielding material, the substrate with the light shielding film, the color filter, and the liquid crystal display Details of the element and the liquid crystal display device will also be described in detail.

<Fine particle-containing composition>
The fine particle-containing composition of the present invention is derived from fine particles containing a metal compound (hereinafter simply referred to as “metal compound fine particles”) and an ethylenically unsaturated monomer containing at least one thioether structure in the side chain. It preferably contains a polymer compound having a repeating unit (hereinafter also referred to as “polymer dispersant”), and further contains a compound that is cured by heat or light. Can be configured.

  In the present invention, the metal compound fine particles are dispersed and used as a colorant (particularly a black colorant), and the polymer dispersant in the present invention is used as a dispersant for dispersing the metal compound fine particles. This contributes to particle behavior such as prevention of agglomeration of fine particles of metal compounds, and suppresses changes in color caused by alteration of resin components and fine particles in high temperature environments, such as when exposed to high temperatures in the manufacturing process. Therefore, the dispersibility during dispersion and the dispersion stability after dispersion are improved, and the hue is good and a high optical density can be ensured.

  The fine particle-containing composition of the present invention is a polymer compound in which the metal compound fine particles have a repeating unit derived from an ethylenically unsaturated monomer having a thioether structure (described later) in the side chain (the polymer dispersant according to the present invention). ) Is preferably dispersed therein.

-Metal compound fine particles-
The fine particle-containing composition of the present invention contains at least one metal compound fine particle as a (particularly black) colorant. By using metallic fine particles as a colorant, a high-density image formability is possible with a thin film, which is particularly effective for forming a black image such as a light-shielded image (including a black matrix).

  In the present invention, “metal” in the metal compound fine particle is based on “metal” (page 352) described in “Iwanami Physical and Chemical Dictionary (5th edition)” (1998, published by Iwanami Shoten). The “metal compound” is a compound of a metal and an element other than the metal, and the metal here is also synonymous with the metal in the metal compound fine particles.

In the present invention, the metal compound fine particles include composite fine particles of a metal and a metal compound and composite fine particles of a metal compound and a metal compound in addition to the fine particles made of a metal compound.
The metal compound fine particles can be prepared by oxidizing or sulfurating metal fine particles. Hereinafter, the metal compound fine particles will be further described.

The metal compound fine particles are not particularly limited and can be appropriately selected. For example, the metal compound fine particles are selected from metal groups included in the fourth period, the fifth period, and the sixth period of the long-period periodic table (IUPAC 1991). It is preferable to contain a metal as a main component, and from a group of metals included in Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14. It is preferable to contain a selected metal as a main component.
Among these metals, metals of the fourth period, the fifth period, or the sixth period, and metals of Group 2, Group 10, Group 11, Group 12, or Group 14 are more preferable.

  The shape of the metal compound fine particles is not particularly limited, and is an amp shape, a potato shape, a rod shape (a needle shape, a cylindrical shape, a rectangular column shape such as a rectangular parallelepiped, a rugby ball shape, etc.), a flat shape (a scale shape, an elliptical plate shape, a plate shape). Shape), fibrous shape, confetti shape, coil shape and the like. Preferred are plate-like particles and rod-like (rod-like) shapes.

  Preferred examples of the metal constituting the metal compound fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, Examples thereof include at least one selected from calcium, titanium, bismuth, antimony, lead, and alloys thereof. Furthermore, examples of the metal constituting the preferred metal compound fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or alloys thereof, and particularly preferably copper, silver, Examples thereof include at least one selected from gold, platinum, tin, and alloys thereof.

  Among these, gold, silver, copper, and tin are preferable, and silver is particularly preferable because fine particles can be easily obtained. The metal compound fine particles in the present invention may be a compound of an alloy of the metal, and a preferable alloy includes an alloy of silver and tin.

  The number average particle diameter of the metal compound fine particles is not particularly limited as long as it does not exceed the film thickness, but is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 500 nm, and still more preferably in the range of 10 to 200 nm. When the number average particle diameter is within the above range, the production is easy, and when a color filter is produced using the metal compound fine particles within the above range, a good black (not brownish hue due to characteristics) is visually observed. The black matrix such as a black matrix is obtained, the particle diameter is too large, the stability of the dispersion after dispersion of the metal compound fine particles is lowered, and the light shielding property is not deteriorated.

  Here, "particle size" refers to the diameter when the area of the electron micrograph image of the particle is a circle of the same area, "number average particle size" is to determine the particle size for a number of particles, It means the average value of 100 particles obtained. The particle size distribution is not particularly limited.

  The metal compound fine particles are a compound of a metal and an element other than the metal, and examples thereof include metal oxides, sulfides, sulfates, and carbonates. Specifically, examples of the metal compound include copper oxide (II), iron oxide, silver oxide, iron sulfide, silver sulfide, copper sulfide (II), and titanium black. Of these, metal sulfides are particularly preferable in terms of color tone and ease of fine particle formation, and silver sulfide is particularly preferable in terms of color tone, ease of fine particle formation, and stability.

  The metal compound fine particles may have a uniform composition or a non-uniform composition. As an example of the non-uniform composition, there can be mentioned a coating layer having a composition different from the inside on the surface.

  The metal compound fine particles in the present invention are not particularly limited, and can be produced by a known method such as a gas phase method or a liquid phase method. The method for producing metal compound fine particles is described in, for example, “Latest Trends in Technology and Application of Ultrafine Particles II” (Sumibe Techno Research Co., Ltd., issued in 2002).

  The metal compound fine particles can also be prepared by oxidizing or sulfiding rod-shaped metal fine particles.

The metal fine particles can be commercially available, or can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
For rod-shaped silver fine particles, for example, see Adv. Mater. The description of 2002, 14, 80-82 can be referred to, that is, in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide) after adding further silver salt using spherical silver fine particles as seed particles. Thus, a silver rod or a wire can be obtained by using a reducing agent having a relatively low reducing power such as ascorbic acid. In addition, the same description is described in Mater. Chem. Phys. 2004, 84, 197-204, Adv. Funct. Mater. 2004, 14, 183-189.

Also, Mater. Lett. 2001, 49, 91-95, a method using electrolysis is described in J. Org. Mater. Res. 2004, 19, 469-473 describe a method for producing a silver rod by irradiating microwaves, respectively. In addition, for an example in which reverse micelle and ultrasonic waves are used in combination, J. Org. Phys. Chem. B, 2003, 107, 3679-3683.
As for gold, J. Phys. Chem. B 1999, 103, 3073-3077 and Langmuir 1999, 15, 701-709; Am. Chem. Soc. 2002, 124, 14316-14317.

  Rod-shaped particles can be prepared by a reduction method in the presence of a surfactant. Basically, various rod-shaped particles can be prepared by controlling the type of surfactant, the type of reducing agent, adjusting the amount of addition, and controlling the pH. Specifically, a surfactant that has little interaction with the metal is used first, and at the stage of reduction and particle growth, a surfactant that interacts greatly with the metal is added to suppress further particle growth. . That is, the shape can be controlled by the type and time of the reducing agent.

The metal compound fine particles in the present invention include composite fine particles of metal and metal compound and composite fine particles of metal compound and metal compound.
For example, composite fine particles of silver sulfide and another metal (for example, tin) or a metal compound (for example, tin sulfide) are preferable.

The shape of the composite fine particles in the metal compound fine particles is not particularly limited, and examples thereof include those having different compositions between the inside and the surface of the particles, and those obtained by combining two types of particles. Further, each of the metal compound and the metal constituting the composite fine particle may be one type or two or more types.
Specific examples of the “composite fine particles of metal and metal compound” include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like.

  In addition to the above, the metal compound fine particles in the present invention may be composite particles having a core-shell structure. The composite particles having a core / shell structure are those in which the surface of the core material is coated with the shell material. When using composite particles having a core-shell structure, examples of the shell material include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe. , Se, Te, CuCl, CuBr, CuI, TlCl, TlBr, TlI, and a solid solution thereof or a solid solution containing 90 mol% or more of these, or copper, silver, gold, platinum, palladium, nickel And at least one metal selected from tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or alloys thereof. . These shell materials are preferable in that they have a light absorption peak that resonates between quantum levels discretized by the quantum confinement effect in the wavelength range of 300 to 800 nm used.

Among the above, a preferable core material is at least one selected from copper, silver, gold, palladium, nickel, tin, bismuth, ammotin, lead, or an alloy thereof.
The shell material is also preferably used as a refractive index adjusting agent for the purpose of reducing the reflectance.

  As a core material of the composite particles having a core-shell structure, for example, at least one metal selected from copper, silver, gold, palladium, or an alloy thereof can be used.

There is no restriction | limiting in particular in the preparation methods of the composite particle which has a core-shell structure, A typical method is shown below.
(1) A method of forming a metal compound shell on the surface of a metal fine particle produced by a known method by oxidation, sulfurization, or the like. For example, there is a method in which metal fine particles are dispersed in a dispersion medium such as water and sulfides such as sodium sulfide and ammonium sulfide are added. By this method, the particle surface is sulfided to form core-shell composite particles.
In this case, the metal fine particles to be used can be produced by a known method such as a gas phase method or a liquid phase method. For the method for producing the metal fine particles, for example, “Latest Trend II in Ultrafine Particle Technology and Applications” Betechno Research Co., Ltd., published in 2002).
(2) A method of continuously forming a metal compound shell on the surface in the process of producing metal fine particles. For example, by adding a reducing agent to a metal salt solution, reducing part of the metal ions to produce metal fine particles, adding sulfide to this, and forming metal sulfides around the produced metal fine particles Core-shell composite particles are formed.

