KR20070053712A - Black material, black particle dispersion liquid, black light-blocking film using same, and base with black light-blocking film - Google Patents

Abstract

The black material of the present invention comprises secondary particles in which primary particles composed of metals and / or metal oxides having a particle diameter of 1 nm or more and 200 nm or less are collected, and the particle diameter of the secondary particles is 5 nm or more and 300 nm or less, The outermost layers of the secondary particles are gold (Au), platinum (Pt), palladium (Pd), silver (Ag), ruthenium (Ru), copper (Cu), silicon (Si), titanium (Ti), tin ( Sn), nickel (Ni), characterized in that it comprises at least 50% by weight of one or two or more elements or oxides thereof. Moreover, the black fine particle dispersion of this invention contains the said black material and the polymer dispersing agent, It is characterized by the above-mentioned. The black fine particles of the present invention are characterized in that the surface of the black material is covered with an insulating film made of an organic polymer compound.

Description

BLACK MATERIAL, BLACK PARTICLE DISPERSION LIQUID, BLACK LIGHT-BLOCKING FILM USING SAME, AND BASE WITH BLACK LIGHT-BLOCKING FILM}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to black materials (black fine particles), and is particularly preferably used for black matrices of various display devices such as recording materials, liquid crystal displays, and the like, and relates to black materials having high blackness and excellent light shielding properties. . The present invention also relates to a black fine particle dispersion and a black light shielding film and a substrate with a black light shielding film using the same, and are particularly preferably used for recording materials, black matrices of various display devices, black decorative films, etc., and have high blackness and excellent light shielding properties. Membrane technology.

This application is Japanese Patent Application No. 2004-273348 filed September 21, 2004, Japanese Patent Application No. 2005-040257 filed February 17, 2005, Japanese Patent Application No. 2005- filed February 17, 2005. Claims are made on the basis of 040258 and the content is incorporated herein.

Conventionally, as a black material, metal materials and inorganic materials, such as carbon black, a low titanium oxide, iron oxide, chromium, and silver fine particles, are known (for example, refer patent document 1).

These black materials are black or light shielding materials such as black light shielding film, black light shielding glass, black paper, black cloth, black ink, black matrix material of plasma display (PDP) or liquid crystal display (LCD), black seal material, black mask material, etc. It is used as a material which gives.

On the other hand, in the case of blackening gold, platinum group elements, or these alloys, a method of forming a film of black oxide on the surface of the base metal of these metals or alloys is adopted. It was easy to peel from a base material, and the durable black gold alloy was not obtained. Therefore, by adding and oxidizing a metal such as copper, nickel and iron to gold, platinum group elements, or alloys thereof, or an alloy in which silver is added to any of the above metals or alloys, a black oxide made of a metal oxide having good adhesion to the surface The black alloy which provided the layer is proposed (refer patent document 2).

In addition, in the field of photosensitive materials, the optical information exposed from the back surface is recorded at an appropriate density by improving sharpness, and in the aqueous gelatin as a photosensitive material for photographs in which the infrared detection characteristic during development is improved. The black colloidal silver dispersion which disperse | distributed black colloidal silver is proposed (refer patent document 3).

By the way, the liquid crystal display (LCD) which is conventionally thin and is capable of full color display as a large flat display is known.

In this color liquid crystal display, each pixel of R (red), G (green), and B (blue) arranged in a matrix on a transparent substrate has a high light shielding property in order to improve contrast in its display surface. Black matrix is formed.

In particular, in the active matrix type liquid crystal display (TFT-LCD) using a thin film transistor (TFT), the black matrix prevents leakage current in which the light of the TFT is induced, and at the same time other than the display surface of each pixel. The image quality of the display device can be improved by blocking the transmission of light and improving the contrast of each pixel.

This black matrix may be formed on the TFT array substrate side or on the color filter side.

When formed on the TFT array substrate side, since the black matrix is in direct contact with the pixel electrode and the TFT, high insulation is required for the black matrix.

On the other hand, when formed in the color filter side, especially in the case of the liquid crystal display (LCD) of a transverse electric field drive system, high insulation is calculated | required also in the black matrix at the color filter side.

This black matrix has conventionally been formed such that a metal film such as Cr having high light shielding property covers portions other than the transparent pixel electrode by vacuum deposition or sputtering, but in recent years, it has a high light shielding property as a material to replace it. The material for forming a black matrix which is simple in the manufacturing process and which can be reduced in cost is also developed and has been provided for practical use.

As such a black matrix forming material, the dispersion liquid which disperse | distributed the carbon black and titanium black which the surface was coat | covered and insulated with resin or silicon oxide, for example in an organic solvent (for example, refer patent document 4, 5). The dispersion liquid (for example, refer patent document 6, 7) which disperse | distributed metal microparticles | fine-particles, such as silver fine particles, in an organic solvent is proposed.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-127433

Patent Document 2: Japanese Patent Application Laid-Open No. 10-8235

Patent Document 3: Japanese Patent Application Laid-Open No. 2000-155387

Patent Document 4: Japanese Patent Application Laid-Open No. 2002-201381

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-267832

Patent Document 6: Japanese Patent Application Laid-Open No. 2004-317897

Patent Document 7: Japanese Patent Application Laid-Open No. 2004-334180

Problems to be Solved by the Invention

However, although metal materials and inorganic materials, such as conventional carbon black, low titanium oxide, and iron oxide, are black, light shielding property (shielding property) is inadequate. Therefore, in order to shield light using the film | membrane containing these black materials, it is necessary to form a film | membrane with a thickness in a base material by apply | coating thickly the coating liquid containing a black material, or applying the coating liquid several times repeatedly. have.