  Among the above-mentioned metal compound fine particles, fine particles having an aspect ratio (ratio of major axis length of particles / minor axis length of particles) of 2 to 100 can control the absorption spectrum and make the hue close to black. Is preferable. Among these, the aspect ratio is preferably 4 to 80, more preferably 10 to 60, and particularly preferably 15 to 50 in that the absorption spectrum can be controlled and the hue can be made closer to black. When the aspect ratio is within the above range, it is relatively easy to obtain black particles, absorption in the visible light region is good, and image quality (resolution) is not reduced.

  The aspect ratio means a value obtained by dividing a major axis length defined as described later by a minor axis length of metal compound fine particles, and is an average value of values obtained by measuring 100 metal compound fine particles. The projected area of the particles can be obtained by measuring the area on the electron micrograph and correcting the photographing magnification.

Next, the diameter (major axis length, minor axis length) will be described using metal compound fine particles as an example.
The particle diameter of the metal compound fine particles is defined as a triaxial diameter. Then, a box (cuboid) in which one metal compound particle fits exactly (tightly) is considered, and the length L, width b, height or thickness t of the box is defined as the dimension of the metal compound particle. . There are several ways to store the metal compound particles in the box. In the present invention, the following method is adopted.
First, the metal compound particles are placed on a flat surface so that the center of gravity is the lowest and remains stable. Next, the metal compound 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 defined as “width b”.
Next, the metal compound particles are sandwiched between two parallel flat plates that are perpendicular to the two flat plates that determine the width b and also perpendicular to the flat surface, and the distance between the two flat plates is defined as “length L”. To do. Finally, the top plate is placed parallel to the plane so as to contact the highest position of the metal compound particles, and the distance between the top plate and the plane is defined as the height or thickness t. (This method forms a rectangular parallelepiped defined by a flat surface, two flat plates and a top plate.) In addition, the axis corresponding to the longest three-axis diameters b, L, and t of the metal compound particles is defined as “long `` Axis '', the length in the major axis direction is `` major axis length '', and the diameter when the projected area obtained by irradiating metal compound particles with light parallel to the major axis is converted to a perfect circle is `` It is defined as “short axis length”.

  The minor axis length of the metal compound fine particles is preferably within the range of 4 to 50 nm, more preferably within the range of 15 to 50 nm, and most preferably within the range of 15 to 30 nm. The major axis length (maximum length) of the metal compound fine particles is preferably in the range of 10 to 1000 nm, more preferably in the range of 100 to 1000 nm, and preferably in the range of 400 to 800 nm.

  By adjusting the aspect ratio (mixing particles with different aspect ratios), that is, using fine particles with the same metal and different aspect ratios together, the metal compound fine particles can control the absorption spectrum and make the hue closer to black. it can. In order to approach black, it can also be obtained by combining particles having various aspect ratios such as other metals and metal compound fine particles.

  When the metal compound fine particles in the present invention are changed from a spherical shape to, for example, a rod shape, the amount of visible light absorption is also increased by a factor of about 2, and the total absorption coefficient becomes larger than in the case of spherical particles, and the transmission density can be increased. It is. Thereby, it is possible to reduce the thickness while maintaining a high concentration.

The metal compound fine particles may be used alone or in combination of two or more. Furthermore, the composite fine particles in which metal fine particles are combined with metal fine particles may be used.
The content of the metal compound fine particles in the fine particle-containing composition varies depending on the type and properties of the fine particles, but is preferably 10 to 98% by mass and more preferably 20 to 95% by mass with respect to the total solid content of the composition. 30 to 93% by mass is preferable. When the content is within the above range, a high concentration can be obtained with a thin film, and developability is not hindered.

-Polymer compound-
The fine particle-containing composition of the present invention is at least one polymer compound having a repeating unit derived from an ethylenically unsaturated monomer containing at least one thioether structure in the side chain as a dispersant for the metal compound fine particles. (Polymer dispersant in the present invention). Since a polymer compound having a thioether structure is used as a dispersing agent, when the above-described metal-based fine particles are dispersed and contained, the dispersibility during dispersion and the dispersion stability after dispersion are improved, and the hue (especially black) Phase) is good, and an image having a high optical density can be formed.

  Among them, as a polymer compound having in the molecule a repeating unit derived from an ethylenically unsaturated monomer having at least one thioether structure in the side chain, at least one repeating unit represented by the following general formula (I) is used. A polymer compound having one kind is particularly preferred.

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

In the general formula (I), R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms. The group, the aryl group, and the aralkyl group may each independently be unsubstituted or substituted, and may form a saturated or unsaturated cyclic structure.

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

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

The aryl group having 6 to 14 carbon atoms in total represented by R ² may be unsubstituted or substituted, for example, aryl such as phenyl group, toluyl group, xylyl group, naphthyl group, anthracenyl group, etc. Groups. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
Among the above, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

The aralkyl group having 7 to 16 carbon atoms represented by R ² may be unsubstituted or substituted, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and an anthracenylmethyl group. An aralkyl group is mentioned. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
Among the above, an aralkyl group having 7 to 11 carbon atoms is preferable, and a benzyl group is particularly preferable.

In the general formula (I), Z represents —O— or —NH—. Y represents a divalent linking group having 1 to 8 carbon atoms in total.
The divalent linking group having 1 to 8 carbon atoms represented by Y is, for example, an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, pentylene group), alkenylene group (eg, ethenylene group, Propenylene group), alkynylene group (eg, ethynylene group, propynylene group), arylene group (eg, phenylene group), divalent heterocyclic group (eg, 6-chloro-1,3,5-triazine-2, 4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl group), -O-, -CO-, -NR- (R is a hydrogen atom, Represents an alkyl group or an aryl group), or a combination thereof (for example, —NHCH ₂ CH ₂ NH—, —NHCONH—, etc.).

The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group represented by Y, and the alkyl group or aryl group represented by R may have a substituent. Examples of the substituent are the same as those of the aryl group represented by R ² . The alkyl group and aryl group represented by R are synonymous with the alkyl group and aryl group represented by R ² described above.

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

The polymer dispersant in the present invention may be a polymer compound containing two or more sulfur atoms by copolymerizing not only one type of repeating unit represented by the general formula (I) but also two or more types. . In addition, the thioether structure constituting the side chain is not only one sulfur atom but also a side chain having two or more sulfur atoms by constituting Z and R ² with a group having a sulfur atom. Can do.

  The polymer dispersant in the present invention is a monomer having a thioether structure as a side chain in a desired polymer compound, or homopolymerization of a monomer having a thioether structure in a side chain, or a monomer having a thioether structure in a side chain. And can be obtained by copolymerization with other monomers. Preferably, a thioether structure is introduced into the side chain of the ethylenically unsaturated monomer, or homopolymerization of an ethylenically unsaturated monomer containing a thioether structure in the side chain, or an ethylenically unsaturated group containing a thioether structure in the side chain. It can be obtained by copolymerization of a saturated monomer and another copolymer component.

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

Among the above, in particular, R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, an ethyl group, a normal propyl group, a normal butyl group, a tert-butyl group, or a phenyl group, and Z is − A compound that is O- and Y is an ethylene group is preferred.

The polymer dispersant in the present invention may be a copolymer of the repeating unit represented by the general formula (I) and another vinyl monomer.
Other vinyl monomers include aromatic vinyl compounds (eg, styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, etc.), vinyl cyanide (eg, (meth) acrylonitrile, and α- Chloroacrylonitrile, etc.), carboxylic acid vinyl esters (eg, vinyl acetate, vinyl benzoate, vinyl formate, etc.), aliphatic conjugated dienes (eg, 1,3-butadiene, isoprene, etc.), (meth) acrylic acid alkyl esters (eg, Examples such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate), (meth) acrylic acid alkylaryl esters ( Example, benzyl (meth) acrylate ), (Meth) acrylic acid substituted alkyl esters (eg, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.)), alkyl (meta ) Acrylamide (eg, (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, and tert-octyl (meth) acrylamide) Substituted alkyl (meth) acrylamides (eg, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, etc.), polymerizable oligomers (eg, one-end methacryloylated polymer) Methacrylate oligomer having a methacryloyl group at one end a polystyrene oligomer, and having a methacryloyl group at one end of polyethylene glycol, and the like) are preferably used.

  The polymerization ratio of the repeating unit represented by the general formula (I) in the polymer compound having at least one thioether group (polymer dispersing agent in the present invention) is preferably 1 to 100% in terms of mass fraction. -80% is more preferable, and 10-50% is particularly preferable. When the polymerization ratio is within the above range, it is effective to improve the dispersibility during dispersion and the dispersion stability after dispersion, and to improve the hue and optical density.

  In addition, the polymer dispersant is preferably a polymer compound having an acid group in the molecule in that alkali developability can be imparted as necessary. As the acid group, for example, a group such as carboxylic acid group, sulfonic acid, phosphoric acid, boronic acid, phenols, and sulfoamide is preferable, and a polymer compound having at least one carboxylic acid group is particularly preferable.

  When alkali development is required, the polymer dispersant preferably has an acid value of 20 to 250 mgKOH / g, more preferably 50 to 200 mgKOH / g, and 70 to 180 mgKOH / g. Is most preferred. When the acid value is within the above range, the dispersibility during dispersion and the dispersion stability after dispersion are good, and the alkali developability is also good.

  The molecular weight of the polymer dispersant is preferably 2,000 to 1,000,000, more preferably 3,000 to 200,000, and most preferably 5,000 to 100,000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, it is effective for improving dispersibility, good film strength can be obtained, and developability is not hindered.

  The content of the polymer compound having at least one thioether group in the fine particle-containing composition is preferably 1 to 40% by mass, more preferably 3 to 30% by mass with respect to the mass of the metal compound fine particles described above. Preferably, 5 to 20% by mass is more preferable. When the content is within the above range, the fine particles are sufficiently adsorbed to improve the dispersibility, and are effective in improving the hue and optical density by suppressing the change in hue due to heat. There is nothing to do.