When these black materials are used as a recording material for drawing black lines on a white substrate, the light shielding property is weak, so that the boundary line portion with the underlying white substrate is blurred, and there is a problem that sharp lines cannot be drawn.

Moreover, when these black materials are used as a light shielding material, in order to improve light shielding property, it is necessary to increase the volume ratio of the black material in a material, and content of a binder falls relatively. Therefore, when a black coating film was produced using these black materials, there existed a problem that the intensity | strength of a coating film fell and it could not hold | maintain a coating film for a long time, and the reliability of a light shielding film could not be maintained.

In addition, chromium is excellent in blackness and light shielding, but has a problem in that the applicable products are limited for various reasons, such as heavy metals, large environmental loads, and high cost.

In addition, although silver particles produced by reducing silver bromide used in photographic films and the like are excellent in blackness and light shielding properties, silver itself is a precious metal and expensive, and thus, some high-priced products are distinct and generally used as black materials for general-purpose products. It is not used.

In addition, although silver particles and black silver colloids produced by reducing silver bromide used in photographic films and the like are excellent in blackness and light shielding properties, these black silver particles can be synthesized only in the presence of gelatin, and after synthesis, gelatin and Silver particles cannot be separated completely.

In addition, since gelatin is not dissolved in an organic solvent, it is impossible to disperse it in an organic solvent, and therefore, the gelatin may be used only as an aqueous paint, thereby having a problem that the width of the paint is very narrow.

In addition, when a black coating film was produced using silver colloid, this black coating material was excellent in light-shielding property, but there was a problem that it could not express outstanding blackness because it had a color by metallic color and plasmon absorption.

The first object of the present invention is to solve the above problems, and an object of the present invention is to provide an inexpensive black material having high blackness, excellent light shielding properties, and low environmental load.

The second aspect of the present invention has been made in order to solve the above problems, and it is possible to obtain a neutral black color and to have excellent light shielding properties, and a low environmental load, and an inexpensive black fine particle dispersion, and a black light shielding film and a black light shielding film substrate using the same. The purpose is to provide.

By the way, when a black matrix is manufactured with the dispersion liquid which used the conventional carbon black or titanium black, since light-shielding property is lacking, it is necessary to thicken a film thickness by high concentration of a dispersion liquid, an overcoat, etc. However, when the film thickness is increased, the overlap between the black matrix and each pixel becomes large, and the flatness of the color filter decreases, and the nonuniformity occurs in the cell gap of each pixel. Therefore, there is a problem that it is difficult to form uniform pixels.

When nonuniformity arises in a cell gap, color unevenness tends to generate | occur | produce on a display surface, As a result, the quality of a display surface will fall.

In addition, when the overlap between the black matrix and each pixel becomes large, there is a problem that the occupied area of the black matrix in each pixel becomes large and the aperture ratio of each pixel decreases. When the aperture ratio is lowered, the luminance of each pixel is lowered, and as a result, the luminance of the entire display surface of the display device is lowered.

Although carbon black and titanium black are surface-treated by the gas phase method or liquid phase method, it is difficult to disperse the particles in the gas phase when the surface process is carried out by the gas phase method, so that the particles are mixed with the substance to be surface-treated in contact with the particles. Therefore, the uniformity of the surface treatment is poor, and the aggregation of the particles is also a problem. Therefore, there is also a method in which an alkoxide, such as tetraethoxysilane, is vapor-adsorbed on the surface of the particle, followed by removal of excess alkoxide under reduced pressure. However, this method has a problem that the operation is complicated and time and cost are required. have.

When the surface treatment is performed by the liquid phase method, the surface treatment can be performed in a state where the particles are dispersed in the liquid phase. Thus, the surface treatment can be performed more uniformly than the vapor phase method. Since it is obtained in a powder state, it is very difficult to disperse them in water or an organic solvent.

On the other hand, when a black matrix is produced from a dispersion using conventional metal fine particles, there is a problem that high insulation cannot be obtained from the black matrix in which only the metal fine particles are dispersed.

In particular, in the case of the dispersion using black silver fine particles, since the silver fine particles are synthesized using gelatin, gelatin cannot be completely removed after the synthesis, and therefore, it is difficult to uniformly disperse the silver fine particles in an organic solvent. In this case, silver fine particles cannot be synthesized unless gelatin is used.

Accordingly, the third aspect of the present invention has been made to solve the above problems, and it is easy to disperse in a solvent and has a high degree of blackness, and furthermore, a black fine particle, a black fine particle dispersion, and a black light shielding film and a substrate with a black light shielding film It aims to provide.