-Compounds that cure by heat or light-
The fine particle-containing composition of the present invention preferably contains at least one compound that is cured by heat or light (hereinafter, also referred to as “curable compound”) from the viewpoint of enhancing the strength of the formed film.
Examples of the compound that is cured by heat or light include a polymerizable compound, and the polymerizable compound is selected from compounds having at least one ethylenically unsaturated bond, preferably two or more.

Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester Examples include acrylate oligomers.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (i) to a polyisocyanate compound having two or more isocyanate groups. A urethane compound etc. are mentioned.
_{CH 2 = C (R 4)} COOCH 2 CH (R 5) OH general formula (i)
(However, R ₄ and R ₅ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, In addition, a polymerizable composition excellent in photosensitive speed can be obtained.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

Among these, it is preferable to use polyfunctional acrylic monomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like.
Two or more kinds of curable compounds may be mixed and used in addition to being used alone.

  When the curable compound is used, the addition amount of the curable compound in the fine particle-containing composition is not particularly limited, and is generally 5 to 50% by mass with respect to the total solid content of the composition. Yes, 10-40 mass% is preferable. When the addition amount is within the above range, the photosensitivity and the strength of the film constituting the image are good, and the adhesiveness of the film when the film is formed does not become excessive.

  The curable compound is a compound that can be cured (particularly polymerized) using light or heat. When the fine particle-containing composition is configured to be photocurable or thermosetting, it is preferable to use a polymerization initiator in combination. Among these, it is more preferable that a photopolymerization initiator is added to constitute photocurability.

-Photopolymerization initiator-
Preferred photopolymerization initiators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) keto Examples include oxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, and (k) compounds having a carbon halogen bond. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones (a) Aromatic ketones preferred as the photopolymerization initiator used in the present invention include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. Fouassier, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example, the following is mentioned.

  Among them, examples of particularly preferred (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, for example, the following compounds.

  Examples of the α-substituted benzoin compounds described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example, the following compounds.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-181345 include the following compounds.

  Examples of the α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, such as the following compounds.

  P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  The acylphosphine sulfide described in JP-B-2-9597, for example, the following compounds may be mentioned.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

  Among the above, α-aminobenzophenones are preferable.

(B) Onium salt compound As the (b) onium salt compound preferable as the photopolymerization initiator used in the present invention, compounds represented by the following general formulas (1) to (3) may be mentioned.

In General Formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In General Formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of onium salts that can be suitably used in the present invention include those described in paragraphs [0030] to [0033] of Japanese Patent Application No. 11-310623 and Japanese Patent Application No. 2000-160323. Listed in paragraph numbers [0015] to [0046], Japanese Patent Application No. 2000-266797, Japanese Patent Application No. 2001-177150, Japanese Patent Application No. 2000-160323, Japanese Patent Application No. 2000-184603, Japanese Patent Application No. 2000-184603 Specific aromatic sulfonium salt compounds described in 2000-310808, Japanese Patent Application No. 2002-265467, and Japanese Patent Application No. 2002-366539 can be exemplified.

  The onium salt used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less.

(C) Organic peroxide Preferred as the photopolymerization initiator used in the present invention (c) The organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiary butyl peroxy) -3,3. 5-trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene high Dropper oxide, parameter hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl Cumyl peroxide, dicumyl peroxide, bis (tertiarybutylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-xanoyl peroxide, peroxy Succinic oxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate Bonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxyacetate, tertiary butyl peroxypivalate, tertiary butyl peroxyneodecanoate, tarsha Tributyl peroxyoctanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t -Butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra -(T-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) Examples include benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate), and the like.

  Among them, 3,3′4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3′4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3′4 4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylper) Peroxyesters such as (oxycarbonyl) benzophenone, 3,3′4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred.

(D) Thio compound As a preferable (d) thio compound as a photoinitiator used by this invention, the compound which has a structure represented by following General formula (4) is mentioned.

(Wherein R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, R ²⁷ represents a hydrogen atom or an alkyl group. R ²⁶ and R ²⁷ are bonded to each other to form an oxygen, sulfur and nitrogen atom. This represents a group of nonmetallic atoms necessary to form a 5- to 7-membered ring that may contain a selected heteroatom.)

As an alkyl group in the said General formula (4), a C1-C4 thing is preferable. As the aryl group, those having 6 to 10 carbon atoms such as phenyl and naphthyl are preferable, and as the substituted aryl group, a halogen atom such as a chlorine atom and an alkyl such as a methyl group as described above. And those substituted with an alkoxy group such as a group, a methoxy group, and an ethoxy group. R ²⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula (4) include the following compounds.

(E) Hexaarylbiimidazole compound (e) Hexaarylbiimidazole compounds preferable as the photopolymerization initiator used in the present invention include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, for example, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.
Among the above, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole is preferable.

(F) Ketooxime ester compound Preferred as the photopolymerization initiator (f) ketoxime ester compound used in the present invention is 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one , 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

(G) Borate compound As an example of the (g) borate compound preferable as a photoinitiator used for this invention, the compound represented by following General formula (5) can be mentioned.

(Wherein R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same as or different from each other, each substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be combined with each other to form a cyclic structure; . ^However, among R ^28, R ^{29, R 30} and ^{R 31,} at least one is a substituted or unsubstituted alkyl ^{group. (Z 5) +} represents an alkali metal cation or a quaternary ammonium cation.)

Examples of the alkyl group of R ^{28 to} R ³¹ include linear, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. As also substituted alkyl group, the alkyl group as described above, a halogen atom (e.g., -Cl, etc. -Br), a cyano group, a nitro group, an aryl group (preferably phenyl group), hydroxy group, -COOR ³² ( Here, R ³² represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group, —OCOR ³³ or —OR ³⁴ (where R ³³ and R ³⁴ are alkyl groups having 1 to 14 carbon atoms, or An aryl group) and those having a substituent represented by the following formula are included.

(Wherein R ³⁵ and R ³⁶ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group)

The aryl groups of R ²⁸ to R ^31, a phenyl group, contains 1-3 aryl rings such as naphthyl group, a substituted aryl group, a substituted substituted alkyl group described above in the aryl group as described above Those having a group or an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group of R ^{28 to} R ³¹ include linear, branched and cyclic groups having 2 to 18 carbon atoms. Examples of the substituent of the substituted alkenyl group include those listed as the substituents of the substituted alkyl group. Examples of the alkynyl group of R ^{28 to} R ³¹ include linear or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituent of the substituted alkyl group. included.
In addition, examples of the heterocyclic group of R ^{28 to} R ³¹ include a 5- or more-membered heterocyclic group containing at least one of N, S, and O, and preferably a 5- to 7-membered heterocyclic group. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent. Specific examples of the compound represented by the general formula (5) are described in U.S. Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. And the compounds shown below.

(H) Azinium Compound Preferred examples of the (h) azinium salt compound used as the photopolymerization initiator used in the present invention include JP-A-63-138345, JP-A-63-142345, and JP-A-63-142346. Examples include compounds having an N—O bond described in Japanese Utility Model Laid-Open Nos. 63-143537 and 46-42363.

(I) Metallocene Compound (i) Metallocene compounds preferred as the photopolymerization initiator used in the present invention include those disclosed in JP 59-152396, JP 61-151197, JP 63-41484, and JP Examples thereof include titanocene compounds described in JP-A-2-249 and JP-A-2-4705, and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-benzyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl] ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bi [2,6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetyl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-chloro Benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium and the like.

(J) Active ester compound Preferred as the photopolymerization initiator used in the present invention (j) is an imide sulfonate compound described in JP-B-62-2223, JP-B-63-14340, JP-A-59-174831. And the active sulfonates described in No. 1.

(K) Compound Having Carbon Halogen Bond Preferred examples of the compound (k) having a carbon halogen bond as the photopolymerization initiator used in the present invention include those represented by the following general formulas (6) to (12).

(In the general formula, X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ , where R ³⁸ represents an alkyl group, And represents a substituted alkyl group, an aryl group, or a substituted aryl group, and R ³⁷ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

(Wherein, R ³⁹ represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group, X ³ is a halogen And n is an integer of 1 to 3.)

(However, R ⁴⁰ is an aryl group or a substituted aryl group, R ⁴¹ is a group or halogen shown below, and Z ⁶ is —C (═O) —, —C (═S) — or —SO). _2- , X ³ is a halogen atom, and m is 1 or 2.)

(R ⁴² and R ⁴³ are an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R ⁴⁴ is the same as R ³⁸ in the general formula (6).)

(In the general formula, R ⁴⁵ is an optionally substituted aryl group or heterocyclic group, R ⁴⁶ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1) 2 or 3.)

(General formula (10) represents a carbonylmethylene heterocyclic compound having a trihalogenomethyl group. L ⁷ is a hydrogen atom or a substitution of the general formula: CO— (R ⁴⁷ ) q (C (X ⁴ ) ₃ ) r. Q ² is a sulfur, selenium or oxygen atom, dialkylmethylene group, alkene-1,2-ylene group, 1,2-phenylene group or N—R group (R is an alkyl group, substituted alkyl group, alkenyl group) And M ⁴ is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group, and R ⁴⁸ is an alkyl group. , an aralkyl group or an alkoxyalkyl group, R ⁴⁷ is a divalent aromatic radical of a carbocyclic or heterocyclic, X ⁴ is chlorine, bromine or iodine atom, q = 0 and r = 1 It is there or q = 1 and r = 1 or 2.)

(General formula (11) represents a 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative. X 5 is a halogen atom, t is an integer of 1 to 3, and s is 1 to 4. is an integer, R 49 is a hydrogen atom or a CH 3-t X 5 t group, R 50 is s-valent optionally substituted unsaturated organic group.)