Means to solve the problem

The present inventors have diligently studied materials having excellent blackness and excellent light shielding properties. As a result, the inventors have gathered primary particles composed of metals and / or metal oxides having a particle diameter of 1 nm or more and 200 nm or less, and have a particle diameter of 5 nm or more and 300 nm or less. Primary particles and the outermost layer of the secondary particles contain at least 50% by weight of one or two or more elements selected from Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, Ni or these oxides. By having one structure, it discovered that the black material which was excellent in blackness and was excellent in light shielding property was found, and came to complete this invention.

That is, the first black material of the present invention is composed of secondary particles in which primary particles composed of metals and / or metal oxides having a particle diameter of 1 nm or more and 200 nm or less are aggregated, and the particle diameter of the secondary particles is 5 nm. The outermost layer of the secondary particles is at least 300 nm and at least 50% by weight of one or two or more elements selected from Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, Ni, or oxides thereof. It is characterized by containing.

It is preferable that the space part is formed in the said secondary particle.

It is preferable that a space part is formed in the inside of the outer shell layer which consists of said outermost layer or the outermost layer, and the said secondary particle is a multiple layer.

It is preferable that the said secondary particle is core-shell-shaped in which the outer surface of the substance used as a nucleus is coat | covered with the outermost layer or the outer shell layer which consists of multiple layers containing the outermost layer.

It is preferable that the said shell layer is dense.

Moreover, the present inventors earnestly examined the material which was excellent in blackness and was excellent in light-shielding property, As a result, the average particle diameter which the primary particle of the microparticles | fine-particles which consist of metal and / or metal oxide whose average particle diameter is 1 nm or more and 200 nm or less is aggregated. When the black fine particle dispersion containing the secondary particle which is 5 nm or more and 300 nm or less and a polymeric dispersing agent is used, it discovered that the black shading film, the black decorative film, etc. which were high in blackness and excellent in light-shielding property can be obtained, It was completed.

That is, the second black fine particle dispersion of the present invention has a secondary particle having an average particle diameter of 5 nm or more and 300 nm or less, in which primary particles of fine particles composed of a metal and / or metal oxide having an average particle diameter of 1 nm or more and 200 nm or less are collected. It is characterized by containing a particle | grain and a polymeric dispersing agent.

It is preferable that the said microparticles | fine-particles contain 1 type (s) or 2 or more types chosen from the group of silver, tin, and nickel.

It is preferable that the polymer dispersant contains 1 wt% or more and 10 wt% or less with respect to the total weight of the fine particles.

The polymer dispersant is preferably polyvinylpyrrolidone.

It is preferable that the space part is formed in the said secondary particle.

It is preferable that a space part is formed in the inner side of the outer shell layer which consists of a outermost layer or the outermost layer which consists of multiple layers including the said outermost layer.

It is preferable that the said secondary particle is core-shell-shaped in which the outer surface of the material used as a nucleus is coat | covered with the outermost layer or the outer shell layer which consists of multiple layers containing the outermost layer.

The black light shielding film of the present invention is characterized by applying the black fine particle dispersion of the present invention.

The base material with a black light shielding film of this invention is equipped with the black light shielding film of this invention in one main surface of a base material, It is characterized by the above-mentioned.

It is preferable that the said black light-shielding film has an OD value of CIE brightness L ^* of 10 or less, chromaticity a ^* of -1 or more and 1 or less, chromaticity b ^* of -1 or more, and optical density of 3 or more.

In addition, the present inventors have diligently studied in a material that is easy to disperse in a solvent, has a high blackness, and has high insulating properties. It is easy to disperse | distribute in a solvent by changing into the secondary particle which the average particle diameter of 5 micrometers or more and 300 nm or less which the primary particle of the microparticles | fine-particles which consist of an oxide collect | aggregates, and coat | covering the surface of this secondary particle with an insulating film, It was found that black fine particles having a high and high insulating property can be obtained, and have completed the present invention.

That is, the third black fine particles of the present invention are secondary particles having an average particle diameter of 5 nm or more and 300 nm or less, in which primary particles of fine particles composed of metal and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less are collected. The surface is covered with an insulating film.

It is preferable that the said insulating film is a metal oxide or an organic high molecular compound.

It is preferable that the said microparticles | fine-particles contain 1 type (s) or 2 or more types chosen from the group of silver, tin, and nickel.

The black fine particle dispersion of this invention contains the black fine particle of this invention, It is characterized by the above-mentioned.

The black light shielding film of the present invention is characterized by applying the black fine particle dispersion of the present invention.

The base material with a black light shielding film of this invention is equipped with the black light shielding film of this invention on one main surface of a base material, It is characterized by the above-mentioned.

Effects of the Invention

According to the first black material of the present invention, the secondary particles are composed of primary particles composed of metals and / or metal oxides having a particle diameter of 1 nm or more and 200 nm or less, and the secondary particles have a particle diameter of 5 nm or more. 300 nm or less, and the outermost layer of the secondary particles contains at least 50% by weight of one or two or more elements selected from Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, Ni or these oxides Since the black material of the black material itself can be increased, the light shielding property can be improved.

Moreover, also when the black coating film is produced using this black material, there is no possibility that the intensity | strength of a coating film may fall, and a coating film can be maintained for a long time.

In addition, the outermost layer of the secondary particles was composed of one or two or more elements selected from Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, and Ni or 50% by weight of these oxides. Because of the environmental load is small and inexpensive.

As described above, it is possible to provide an inexpensive black material having high blackness and excellent light shielding property and low environmental load.

According to the second black fine particle dispersion of the present invention, secondary particles having an average particle diameter of 5 nm or more and 300 nm or less, in which primary particles of fine particles composed of metals and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less, are collected; And a polymer dispersant, a black light blocking film and a black decorative film having a neutral black color and high light shielding properties can be obtained.

Moreover, when a coating film is produced using this black fine particle dispersion, since the secondary particle itself disperse | distributed in the black fine particle dispersion is excellent in blackness and light-shielding property, since the quantity of black fine particles with respect to the binder in a coating film can be reduced, The intensity | strength of this does not fall, and a coating film can be maintained for a long time.

According to the above, the black light shielding film and the black decorative film which are high in blackness and are excellent in light-shielding property, and also are low in environmental load and are small can be provided.

According to the third black fine particles of the present invention, the surface of secondary particles having an average particle diameter of 5 nm or more and 300 nm or less, in which primary particles of fine particles composed of a metal and / or metal oxide having an average particle diameter of 1 nm or more and 200 nm or less are collected. Since it was coat | covered with the insulating film, it can make it easy to disperse | distribute to a solvent, the blackness of black fine particle itself can be improved, and insulation can be improved.

According to the black fine particle dispersion of this invention, since the black fine particle of this invention was contained, the dispersibility of black fine particles can be improved and applicability | paintability can be improved.

According to the black light shielding film of this invention, since it was obtained by apply | coating the black fine particle dispersion liquid of this invention, even if film thickness is thin, light shielding property and insulation can be improved.

When the black light shielding film is applied to a black matrix of a flat panel display device such as a liquid crystal display, by reducing the film thickness, the overlap between the black matrix and each pixel can be reduced, and the nonuniformity of the cell gap of each pixel can be reduced. Can be made uniform. Therefore, color nonuniformity hardly arises on a display surface, and the quality of a display surface can be improved. In addition, the aperture ratio of each pixel can be improved, and the luminance of the entire display surface of the display device can be improved.

To practice the invention  Preferred form for

Embodiment (1st of this invention):

First, the preferable aspect of the black material which is 1st of this invention is demonstrated.

In addition, this form is concretely explained in order to understand the meaning of invention better, and it does not limit this invention unless there is particular notice.

The black material of this embodiment consists of secondary particle which the primary particle which consists of a metal and / or metal oxide whose particle diameter is 1 nm or more and 200 nm or less aggregates, The particle diameter of this secondary particle is 5 nm or more and 300 nm or less The outermost layer of the secondary particles is black in which one or two or more elements selected from Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, and Ni or 50% or more of these oxides are contained. Material.

This secondary particle should just have the outermost layer containing 50 weight% or more of 1 type, 2 or more types of elements chosen from Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, Ni, or these oxides. It does not restrict | limit about the material composition of the part except this outermost layer.

The secondary particles are most preferably in the form of a space portion formed therein, and then the outer surface of the outer surface of the material serving as the core or the form of the space portion formed inside the outer shell layer composed of a plurality of layers. Or the form which is core-shell shape formed by covering by the outer shell layer which consists of multiple layers including the said outermost layer is preferable.

Next, the cross-sectional shape of this black material is demonstrated.

This black material can adopt the following various structures.

(1) wheat structure

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing the cross-sectional structure of a black material of the present embodiment, in which 1 is a black material and primary particles 2 made of a metal and / or metal oxide having a particle diameter of 1 nm or more and 200 nm or less. Aggregated into secondary particles 3 having a particle diameter of 5 nm or more and 300 nm or less, and the outermost layer of the secondary particles 3 is Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, Ni. It is comprised by the microparticles | fine-particles 4 which are 1 type, or 2 or more types of elements chosen from these, or primary particles containing 50 weight% or more of these oxides. The black material 1 has a mill structure in which the primary particles 2 are closely assembled so that there is no space therein.

(2) hollow structure (first of the present invention)

FIG. 2: is sectional drawing which shows the other example of the cross-sectional structure of the black material of this embodiment typically, The point which this black material 11 differs from the black material 1 of FIG. 1 is the inside of the secondary particle 3 The space part 12 was formed in this.

(3) hollow structure (second of the present invention)

FIG. 3: is sectional drawing which shows the other example of the cross-sectional structure of the black material of this embodiment typically, The point which this black material 21 differs from the black material 11 of FIG. It is the point which comprised the shell layer 22 and made the inside of this outer shell layer 22 into the space part 23. As shown in FIG.