(General formula (12) represents a 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative. X ⁶ is a halogen atom, v is an integer of 1 to 3, and u is an integer of 1 to 4. An integer, R ⁵¹ is a hydrogen atom or a CH _3-v X ⁶ _v group, and R ⁵² is an u-valent unsaturated organic group which may be substituted.)

  Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6- Scan (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A No. 53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho) 1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloro Til-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples include compounds described in German Patent No. 3333724, such as bis-trichloromethyl-S-triazine, and the like.

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2, 4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. be able to. Furthermore, for example, the following compounds described in JP-A-62-258241 can be exemplified.

  Furthermore, for example, the following compounds described in JP-A-5-281728 can be mentioned.

  Or even more P. Hutt, E .; F. Elslager and L. M.M. The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Journalof Heterocyclic Chemistry”, Volume 7 (No. 3) by Herbel, page 511 et seq. (1970) Examples of the group include the following compounds.

(L) Azo-based compound Preferred as the photopolymerization initiator used in the present invention (i) As the azo-based compound, 2,2′-azobisisobutyronitrile, 2,2′-azobispropionitrile, 1 , 1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- Azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylpropionamide) Oxime), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2- Hydroxye L] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 '-Azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (2,4,4- Trimethylpentane) and the like.

  As a still more preferable example of the photopolymerization initiator in the present invention, one or more selected from the above-mentioned (a) aromatic ketones, (e) hexaarylbiimidazole compounds, and (f) ketoxime ester compounds. Can be mentioned.

Two or more kinds of photopolymerization initiators may be mixed and used in addition to one kind alone.
When the fine particle-containing composition of the present invention contains a photopolymerization initiator, the addition amount of the photopolymerization initiator in the fine particle-containing composition is 0.1 to 20% by mass relative to the total solid content of the composition. Is generally 0.3 to 15% by mass. When the content is within the above range, it is possible to effectively prevent the photosensitivity and the strength of the film constituting the image from decreasing.

  In the present invention, in terms of pattern formation by alkali development, the metal compound fine particles are metal sulfide, and the initiator is the above-mentioned (a) aromatic ketones, (e) hexaarylbiimidazole compound, and (f) keto. More preferably, it is one or more selected from oxime ester compounds, and the polymer dispersant is a polymer compound having a thioether structure in the side chain and further having a carboxylic acid.

  Further, when the metal compound fine particles are used as an aqueous dispersion, an aqueous one is useful as the photosensitive resin composition. Examples of the aqueous photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A No. 8-271727, and commercially available products such as “SPP-” manufactured by Toyo Gosei Co., Ltd. M20 "," SPP-H-13 "and the like.

-Other ingredients-
In addition to the above, the fine particle-containing composition of the present invention is suitably constituted by using other components such as metal fine particles, the following known pigments, surfactants, polymers that can be used in combination, dispersants, and dispersion stabilizers as necessary. can do.

~ Metallic fine particles ~
As the metal fine particles, those described in the section of the metal compound fine particles can be used within the range of the use amount of the metal compound fine particles.

~ Pigment ~
As the pigment, a black pigment such as carbon black can be used.
The addition amount of the pigment is preferably 50% by mass or less, particularly preferably 30% by mass or less, based on the above-described metal compound fine particles. If the added amount of the pigment exceeds 50% by mass, the thickness of the light shielding film necessary for obtaining the required optical density increases, and the quality of red, blue, and green pixels formed on the light shielding film may decrease. is there.

  In addition to black, blue and other pigments may be included for color adjustment. In the case of adding a pigment other than black, the addition amount is preferably 40% by mass or less, and more preferably 20% by mass or less, based on the above-described metal compound fine particles. When the added amount exceeds 40% by mass, the color of the film may be deteriorated when the film is formed.

~ Surfactant ~
A surfactant can be added to the fine particle-containing composition of the present invention for the purpose of improving coating properties and dispersion stability of fine particles. As the surfactant, nonionic, anionic and cationic surfactants can be used without particular limitation. Among these, an anionic surfactant is particularly preferable from the viewpoint of liquid stability. Moreover, a fluorine-type surfactant is a preferable surfactant.

As preferable examples of the surfactant, C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) ₁₄ H, C ₈ F ₁₇ SO ₃ Li, C ₇ F ₁₅ COONH ₄ , C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OPO (OH) ₂ or the like. Furthermore, as a commercial item, F110, F113, F120, F150, F176PF, F177, F780 (all are the Dainippon Ink and Chemicals Co., Ltd. make, oligomer type fluorine-type surfactant) etc. can be mentioned.

~ Polymer that can be used together ~
In the fine particle-containing composition of the present invention, a polymer other than the polymer dispersant in the present invention described above is used as a binder having alkali developability or in order to further improve the dispersion stability of the metal compound fine particles described above. Can be used in combination. The type of the polymer is not particularly limited, and the required properties, the components to be copolymerized, the acid value, and the molecular weight are synonymous with the “polymer dispersant in the present invention”.

~ Dispersion stabilizer ~
In the fine particle-containing composition of the present invention, a dispersion stabilizer can be used. As the dispersion stabilizer, for example, those described in “Pigment Dispersion Technology” (Technical Information Association, Inc., issued in 1999) can be used. .

--Preparation of fine particle-containing composition--
The fine particle-containing composition of the present invention can be prepared by mixing and dispersing (preferably adding a solvent) the metal compound fine particles, the polymer dispersant of the present invention, and other components that can be added as necessary. Preferably, by preparing a fine particle dispersion in which metal compound fine particles are previously dispersed in a solvent together with the polymer dispersant in the present invention, a compound that is cured by heat or light and another component that can be added are added and mixed. Can be prepared.
What added the compound hardened | cured with the said heat or light becomes a photosensitive fine particle containing composition.

The fine particle-containing composition of the present invention can be suitably configured using a known photosensitive resin composition.
Examples of the photosensitive resin composition include a photosensitive resin composition containing a compound (polyfunctional monomer and / or oligomer) curable with heat or light as described above and a photopolymerization initiator, and JP-A-10-160926. Those described in paragraph numbers [0016] to [0022] and [0029] are preferred. Furthermore, other photopolymerizable monomers may be used in combination.

  The solvent used for the preparation can be used without any particular limitation, and those having an SP value of 9.0 or more are particularly preferable. When the SP value is 9.0 or more, the dispersibility is particularly good, and a sufficient optical density can be achieved even with a thin film.

  The SP value is also referred to as a solubility parameter, and is represented by the square root of the cohesive energy density. Means the following.

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

  The fine particle-containing composition of the present invention is a known mixture such as an ultrasonic disperser, a paint shaker, a ball mill, or an Eiger mill obtained by mixing a mixed liquid obtained by mixing metal compound fine particles with at least the polymer dispersant (and preferably a solvent) of the present invention. It can prepare by carrying out the dispersion process using a disperser. Among these, an ultrasonic disperser is preferable.

  The fine particle-containing composition of the present invention is suitable for use in which metal compound fine particles are dispersed and contains a black image (including a black matrix) of a (preferably black) colored film forming ink, a light shielding film, and a color filter. It can use suitably for uses, such as.

<Ink for forming colored film for display device>
The ink for forming a colored film for a display device of the present invention is prepared using the fine particle-containing composition of the present invention described above. Since it is configured using the fine particle-containing composition of the present invention, it has high stability during long-term storage as an ink, has a good hue (especially a black hue) and a high optical density.

  An ink for forming a colored film for a display device according to the present invention includes fine metal compound particles and a polymer compound having a repeating unit derived from an ethylenically unsaturated monomer containing at least one thioether structure in the side chain. It is composed of other components such as a compound that can be cured by heat or light and, if necessary, a colorant (preferably a pigment), and may be cured by heating or application of energy rays such as ultraviolet rays after application of the ink. To get.

  The details of the fine particle-containing composition of the present invention are as described above, and in addition to the above components, components necessary for constituting the ink can be appropriately selected and added.

  The ink for forming a colored film for a display device of the present invention is suitable for use in a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, and the like. It is suitable for forming a grid-like or stripe-like black edge (so-called black matrix) around a pixel, a dot-like or linear black pattern for shielding a thin film transistor (TFT), and the like.

<Light shielding film for display device>
The light shielding film for a display device of the present invention is formed using the fine particle-containing composition of the present invention described above or the color film forming ink for a display device of the present invention described above. Since this light-shielding film is constituted using the fine particle-containing composition of the present invention, such as when exposed to high temperatures in the production process, the color change caused by alteration of resin components and fine particles in a high temperature environment , The hue is good (especially the black hue is good) and the optical density is high.

  The light-shielding film for a display device of the present invention is a method (coating method) in which the fine particle-containing composition described above is applied to a desired substrate and dried, or the fine particle-containing composition of the present invention described above on a temporary support. Using a transfer material (light-shielding material) having a light-shielding layer provided by applying and drying, a method of transferring the light-shielding layer to a desired substrate (transfer method) can be used. .

When the light-shielding film for a display device of the present invention is formed into a desired pattern, it is formed by patterning the light-shielding layer provided by the coating method or the transfer method.
Patterning methods include exposure / development, removal of unnecessary parts by laser heat (ablation method), and application of a photosensitive resist film on the light-shielding layer provided on the substrate. -The method of removing the photosensitive resist film after developing and patterning may be mentioned. In the present invention, any of these methods can be used, but the following methods (1) to (3) are preferable in terms of the simplicity of the process and the resolution of patterning.