Although this outer shell layer 22 is made into one layer only of the microparticles | fine-particles 4 here, you may make it the structure which consists of two or more layers.

(4) core shell structure

4 is a cross-sectional view schematically showing another example of the cross-sectional structure of the black material of the present embodiment, wherein the black material 31 differs from the black material 1 in FIG. 1 in the particle-shaped nucleus 32. The outer surface of the structure is coated with a dense outer shell layer 22 composed of only the fine particles 4.

A material constituting the core 32 is not specifically limited, but the fine particle 4 and the excellent adhesion to a material constituting the outer shell layer 22 is preferably, for example, silicon oxide (SiO _2), titanium oxide ( TiO ₂ ), zirconium oxide (ZrO ₂ ), and the like are preferably used.

These black materials 1-31 can be produced using a normal fine particle synthesis method. As the fine particle synthesis method, any method such as gas phase reaction method, spray pyrolysis method, atomization method, liquid phase reaction method, freeze drying method, hydrothermal synthesis method, or the like may be used.

According to the black material of this embodiment, it consists of the secondary particle which the primary particle which consists of a metal and / or a metal oxide whose particle diameter is 1 nm or more and 200 nm or less aggregates, The particle diameter of this secondary particle is 5 nm or more and 300 nm The outermost layer of these secondary particles is composed of one or two or more elements selected from Au, Pt, Pd, Ag, Ru, Cu, Si, Ti, Sn, Ni, or 50% by weight or more of these oxides. As it loses, blackness can be increased and light shielding can be improved.

Embodiment (2nd of this invention):

Next, the preferable aspect of the 2nd black fine particle dispersion of this invention, the black light shielding film, and the base material with a black light shielding film using this is demonstrated.

The black fine particle dispersion of the present embodiment comprises a secondary particle and a polymer dispersion liquid having an average particle diameter of 5 nm or more and 300 nm or less, in which primary particles of fine particles composed of metals and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less are collected. It is contained

This black fine particle dispersion contains a solvent, an organic binder, etc. as needed.

Although these elements are not specifically limited, It is preferable that these microparticles | fine-particles contain 1 type (s) or 2 or more types chosen from the group of silver, tin, and nickel.

Most preferably, the secondary particles have a space in which a space is formed, and next, a space in which a space is formed inside an outermost layer or an outer shell layer including a plurality of layers including the outermost layer, or a nucleus. It is preferable that the core shell form is formed by coating the outer surface of the material to be the outermost layer or the outer shell layer including a plurality of layers including the outermost layer. The secondary particles may be in a form in which the primary particles are only collected through a dispersant or the like, and may be in a form in which the primary particles are in direct contact with each other without passing through a dispersant or the like, or a neck between the primary particles. The form which is bonded together is more preferable.

Next, the cross-sectional shape of the black fine particles which comprise this secondary particle is demonstrated using FIGS. 1-4 used in the said embodiment (1st of this invention).

This black fine particle can adopt the following various structures.

(1) wheat structure

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the cross-sectional structure of the black fine particle of this embodiment typically, In the figure, the code | symbol 1 is black fine particle (black material), Comprising: The metal and / or metal oxide whose average particle diameter is 1 nm or more and 200 nm or less. The formed primary particle size 2 is aggregated to form secondary particles 3 having an average particle diameter of 5 nm or more and 300 nm or less, and the black fine particles 1 are gathered closely by the primary particles 2. It has a mill structure without a large space part other than the space | interval of particle | grains. In addition, the primary particle 2 may consist of one type of metal or metal oxide, or may consist of two or more types of metal and / or metal oxide. Moreover, the shape of this secondary particle does not have a restriction | limiting in particular, The thing of various shapes, such as spherical shape, indefinite form, and plate shape, can be used.

(2) hollow structure (first of the present invention)

FIG. 2: is sectional drawing which shows the other example of the cross-sectional structure of the black fine particle of this embodiment typically, The point which this black fine particle (black material) 11 differs from the black fine particle 1 of FIG. 1 is a secondary particle ( It is the point which formed the space part 12 inside 3). There is no restriction | limiting in particular in the shape of this secondary particle, Various shapes, such as spherical shape, indefinite form, and plate shape, can be used. In addition, this hollow structure may not be a perfect state, and the outer part and the space part 12 may be connected by the pore, for example, in the shape in which the spherical secondary particle of FIG. You may be.

(3) hollow structure (second of the present invention)

FIG. 3 is a cross-sectional view schematically showing another example of the cross-sectional structure of the black fine particles of the present embodiment, wherein the black fine particles (black material) 21 differ from the black fine particles 11 of FIG. It is the point which comprised the outer shell layer 22 only by making the inner side of this outer shell layer 22 into the space part 23. As shown in FIG.

Although this outer shell layer 22 is made into one layer of the microparticles | fine-particles 4 here, you may make it the structure which consists of two or more layers. Moreover, the shape of this black fine particle does not have a restriction | limiting in particular, Various shapes, such as spherical shape, indefinite form, and plate shape, can be used. In addition, this hollow structure may not be perfect, the outer part and the space part 23 may be connected to a pore, for example, the spherical black fine particle of FIG. 3 may be divided into several pieces.

(4) core shell structure

4 is a cross-sectional view schematically showing another example of the cross-sectional structure of the black fine particles of the present embodiment, wherein the black fine particles (black material) 31 differs from the black material 1 of FIG. It is the structure which coat | covered the outer surface of the nucleus 32 with the outer shell layer 22 which consists only of the microparticles | fine-particles 4. As shown in FIG. In addition, the outer shell layer 22 may not be in a perfect state, and the outside and the core 32 may be connected to the pores. There is no restriction | limiting in particular in the shape of this black fine particle, A thing of various shapes, such as spherical shape, indefinite form, and plate shape, can be used.

Although it does not specifically limit as a material which comprises the nucleus 32, The material excellent in adhesiveness with the microparticles | fine-particles 4 which comprise the outer shell layer 22 is preferable, For example, silver, tin, nickel, silicon oxide (SiO) is preferable. ₂ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), and the like are preferably used.

The polymer dispersant improves the dispersibility of the fine particles by improving the wettability of the surface of the fine particles and, as a result, improves the uniformity of the dispersion. For example, polyvinylpyrrolidone (PVP), polyethylene glycol, polyacrylamide, and the like. This is preferably used.

The polymer dispersant is preferably 1% by weight or more and 10% by weight or less with respect to the total weight of the fine particles contained in the black fine particle dispersion, more preferably 2% by weight or more and 8% by weight or less. Is at least 3% by weight and at most 6% by weight.

Although it does not specifically limit as a solvent, For example, monohydric alcohols, such as water, methanol, ethanol, n-propanol, 2-propanol, butanol, dihydric alcohols, such as ethylene glycol, (beta) -oxyethyl methyl ether ( Ethylene glycol ethers such as methyl cellosolve), β-oxyethyl ether (ethyl cellosolve), β-oxyethylpropyl ether (propyl cellosolve), and butyl-β-oxyethyl ether (butyl cellosolve) Cellosolves), glycols such as ethylene glycol and propylene glycol, ketones such as acetone, methyl ethyl ketone and diethyl ketone, esters such as ethyl acetate, butyl acetate and benzyl acetate, methoxyethanol and ethoxyethanol Ether alcohols, propylene glycol monomethyl ether acetate, and the like.

The black fine particles in the black fine particle dispersion of this embodiment can be produced using a normal fine particle synthesis method. As the fine particle synthesis method, any method such as gas phase reaction method, spray pyrolysis method, atomization method, liquid phase reaction method, freeze drying method, hydrothermal synthesis method, or the like may be used.

According to the black fine particle dispersion of this embodiment, the secondary particle whose average particle diameter is 5 nm or more and 300 nm or less which the primary particle of microparticles | fine-particles which consist of metal and / or metal oxide whose average particle diameter is 1 nm or more and 200 nm or less is aggregated is contained. As a result, blackness can be increased, and light-shielding properties can be improved.

Further, by containing the polymer dispersant in an amount of 1% by weight or more and 10% by weight or less with respect to the total weight of the fine particles contained in the black fine particle dispersion, good dispersion stability can be obtained and good black light shielding property can be obtained.

In addition, by using polyvinylpyrrolidone as the polymer dispersant, better dispersion stability can be obtained. Since the polyvinylpyrrolidone can be dissolved in an organic solvent, by using polyvinylpyrrolidone as a polymer dispersant, fine particles can be dispersed in various solvents, and as a result, application to various paints is possible.

According to the above, the black fine particle dispersion liquid which is high in blackness, is excellent in light-shielding property, and is small in environmental load and which is a raw material of a black light-shielding film can be provided.

The black light shielding film of this embodiment can be obtained by apply | coating the black fine particle dispersion of this embodiment on a base material, and drying after that.

When this black light shielding film is formed in one main surface of a base material, it becomes a base material with a black light shielding film.

Although it does not specifically limit as a base material, A glass base material and a plastic base material (organic polymer base material) are mentioned. Moreover, a flat plate, a film form, a sheet form, etc. are mentioned as the shape. Moreover, a plastic sheet, a plastic film, etc. are very suitable as said plastic base material.

Although it does not specifically limit as a material of a glass base material, For example, it can select from a soda glass, a kali glass, an alkali free glass, etc. suitably.

Although it does not specifically limit as a material of a plastic base material, For example, cellulose acetate, polystyrene (PS), polyethylene terephthalate (PET), polyether, polyimide, epoxy, phenoxy, polycarbonate (PC), polyvinyl fluoride It can select suitably from a lidene, a triacetyl cellulose, a polyether sulfone (PES), polyacrylate, etc.

As a coating method, the method currently used, for example, the bar coating method, the spin coating method, the spray coating method, the inkjet method, the dip method, the roll coating method, the screen printing method, etc. are used preferably.

Since the dispersion liquid apply | coated on the base material contains a solvent, a solvent is removed by the subsequent drying process.