(1) A non-photosensitive fine particle-containing composition is applied onto a substrate and dried to form a light-shielding layer. A photoresist is applied onto the light-shielding layer, and the formed photoresist film is exposed and developed. A method of dissolving and removing the underlying light shielding layer together with the photoresist film after patterning;
(2) A photosensitive fine particle-containing composition is applied onto a substrate and dried to form a photosensitive light-shielding layer. The formed photosensitive light-shielding layer is exposed and developed (uncured portions are removed). Patterning method;
(3) A photosensitive fine particle-containing composition is applied onto a temporary support and dried to form a photosensitive light-shielding layer in advance to form a laminate (photosensitive transfer material). After laminating on the substrate, the temporary support is removed and the photosensitive light-shielding layer is transferred to the substrate, and then the photosensitive light-shielding layer transferred and formed on the substrate is exposed and developed (uncured portions are removed). Patterning method;

  In any of the above methods (1) to (3), the light-shielding layer can be formed by a simple process compared to the conventional methods using vapor deposition or sputtering, and the light-shielding film is formed in a desired pattern. can do.

~ Step of applying (coating etc.) fine particle-containing composition ~
As a method for applying the fine particle-containing composition to a substrate or a temporary support, a coating method is suitable, and the coating method is not particularly limited. For example, a spin coating method described in JP-A No. 5-224011 A die coating method described in JP-A-9-323472 can be used.

  When applied to the temporary support, as will be described later, it can be a transfer material composed of a temporary support, a light-shielding layer comprising a fine particle-containing composition, and optionally a thermoplastic resin layer and an intermediate layer. .

-Exposure and development process-
The exposure can be performed in a desired pattern using a known light source. The light source may be selected according to the photosensitivity of the photoresist film or the photosensitive light-shielding layer. For example, a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or an argon laser can be used. Moreover, you may use together the optical filter etc. which are 2% or less of the light transmittance of the wavelength of 400 nm or more as described in Unexamined-Japanese-Patent No. 6-59119.

  The exposure may be batch exposure in which the entire surface to be exposed is exposed by one exposure, or may be divided exposure in which the surface to be exposed is divided and exposed in multiple times. Furthermore, an exposure method performed while scanning an exposed surface using a laser may be applied.

  Development after exposure can be performed using a developer. As the developer, a dilute aqueous solution of an alkaline substance is suitable, and a solution to which a small amount of an organic solvent miscible with water is added can also be used.

  Examples of the alkaline substance include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine Tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide) or trisodium phosphate are suitable. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14. Depending on the properties of the photosensitive light-shielding layer such as oxidation, for example, the pH of the developer can be changed so that development by film-like detachment can be performed.

  Examples of the water-miscible organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are suitable. The concentration of the organic solvent miscible with water is generally 0.1 to 30% by mass.

  A known surfactant can be further added to the developer. The concentration when the surfactant is added is preferably 0.01 to 10% by mass.

The developer may be used as a bath solution or a spray solution. Uncured portions such as a light-sensitive light-shielding layer can also be removed in a solid form (preferably in a film form). In this case, a method such as rubbing with a rotating brush or a wet sponge in a developer, Or the method of utilizing the injection pressure at the time of spraying a developing solution is preferable. The temperature of the developer is usually preferably in the range of about room temperature to 40 ° C.
It is also possible to provide a water washing step after development.

~ Heating and other processes ~
After the development, it is preferable to perform a heat treatment. By the heat treatment, curing of the photosensitive light-shielding layer cured by exposure can be promoted, and the solvent resistance and alkali resistance can be further increased. As a heating method, a method of heating the substrate after development in an electric furnace, a dryer or the like, a method of heating with an infrared lamp, or the like can be applied.

The light-shielding film for a display device of the present invention is preferably a film obtained by performing a heat treatment after development from the viewpoint of increasing the film strength. The heat treatment is preferably performed at 180 to 300 ° C. for 5 to 60 minutes, more preferably at 200 to 270 ° C. for 10 to 50 minutes, and more preferably at 200 to 250 ° C., depending on the composition and thickness of the light shielding film. It is particularly preferred to carry out for ~ 50 minutes.
Further, after the development and before the heat treatment, further exposure may be performed to accelerate the curing, and the exposure in this case can also be performed by the same method as in the exposure described above.

In addition to the above, in the case of forming a photosensitive light-shielding layer, a step of further providing a protective layer on the light-shielding layer may be provided after the light-shielding layer is formed and before exposure to a pattern.
The protective layer functions as an oxygen blocking layer for blocking oxygen during pattern exposure to increase the exposure sensitivity of the photosensitive light blocking layer, and is a layer containing an oxygen blocking resin such as polyvinyl alcohol as a main component. Is preferred. This layer is unnecessary after the formation of the light-shielding film (light-shielded image), and is removed by development.

  The thickness of the light-shielding film for a display device of the present invention is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm. When the thickness is within the above range, the necessary optical density is secured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where the light shielding film is not provided) increases. Thus, there is no inconvenience when forming RGB pixels on this in a later step.

  The transmission density (optical density) of the light-shielding film for display device of the present invention is preferably 2.5 or more, more preferably 2.8 or more, and particularly preferably 3.0 or more. When the optical density is within the above range, high contrast and high display quality can be ensured.

-Board-
As the substrate, a glass substrate generally used in a display device is preferable.
As the glass substrate, for example, a glass substrate using a known glass such as soda glass, low alkali glass or non-alkali glass is suitable. The glass substrate is described, for example, in “Introduction to Liquid Crystal Display Engineering” (Hanae Suzuki, published by Nikkan Kogyo Shimbun (1998)). As other substrates, transparent plastics such as silicon wafers and polyolefins can also be used. Furthermore, a TFT element substrate on which TFT elements are arranged can also be used.

  The thickness of the substrate is preferably in the range of 0.5 to 3 mm, and more preferably in the range of 0.6 to 2 mm.

  The light-shielding film for a display device of the present invention is preferably blacker from the viewpoint of the contrast and visibility of the display image. Being blacker can be evaluated as a color difference from an ideal black target chromaticity when the chromaticity of the light shielding film is expressed by an (x, y) value in the xyz color system. That is, the smaller the color difference value is, the closer it is to an ideal black color, and the farther the color difference is, the farther from black. Specifically, the difference from the target chromaticity when the ideal black target chromaticity (x, y) value is (0.33, 0.33) is expressed as ΔE value of the XY color system. It can be evaluated by expressing.

<Light shielding material>
The light-shielding material of the present invention is a light-shielding material used for forming a light-shielding film for a display device, and has at least one fine particle-containing layer on a support, and further includes a thermoplastic resin layer, an intermediate layer as necessary. A protective film that covers the outermost layer and the outermost layer can be provided.

The fine particle-containing layer according to the present invention includes at least a fine particle containing a metal compound and a polymer compound having a repeating unit represented by the general formula (I).
In the present invention, the light shielding material preferably further contains a compound that is cured by heat or light, and is configured to be thermosetting or photocurable, and it is preferable to add a photopolymerization initiator.
Moreover, it can comprise using other components, such as a coloring agent (preferably black coloring agent), as needed.

  In the fine particle-containing layer, the details of other components such as the metal compound fine particles, the polymer dispersant in the present invention, the compound cured by heat or light, and the colorant are described above. The same applies to the preferred embodiment.

The light-shielding material of the present invention is preferably a transfer material configured such that the fine particle-containing layer provided on the support can be transferred to the transfer target.
Hereinafter, a photosensitive transfer material provided with a photosensitive light-shielding layer will be described in detail as an example. However, the present invention is not limited to this.

  The light-shielding material of the present invention is preferably composed of a photosensitive transfer material suitable for the method (3) mentioned as one of the suitable methods for forming the light-shielding film for a display device described above. This photosensitive transfer material comprises a temporary support and a photosensitive light-shielding property formed by applying the photosensitive fine particle-containing composition of the present invention to the temporary support directly or via another layer and drying. It can consist of layers.

  The layer thickness of the photosensitive light-shielding layer is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm. When the thickness is within the above range, the necessary optical density is secured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where the light shielding film is not provided) increases. Thus, there is no inconvenience when forming RGB pixels on this in a later step.

  In the photosensitive transfer material, a form in which a thermoplastic resin layer is provided between the temporary support and the photosensitive light-shielding layer is preferable, and further, an alkali-soluble property is provided between the thermoplastic resin layer and the photosensitive light-shielding layer. A form in which an intermediate layer is provided is more preferable. A protective film may be provided on the exposed surface of the photosensitive light-shielding layer.

  The temporary support is preferably made of a flexible material that is chemically and thermally stable. Specifically, a thin sheet of Teflon (registered trademark), polyethylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. Moreover, when providing the below-mentioned thermoplastic resin layer, a thing with favorable peelability from this layer is preferable. As thickness of a temporary support body, 5-300 micrometers is suitable, and 20-150 micrometers is especially preferable.

  When the light-shielding material of the present invention is configured in a form other than the transfer material capable of transferring the fine particle-containing layer, the temporary support can be configured in place of the substrate described above. In this case, a light-shielded image (including a black matrix) having a desired pattern can be formed on the substrate, and the substrate on which the light-shielded image is formed can be used as it is as a substrate constituting the display device. .

-Thermoplastic resin layer-
The thermoplastic resin layer contains at least a resin having thermoplasticity, and can be generally formed using a preparation solution containing a thermoplastic resin prepared using a solvent.

Examples of the resin constituting the thermoplastic resin layer include acrylic resins, polystyrene resins, polyesters, polyurethanes, rubber resins, vinyl acetate resins, polyolefin resins, and copolymers thereof. It is desirable that the resin constituting the thermoplastic resin layer is alkali-soluble.
Moreover, what is described in Paragraph Nos. [0046]-[0048] of Unexamined-Japanese-Patent No. 2004-317897 can be used as resin which comprises a thermoplastic resin layer.

  The thickness of the thermoplastic resin layer is preferably 3 μm or more. When the thickness of the thermoplastic resin is within the above range, it is possible to completely absorb the unevenness of the surface of the transferred material (underlying) of 1 μm or more. The upper limit is preferably about 100 μm or less, more preferably about 50 μm or less, from the viewpoint of the ability to remove alkaline aqueous solution and the suitability for production.