For example, the solvent contained in the dispersion is acidified by leaving the substrate coated with the dispersion at room temperature (25 ° C.) or by heating at a predetermined temperature, for example, 50 ° C. to 80 ° C. in the air. V) to a black light shielding film.

The black shading film has an OD value of CIE lightness L ^* of 10 or less, chromaticity a ^* of -1 or more and 1 or less, chromaticity b ^* of -1 or more and 1 or less, and an optical density standardized by CIE (International Lighting Commission). It is preferable that it is three or more.

The lower the CIE brightness L ^* , the higher the blackness of the black light shielding film, and when used as a black matrix, the display contrast is improved. Since chromaticity a ^* and chromaticity b ^* have a color value even if it is a value of + or a value of-, a value close to 0, that is, a black light shielding film is achromatic is preferable in view of display quality. When the OD value is low, the film thickness of the black light shielding film becomes thick in order to obtain sufficient light shielding properties. In particular, when the black light shielding film is used as a black matrix, problems such as display unevenness occur when the film thickness of the black light shielding film becomes thick.

Embodiment (third of the present invention):

Next, the preferable aspect of the 3rd black fine particle of this invention, a black fine particle dispersion liquid, a black light shielding film, and a base material with a black light shielding film is demonstrated.

In the black fine particles of the present embodiment, the surface of the secondary particles having an average particle diameter of 5 nm or more and 300 nm or less, in which primary particles of fine particles composed of metals and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less, is collected from the insulating film It is covered by.

Although these elements are not specifically limited, It is preferable that these microparticles | fine-particles contain 1 type (s) or 2 or more types chosen from the group of silver, tin, and nickel.

This secondary particle is most preferable in the form in which the space part is formed, Next, the form in which the space part is formed inside the outer shell layer or the outer shell layer which consists of multiple layers including the said outermost layer, or a nucleus The form in which the outer surface of the substance becomes a core shell shape formed by covering the outermost layer or the outer shell layer composed of a plurality of layers including the outermost layer is preferable. The secondary particles may be in the form of primary particles only aggregated through a dispersant or the like, but the primary particles are directly in contact with each other without a dispersant or the like, and are bonded together with a neck between the primary particles. The form which exists is more preferable.

The fine particles which are the constituents of the black fine particles can be produced using a conventional fine particle synthesis method. As the fine particle synthesis method, any method such as gas phase reaction method, spray pyrolysis method, atomization method, liquid phase reaction method, freeze drying method, hydrothermal synthesis method, or the like may be used.

The insulating film is made of highly insulating fine particles by insulating the surface of secondary particles having an average particle diameter of 5 nm or more and 300 nm or less, where primary particles of fine particles composed of metals and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less are collected. A metal oxide or an organic high molecular compound is preferable.

As the metal oxide, an insulating metal oxide such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), or the like is preferably used. do.

Moreover, as organic polymer compound, resin which has insulation, for example, polyimide, polyether, polyacrylate, a polyamine compound, etc. is used preferably.

In order that the film thickness of an insulating film can fully maintain the insulation of the said microparticle surface, the thickness of 1-100 nm is preferable, More preferably, it is 5-50 nm.

This insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, when alkoxides such as tetraethoxysilane and aluminum triethoxide are used, an insulating film having a uniform film thickness at a relatively low temperature can be formed.

Next, the cross-sectional shape of the black fine particles of this embodiment is demonstrated.

These black fine particles can adopt the following various structures.

(1) wheat structure

FIG. 5 is a cross-sectional view schematically showing the cross-sectional structure of the black fine particles of the present embodiment, wherein in the drawing, reference numeral 1 denotes black fine particles, and primary particles composed of a metal and / or metal oxide having an average particle diameter of 1 nm or more and 200 nm or less. (2) aggregates into secondary particles (3) having an average particle diameter of 5 nm or more and 300 nm or less, and the black fine particles (1) have a large size other than the particle spacing therein by densely gathering the primary particles (2). It forms a mill structure without a space part, and the surface of the secondary particle 3 is coat | covered with the insulating film 5. In addition, the primary particle 2 may consist of one type of metal or metal oxide, or may consist of two or more types of metal and / or metal oxide. The shape of the secondary particles is not particularly limited, but various shapes such as spherical shape, irregular shape, and plate shape can be used.

(2) hollow structure (first of the present invention)

FIG. 6: is sectional drawing which shows the other example of the cross-sectional structure of the black fine particle of this embodiment typically, The point which this black fine particle 11 differs from the black fine particle 1 of FIG. 1 is the inside of the secondary particle 3 The space part 12 was formed in this. Also in this black fine particle 11, the surface of the secondary particle 3 is coat | covered with the insulating film 5. There is no restriction | limiting in particular in the shape of this secondary particle, Various shapes, such as spherical shape, indefinite form, and plate shape, can be used. In addition, this hollow structure may not be perfect, the outer part and the space part 12 may be connected to a pore, for example, the spherical secondary particle of FIG. 2 may be divided into several pieces. .