  The thermoplastic resin-containing preparation liquid for forming the thermoplastic resin layer is not particularly limited as long as it can dissolve the resin constituting the layer. For example, methyl ethyl ketone, n-propanol, i-propanol, etc. You can choose.

-Intermediate layer-
In the case of providing the thermoplastic resin layer, an intermediate layer is further provided between the thermoplastic resin layer and the photosensitive light-shielding layer for the purpose of preventing layer mixing of the two layers at the time of applying the preparation liquid or for the purpose of blocking oxygen. Is preferably provided.

  The intermediate layer can be composed of at least a resin, and generally uses a resin-containing preparation prepared by using an aqueous solvent having a low compatibility with a solvent used for forming a thermoplastic resin layer or a photosensitive light-shielding layer. Can be formed.

  The resin constituting the intermediate layer is preferably an alkali-soluble resin, and examples of the resin include those described in paragraph [0050] of JP-A No. 2004-317897.

  The thickness of the intermediate layer is preferably in the range of 0.1 to 5 μm, and more preferably in the range of 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is excellent, and the intermediate layer can be removed during development in a short time.

  The fine particle-containing layer constituting the photosensitive transfer material is formed by applying, for example, a metal compound fine particle and a preparation liquid prepared with the polymer dispersant (preferably using a solvent) in the present invention. In addition, there is little change in color due to alteration of the resin component and fine particles in a high-temperature environment, excellent dispersibility during dispersion and dispersion stability after dispersion, good hue, and high optical density.

Next, a method for transferring and forming a fine particle-containing layer on a substrate using a photosensitive transfer material will be mainly described. The transfer is preferably carried out by laminating the surface of the fine particle-containing layer, which is the outermost layer, and the substrate surface in close contact, and peeling and transferring the temporary support.
As the laminating method, a conventionally known laminator, vacuum laminator or the like can be used. An auto-cut laminator can also be used in order to improve friction.

The heating temperature at the time of lamination is preferably about 60 to 150 ° C., and the pressing pressure is preferably about 0.2 to 20 kg / cm ² . In the present invention, the lamination is preferably performed in a range where the line speed of the substrate is about 0.05 to 10 m / min.

  When forming a light-shielding film for a display device using a photosensitive transfer material, after lamination of the photosensitive transfer material and the substrate, the temporary support is peeled off, followed by exposure and development, and further heat treatment after exposure and development. It is preferable to apply. The methods described above can be applied to exposure, development, and heat treatment conditions.

<Substrate with light shielding film>
The substrate with a light shielding film of the present invention uses the fine particle-containing composition of the present invention described above, the ink for forming a colored film for a display device of the present invention described above, or the light shielding material of the present invention described above on the substrate. Thus, a light shielding film is formed.
The light shielding film can be formed by the methods (1) to (3) suitable for forming the light shielding film for a display device described above, and more preferably, the method (3) is used.

  The components constituting the fine particle-containing composition, the colored film forming ink for display device, and the light shielding material are as described above, and the preferred embodiments are also the same. Further, the thickness and transmission density (optical density) of the light shielding film are the same as those in the above-described light shielding film for a display device.

<Color filter>
The color filter of the present invention is described as a pixel group including a plurality of pixels exhibiting different hues on a light-transmitting substrate and a light-shielded image (so-called black matrix) that separates the pixels constituting the pixel group. And a light-shielding film for a display device according to the present invention.

  As the light-transmitting substrate, the above-described substrate, a driving substrate (TFT element substrate or the like) provided with a TFT element or the like can be used.

  The color filter of the present invention is provided with the above-described light shielding film for a display device of the present invention, and the light shielding film for the display device is the fine particle-containing composition of the present invention described above or the display device of the present invention described above. The light-shielding film has a color change that accompanies alteration of resin components and fine particles in a high-temperature environment, such as when exposed to high temperatures during the manufacturing process. Less hue, good hue, high optical density, and excellent display image contrast and wiring shielding.

In the case of using a TFT element substrate, a structure in which a pixel group and a light-shielding film for a display device that separates each pixel constituting the pixel group may be provided on the TFT element substrate.
In addition to the above, the color filter of the present invention may have a configuration in which a TFT element substrate is used, and only a light shielding film (black matrix) for a display device is provided on the TFT element substrate without providing a pixel group. . In this case, a pixel group is formed on a light-transmitting substrate different from the TFT element substrate, and the substrate on which the pixel group is formed is disposed opposite to the TFT element substrate. Thereby, the aperture ratio of the TFT array becomes good.

The pixel group includes a plurality of pixels exhibiting different hues, and can be formed by a conventional method using a plurality of types of colored photosensitive resin compositions and photosensitive transfer materials for forming pixels. Heat treatment is preferably performed after the pixel group is formed.
Regarding the colored photosensitive resin composition and the photosensitive transfer material, for example, JP-A-2005-3861, JP-A-2004-361448, and JP-A-2004-205731 can be referred to.

<Liquid crystal display element, liquid crystal display device>
The liquid crystal display element of the present invention is constructed using the substrate with a light shielding film of the present invention described above. Since the substrate with a light-shielding film of the present invention is composed of the light-shielding film using the fine particle-containing composition of the present invention, the colored film forming ink for display device, or the light-shielding material described above, The color change associated with exposure to light is small, the hue is good, the optical density is high, the contrast of the display image is high, and image display with good display quality is possible.

  A liquid crystal display element will not be specifically limited if it is a liquid crystal display element provided with the board | substrate with a light-shielding film of this invention, It can comprise further using the component of a well-known liquid crystal display element. For example, a color filter substrate, a light-transmitting substrate disposed opposite to the color filter substrate, a liquid crystal layer provided between the substrates, and liquid crystal driving means for driving the liquid crystal in the liquid crystal layer (simple matrix driving method and active matrix driving method) And the above-described color filter of the present invention can be used as a color filter substrate.

  The liquid crystal display device of the present invention is configured using the liquid crystal display element of the present invention. In detail, the liquid crystal display element of the present invention is configured by using the substrate with a light-shielding film of the present invention (the fine particle-containing composition of the present invention, the ink for forming a colored film for a display device, or a light-shielding material). Therefore, there is little change in color accompanying exposure to a high temperature environment, the hue is good, the optical density is high, the contrast of the display image is high, and an image display with good display quality is possible. .

  The liquid crystal display device of the present invention is not particularly limited as long as it is a device manufactured using the liquid crystal display element of the present invention, and can be configured by further using components of a known liquid crystal display device.

  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” and “%” are based on mass.

<Synthesis of polymer dispersant>
-Synthesis of polymer 1-
After heating 200 parts of normal propanol to 80 ° C., a mixture (monomer solution) of 52.2 parts of ethylthioethyl acrylate, 20.0 parts of methacrylic acid, and 127.8 parts of dimethylacrylamide under a nitrogen stream, 2.70 parts of 2,2′-azobis (isobutyric acid) dimethyl (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 100 parts of normal propanol (initiator solution) for 2 hours each It was dripped simultaneously. After completion of dropping, the mixture is further heated at 80 ° C. for 2 hours under a nitrogen stream, and 500 parts of normal propanol is added to obtain a 20% solution of polymer 1 (weight average molecular weight 84000; polymer dispersant according to the present invention). It was.

-Synthesis of polymer 2-
After heating 200 parts of methyl ethyl ketone to 80 ° C., a mixture (monomer solution) of 52.2 parts of ethylthioethyl acrylate, 47.8 parts of methacrylic acid and 100.0 parts of styrene under a nitrogen stream, 2'-azobis (isobutyric acid) dimethyl (trade name: V-601; manufactured by Wako Pure Chemical Industries, Ltd.) 1.70 parts and a mixture of 100 parts of methyl ethyl ketone (initiator solution), respectively, over 2 hours It was dripped simultaneously. After completion of dropping, the mixture was further heated at 80 ° C. for 2 hours under a nitrogen stream, and 500 parts of methyl ethyl ketone was added to obtain a 20% solution of polymer 2 (weight average molecular weight 70000; polymer dispersant according to the present invention). .

-Synthesis of polymer 3-
The monomer solution used in the synthesis of the polymer 2 was replaced with a mixture of 47.7 parts of methylthioethyl acrylate, 47.8 parts of methacrylic acid, and 104.5 parts of styrene. A 20% solution of polymer 3 (weight average molecular weight 68000; polymer dispersant according to the present invention) was obtained.

-Synthesis of polymer 4-
The synthesis of the polymer 2 except that the monomer liquid used in the synthesis of the polymer 2 was replaced with a mixture of 67.9 parts phenylthioethyl acrylate, 47.8 parts methacrylic acid, and 84.3 parts methyl methacrylate. In the same manner, a 20% solution of polymer 4 (weight average molecular weight 78000; polymer dispersant according to the present invention) was obtained.

Example 1
<Preparation of Fine Particle-Containing Composition (Ag ₂ S Dispersion 1)>
Using 1N (1 mol / L) aqueous sodium hydroxide solution, 15.0 g of a 20% solution of polymer 1 was added to 2.5 L of an aqueous solution whose pH was adjusted to 12.0.
The temperature of this solution was controlled at 45 ° C., and an aqueous solution containing 8.5 g of ascorbic acid, an aqueous solution containing 5 g of hydroquinone and 1.5 g of sodium sulfite, and an aqueous solution containing 30 g of silver nitrate were added simultaneously to form black silver nanoparticles A containing liquid was prepared.
The obtained silver fine particles were connected particles in which spherical particles having an arithmetic average particle diameter of 16.5 nm and an aspect ratio of 2.0 were randomly connected.

A 7.2% sodium hydrogen sulfide aqueous solution was added to the prepared silver nanoparticle-containing solution so that the sulfidation rate was 100%.
Centrifugation (12000 rpm, 30 minutes) was performed, the supernatant was removed, distilled water was added, and washing with water was repeated three times. Further, acetone was added, and centrifugal separation treatment (12000 rpm, 30 minutes) was performed. Thereafter, the supernatant was removed, 30.0 g of 1-propanol was added, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifer II type” ultrasonic homogenizer manufactured by Branson. Thereafter, 40 kHz ultrasonic waves were irradiated for 10 minutes with a “Model 200bdc-h 40: 0.8 type ultrasonic homogenizer” manufactured by Branson.

The silver nanoparticle dispersion obtained in this manner had the same shape and color as after the formation of the particles. Moreover, Ag content was measured for the obtained silver nanoparticle dispersion liquid by the atomic absorption method, and 1-propanol was added so that it might become Ag concentration 25.0 mass%. Moreover, the density | concentration in the solvent dispersion of the polymer 1 obtained from drying loss using TG-DTA (Seiko Co., Ltd.) was 1.8 mass%. This nanoparticle dispersion is defined as a fine particle-containing composition (Ag ₂ S dispersion 1).

<Preparation of shading image forming coating solution>
Each component having the following composition was mixed to prepare a light-shielding image-forming coating solution (fine particle-containing composition for black material).
(Composition of fine particle-containing composition for black material)
The above mentioned Ag ₂ S dispersion 1 25 parts UV curable resin C-1 2.0 parts Urethane acrylate monomer (U-4HA, produced by Shin-Nakamura Chemical Co., Ltd.) 2.2 parts Photopolymerization initiator (trade name " CGI-242 "Ciba Specialty Chemicals Co., Ltd.) 0.4 parts, Paramethoxyphenol 0.0002 parts, Fluorosurfactant (trade name" Megafac R30 ", Dainippon Ink and Chemicals) 0.001 part Propylene glycol monomethyl ether acetate 13.5 parts, cyclohexanone 35.6 parts

C-1: Trade name Cyclomer P ACA-250, manufactured by Daicel Chemical Industries, Ltd. [Acrylic copolymer having alicyclic, COOH, and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass) ]

<Formation of shading image>
The obtained coating solution for shading image formation was evaluated for slit coating suitability using a slit coating apparatus provided with a slit head having a slit interval of 100 μm and a coating effective width of 500 mm on a glass substrate (Corning Millennium 0.7 mm thickness). Went. Coating was performed at a coating speed of 100 mm / second by adjusting the distance between the slit and the glass substrate and the discharge amount so that the film thickness after post-baking was 0.8 μm.
Next, after heating (pre-bake treatment) at 100 ° C. for 120 seconds using a hot plate, exposure was performed using a HITACHI exposure machine LE5565 (all wavelengths) with a mask having a line width of 10 μm and a proximity gap of 300 μm. .
Thereafter, a 1.0% developer of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (diluted solution of 1 part by mass of CDK-1 and 99 parts by mass of pure water) ( 25 ° C.) and washed with pure water. Next, it is post-baked in a 220 ° C. clean oven for 30 minutes, and exposed so that the line width of the light-shielded image is about 13 μm so that the color pixel forming region has an opening of 90 μm × 200 μm. A black matrix pattern was formed.

<Production of color filter>
Subsequently, an alkali-free glass substrate (hereinafter referred to as “color filter substrate”) on which a light-shielded image is formed is used, and paragraphs [0075] to [0086] of Japanese Patent Application Laid-Open No. 2004-347831 are used for this color filter substrate. In the same manner, a red (R), green (G), and blue (B) colored pattern (colored pixel) having a predetermined size and shape is formed using the photosensitive resin composition described in 1. to produce a color filter. did.

<Production of liquid crystal display element and liquid crystal display device>
Using the color filter obtained above, a liquid crystal display element was produced as shown below, and a liquid crystal display device was further produced.
First, a thin film transistor (TFT) and a pixel electrode were formed on a separately prepared glass substrate so as to correspond to the RGB pattern of the obtained color filter, and an active matrix substrate was prepared by providing an alignment film. . Next, an ITO film and an alignment film were further formed on the color filter obtained above to obtain a counter substrate. The obtained active matrix substrate and the counter electrode are arranged to face each other so as to form a predetermined interval (so-called cell thickness), and TN liquid crystal is sealed between the two substrates and bonded via a sealant to provide a liquid crystal display. An element was obtained. Then, polarizing plates were arranged in crossed Nicols on the surfaces of both substrates of the obtained liquid crystal display element, and a backlight was further arranged on the active matrix substrate side to obtain a liquid crystal display device.

(Examples 2-4, 6-11)
In Example 1, a fine particle-containing composition was prepared and evaluated in the same manner as in Example 1 except that the polymer compound, the polymerization initiator, and the polyfunctional monomer were changed as shown in Table 1. Got. The evaluation results are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.

(Example 5)
In Example 1, a fine particle-containing composition was prepared in the same manner as in Example 1 except that the 7.2% sodium hydrogen sulfide aqueous solution was added to 50% in order to obtain a sulfurization rate of 100%. While performing the evaluation, a light-shielded image was obtained. The evaluation results are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.

(Example 12)
In Example 1, in place of the fine particle-containing composition of Example 1, an evaluation was performed in the same manner as in Example 1 except that the fine particle-containing composition prepared as follows was used. A shaded image was obtained. The evaluation results are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.

<Preparation of fine particle-containing composition (silver tin sulfide dispersion 1)>
In 1000 ml of pure water, 9.8 g of silver (I) acetate, 27.8 g of tin (II) acetate, 23 g of gluconic acid, 19.2 g of sodium pyrophosphate, 1 g of polyethylene glycol (molecular weight 3,000), and 20% of polymer 2 15.0 g of the solution was added to obtain Solution 1.
Separately, 19.6 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 30 ° C., the solution 2 was added to the solution over 2 minutes, and the stirring was continued gently for 4 hours. The liquid mixture turned black and metal particles having a silver-tin alloy part were obtained. A 7.2% sodium hydrogen sulfide aqueous solution was added to the prepared metal particle-containing liquid having a silver-tin alloy part so that the sulfidation rate was 100%.
Nitric acid was added dropwise to the prepared silver tin sulfide dispersion to adjust the pH to 4, and silver tin sulfide fine particles were agglomerated and precipitated.
The supernatant liquid of the agglomerated silver tin sulfide fine particle liquid was removed, distilled water was added thereto, and the mixture was allowed to stand to remove the supernatant again. This was repeated several times.
1-propanol was added to the above-mentioned aggregated silver tin sulfide fine particles, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a Sonifer type II ultrasonic homogenizer manufactured by Branson. Thereafter, 40 kHz ultrasonic waves were irradiated for 10 minutes with a Branson model (Model) 2000bdc-h 40: 0.8 type ultrasonic homogenizer to obtain a silver tin sulfide dispersion.

During ultrasonic irradiation, the sample liquid was cooled by COOLNICS CTW400 manufactured by Yamato Scientific Co., Ltd. so that the sample liquid was maintained at 25 ° C. The silver tin sulfide dispersion thus obtained had the same shape and color as after the formation of the particles. Moreover, as a result of measuring Ag and Sn content by the atomic absorption method of the obtained silver tin nanoparticle dispersion liquid, they were Ag density | concentration 7.72 mass% and Sn density | concentration 17.25 mass%. Moreover, the density | concentration in the solvent dispersion of the polymer 2 obtained from drying loss using TG-DTA (Seiko Co., Ltd.) was 1.0 mass%.
The silver tin sulfide dispersion was an irregularly shaped particle having an arithmetic average diameter of 42 nm.

(Example 13)
<Creation of transfer material (light-shielding material)>
Using a slit-shaped nozzle on the surface of a 75 μm thick polyethylene terephthalate temporary support (PET temporary support), apply a coating solution for a thermoplastic resin layer prepared according to the following formulation H1 so that the dry thickness is 5 μm. It was applied and dried at 100 ° C. for 3 minutes to form a thermoplastic resin layer. On this thermoplastic resin layer, an intermediate layer coating solution prepared by the following formulation P1 was applied using a slit coater so as to have a dry film thickness of 1.5 μm, and dried at 100 ° C. for 3 minutes. A layer (oxygen barrier film) was laminated. On this intermediate layer, the light-shielding image-forming coating solution prepared in Example 1 was applied using a slit coater so as to have a dry film thickness of 0.8 μm, and dried at 100 ° C. for 3 minutes. A layer (metal black layer) was formed.
As described above, a film in which a thermoplastic resin layer, an intermediate layer, and a photosensitive light-shielding layer are sequentially laminated on a PET temporary support is produced, and a 12 μm-thick polypropylene is further used as a protective film on the light-shielding layer. The film was pressure-bonded to obtain a photosensitive transfer material.

<Prescription H1 of coating solution for thermoplastic resin layer>
Methanol 11.1 parts Propylene glycol monomethyl ether acetate 6.36 parts Methyl ethyl ketone 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio [molar ratio] = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 90,000, Tg≈70 ° C. 5.83 parts styrene / acrylic acid copolymer (copolymerization ratio [molar ratio] = 63/37, weight) Average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .; bisphenol A and pentaethylene glycol mono Compound obtained by dehydration condensation of 2 equivalents of metacrete) 9.1 parts Fluorosurfactant 0.54 parts (trade name: F78 F, Dainippon Ink & Chemicals Co., Ltd.)

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

<Production of substrate with light-shielding film (light-shielded image) by transfer (transfer method)>
A glass cleaner solution is sprayed onto an alkali-free glass substrate for 20 seconds while being washed with a rotating brush having nylon bristles, and after shower washing with pure water, a silane coupling solution (N-β (aminoethyl) γ-aminopropyl) A 0.3% aqueous solution of trimethoxysilane; trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and then shower washed with pure water. Further, this substrate was heated at 100 ° C. for 2 minutes using a substrate preheating device.

Subsequently, after peeling off the protective film of the photosensitive transfer material obtained above, the exposed photosensitive light-shielding layer is overlaid so as to contact the surface of the heated glass substrate, and a laminator Lamic II type [Hitachi Industry Co., Ltd. Using a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm ² , and a conveying speed of 2.2 m / min (lamination). Next, the PET temporary support was peeled off (transfer process).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) equipped with an ultrahigh pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer were arranged to 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 100 μm with the glass substrate standing substantially parallel and vertically, and from the thermoplastic resin layer side through the mask. Pattern exposure was performed at an exposure amount of 70 mJ / cm ² (exposure process).

  After the exposure, a triethanolamine developer T-PD1 (containing 2.5% triethanolamine, nonionic surfactant, and polypropylene antifoaming agent, manufactured by Fuji Photo Film Co., Ltd.) from a flat nozzle at 30 ° C. Shower development was performed by spraying from the top of the thermoplastic resin layer for 50 seconds at a nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were developed and removed. Subsequently, pure water was sprayed with a shower nozzle to uniformly wet the surface of the photosensitive light-shielding layer, and then KOH-based developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd .; KOH and nonionic surface activity) An agent-containing alkali developer) diluted 100 times with pure water was sprayed for 80 seconds from a flat nozzle at 23 ° C. and a nozzle pressure of 0.04 MPa (development process) to obtain a pattern image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and a heat treatment (baking process) was performed at 220 ° C. for 40 minutes to obtain a light-shielded image.

  The evaluation results are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.

(Comparative Example 1)
<Preparation of fine particle-containing composition (silver fine particle composition)>
First, Mater. Chem. Phys. 2004, 84, p. According to the method for preparing fine particles described in 197-204, a dispersion of rod-shaped silver fine particles having various aspect ratios was prepared by changing the pH and reaction temperature during silver salt reduction. After centrifugation (rotation speed 10,000 rpm, 20 minutes), the supernatant was discarded and concentrated as appropriate to obtain rod-shaped silver fine particles.

  Among the rod-shaped silver fine particles obtained above, 20.0 parts of rod-shaped silver fine particles having an average aspect ratio of 54.7, 20.0 parts of a 20% solution of polymer 1 obtained above, and 80.0 normal propanol Were mixed using an ultrasonic disperser (Ultrasonic generator model US-6000 ccvp, manufactured by Nissei Co., Ltd.) to prepare a silver fine particle composition.

(Comparative Examples 2 to 5)
In Example 1, instead of polymer 1, comparative example 2 is “methacrylic acid / benzyl methacrylate copolymer (MAA / BzMA, molar ratio = 27/73, weight average molecular weight: 30,000)”, and comparative example 3 is “Methacrylic acid / benzyl methacrylate copolymer (MAA / BzMA, molar ratio = 27/73, weight average molecular weight: 30,000) and dodecylethyl sulfide (mass ratio = 80: 20)”, Comparative Example 4 is “terminal-SH PVA, trade name: M-205 manufactured by Kuraray Co., Ltd. ”and Comparative Example 5 were prepared in the same manner as in Example 1 except that“ Polymer 5 ”was used. I got an image. The evaluation results are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.

(Comparative Example 6)
In Comparative Example 2, evaluation was performed and a light-shielded image was obtained in the same manner as in Example 1 except that the following carbon black dispersion was used instead of the “silver sulfide fine particle-containing composition”. The evaluation results are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.

(Carbon black dispersion)
The composition of the carbon black dispersion 1 was as follows.
Carbon black (trade name: Nippon 35, manufactured by Degussa Japan Co., Ltd.) 13.1 parts Dispersant 1 (compound 1 below) 0.65 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer) Polymer, molecular weight 37,000) 6.72 parts, propylene glycol monomethyl ether acetate 7953 parts

  When the particle size of the carbon black dispersion 1 was measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., the number average particle size was 20 nm.

(Evaluation)
-1. Evaluation of dispersibility of fine particle-containing composition
The fine particle-containing compositions obtained from the examples and comparative examples were allowed to stand at 25 ° C. for 3 days, and then the fine particle dispersibility was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: The fine particles were uniformly dispersed without settling.
B: Part of the fine particles was settled.
C: Fine particles were completely settled.

-2. Resolution evaluation
A line in which a black photosensitive resin layer is formed on a glass substrate using the fine particle-containing compositions obtained from the examples and comparative examples, and the formed black photosensitive resin layer is narrowed at intervals of 2 μm from 50 μm to 4 μm. Pattern exposure was performed using a mask having a pattern. Thereafter, the development process was performed in the same manner as the development process in <Formation of light-shielded image> in Example 1, and the line width (μm) of the portion where the line remained was measured using an optical microscope, and this was defined as the resolution. Smaller values indicate better resolution.

-3. Pattern shape evaluation
2. The edge portions of the lines were evaluated by directly observing them with an optical microscope at any five points of the line having a line width of 30 μm obtained in the above.
(Evaluation criteria)
A: The edge is straight and good B1: The edge is less than 3 μm and has a rattle B2: There is a black residue on the edge C1: The edge is more than 3 μm and the rattle is C2: Not There is residue throughout the exposed area

-4. Evaluation of reflectivity
The glass substrate side in the light-shielding image obtained by the Example and the comparative example using JASCO Corporation absolute reflectance measuring device ARV-474 combined with JASCO Corporation spectrophotometer V-560 The absolute reflectance (%) on the side opposite to the surface on which the coating film was formed was measured. The measurement angle is 5 degrees and the wavelength is 500 nm.

-5. Evaluation of color tone-
In <Formation of light-shielded image> in Examples and Comparative Examples, the color tone of the light-shielded image (black matrix) before and after baking was visually confirmed and evaluated.

  The polymerization initiator, polyfunctional monomer, and polymer compound used in Examples and Comparative Examples are shown below.

Polymerization initiator Initiator 1 CGI-242 (Ciba Specialty Chemicals)
Initiator 2 Irgacure 379 (Ciba Specialty Chemicals)
Initiator 3 Irgacure 819 (Ciba Specialty Chemicals)
Initiator 4 (2,4-bis (trichloro) -6,4- [4-N, N-diethoxycarbomethyl) -3-bromophenyl-s-triazine)
Multifunctional monomer Monomer 1 U-4HA (manufactured by Shin-Nakamura Chemical)
Monomer 2 UA-306H (manufactured by Kyoeisha Chemical)
Monomer 3 KAYARAD DPHA-40H (Nippon Kayaku)
Monomer 4 KAYARAD DPHA (Nippon Kayaku)

As is clear from Table 1, the examples using both the metal compound fine particles and the polymer dispersant having a thioether structure are excellent in the dispersion stability of the metal compound, and the resolution, pattern shape, and transmission density of the formed light-shielded image. The reflectance and color tone were all good.
On the other hand, although the dispersion stability of Comparative Examples 1 and 6 was good, none of them satisfied all the evaluation items. In Comparative Examples 2, 4, and 5, no shaded image could be obtained.

Claims (20)

A fine particle-containing composition comprising: a fine particle containing a metal compound; and a polymer compound having a repeating unit derived from an ethylenically unsaturated monomer having at least one thioether structure in the side chain. . The fine particle-containing composition according to claim 1, wherein the metal compound is a metal sulfide. The fine particle-containing composition according to claim 2, wherein the metal sulfide is silver sulfide. The fine particle-containing composition according to any one of claims 1 to 3, wherein the polymer compound has at least a repeating unit represented by the following general formula (I).

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total, and R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms in total, an aryl group having 6 to 14 carbon atoms in total, or An aralkyl group having 7 to 16 carbon atoms in total is represented. Z represents —O— or —NH—, and Y represents a divalent linking group having 1 to 8 carbon atoms in total. ] The fine particle-containing composition according to any one of claims 1 to 4, wherein the polymer compound further has an acid group. The fine particle-containing composition according to claim 5, wherein the acid group is a carboxylic acid group. The fine particle-containing composition according to any one of claims 1 to 6, further comprising a compound that is cured by heat or light. The fine particle-containing composition according to any one of claims 1 to 7, further comprising a photopolymerization initiator. The fine particle-containing composition according to claim 8, wherein the photopolymerization initiator includes one or more selected from aromatic ketones, hexaarylimidazole compounds, and ketoxime ester compounds. An ink for forming a colored film for a display device, comprising the fine particle-containing composition according to any one of claims 1 to 9. A light-shielding material used for the formation of a light-shielding film for a display device, comprising fine particles containing a metal compound and a polymer compound having a repeating unit represented by the following general formula (I) on a support A light-shielding material comprising at least one containing layer.

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total, and R ² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms in total, an aryl group having 6 to 14 carbon atoms in total, or An aralkyl group having 7 to 16 carbon atoms in total is represented. Z represents —O— or —NH—, and Y represents a divalent linking group having 1 to 8 carbon atoms in total. ] The light-shielding material according to claim 11, wherein the fine particle-containing layer further contains a compound that is cured by heat or light. The light-shielding material according to claim 11 or 12, further comprising a photopolymerization initiator. The light-shielding material according to any one of claims 11 to 13, wherein the fine particle-containing layer is a layer capable of being transferred to a transfer target. The fine particle-containing composition according to any one of claims 1 to 9, the colored film forming ink for display device according to claim 10, or any one of claims 11 to 14. A light shielding film for a display device using the light shielding material. The board | substrate with a light shielding film which has a light shielding film for display apparatuses of Claim 15. The color filter having a pixel group including a plurality of pixels exhibiting different hues on a light-transmitting substrate and a light-shielding image separating each pixel constituting the pixel group, wherein the light-shielded image is the claim 15. A color filter, which is a light-shielding film for a display device described in 1. A color filter comprising the substrate with a light-shielding film according to claim 16. A liquid crystal display device comprising the substrate with a light-shielding film according to claim 16. A liquid crystal display device comprising the liquid crystal display element according to claim 19.