(3) hollow structure (second of the present invention)

FIG. 7: is sectional drawing which shows the other example of the cross-sectional structure of the black fine particle of this embodiment typically, The point which this black fine particle 21 differs from the black fine particle 11 of FIG. It is the point which comprised the shell layer 22 and made the inside of this outer shell layer 22 into the space part 23. As shown in FIG. Also in this black fine particle 21, the surface of the secondary particle 3 is coat | covered with the insulating film 5.

Although this outer shell layer 22 is made into one layer of the microparticles | fine-particles 4 here, you may make it the structure which consists of two or more layers. Moreover, the shape of this black fine particle does not have a restriction | limiting in particular, The thing of various shapes, such as spherical shape, indefinite form, and plate shape, can be used. In addition, this hollow structure may not be perfect, the outer part and the space part 23 may be connected to a pore, for example, the spherical black fine particle of FIG. 3 may be divided into several pieces.

(4) core shell structure

FIG. 8: is sectional drawing which shows the other example of the cross-sectional structure of the black fine particle of this embodiment typically, The point which this black fine particle 31 differs from the black material 1 of FIG. 1 is that of the nucleus 32 of a particulate form. It is the structure which coat | covered the outer surface with the outer shell layer 22 which consists only of the microparticles | fine-particles 4. Also in this black fine particle 31, the surface of the secondary particle 3 is coat | covered with the insulating film 5. In addition, the outer shell layer 22 may not be in a perfect state, and the outside and the core 32 may be connected to the pores. Although the shape of these black fine particles does not have a restriction | limiting in particular, Various shapes, such as spherical shape, an amorphous form, and plate shape, can be used.

The material constituting the nucleus 32 is not particularly limited, but a material excellent in adhesion with the fine particles 4 constituting the outer shell layer 22 is preferable, for example, silver, tin, nickel, silicon oxide (SiO _2). ), Titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), and the like are preferably used.

In the black microparticles | fine-particles of this embodiment, the surface of the secondary particle whose average particle diameter is 5 nm or more and 300 nm or less which the primary particle of microparticles | fine-particles which consist of metal and / or metal oxide whose average particle diameter is 1 nm or more and 200 nm or less is collected is insulated. Coating increases the blackness as compared with the Ag particles and the Sn particles, improving the light shielding properties and improving the insulation.

The surface of the secondary particles having an average particle diameter of 5 nm or more and 300 nm or less, wherein the primary particles of fine particles composed of metals and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less are collected by an insulating film made of metal oxide. By coating, it becomes excellent in heat resistance compared with metal microparticles | fine-particles, such as Ag particle | grains and Sn particle | grains, and its mechanical strength is high and it is hard to wear.

The black fine particle dispersion of this embodiment contains the black fine particle of this embodiment, and this black fine particle dispersion contains a solvent, an organic binder etc. as needed.

Although it does not specifically limit as a solvent, For example, the solvent illustrated by the said embodiment (2nd of this invention) can be used similarly.

In the black fine particle dispersion of this embodiment, the surface of the secondary particle whose average particle diameter is 5 nm or more and 300 nm or less which the primary particle of microparticles | fine-particles which consist of metal and / or metal oxide whose average particle diameter is 1 nm or more and 200 nm or less is aggregated is used. By containing black microparticles | fine-particles coat | covered with the insulating film, it becomes possible to provide the black fine particle dispersion liquid which is high in blackness, excellent in light-shielding property, and insulation, and becomes a raw material of an inexpensive black light-shielding film.

In addition, by using polyvinylpyrrolidone as the polymer dispersant, better dispersion stability can be obtained. Since this polyvinylpyrrolidone is soluble in an organic solvent, by using polyvinylpyrrolidone as a polymer dispersant, fine particles can be dispersed in various solvents, and as a result, application to various paints becomes possible.

According to the above, the black fine particle dispersion liquid which is a raw material of a black light shielding film with high blackness, excellent light-shielding property, and a low environmental load can be provided.

The black light shielding film of this embodiment can be obtained by apply | coating the black fine particle dispersion liquid of this embodiment on a base material, and drying after that.

When this black light shielding film is formed in one main surface of a base material, it becomes a base material with a black light shielding film.

Although it does not specifically limit as a base material, A glass base material and a plastic base material (organic polymer base material) are mentioned. Moreover, as a shape, a flat plate, a film form, a sheet form, etc. are mentioned. Moreover, a plastic sheet, a plastic film, etc. are very suitable as said plastic base material.

Although it does not specifically limit as a material of a glass base material and a plastic base material, For example, the material of the glass base material and the plastic base material illustrated by the said embodiment (2nd of this invention) can be used similarly.

As a coating method, the method currently used, for example, the bar coating method, the spin coating method, the spray coating method, the inkjet method, the dip method, the roll coating method, the screen printing method, etc. are used preferably.

Since the dispersion liquid apply | coated on the base material contains a solvent, a solvent is removed by the subsequent drying process.

For example, the solvent contained in the dispersion may be prepared by leaving the substrate coated with the dispersion at room temperature (25 ° C.) in the air, or by heating at a predetermined temperature, for example, 50 ° C. to 80 ° C. in the air. It is made into a black shading film.

When using this black light shielding film as a black matrix of display apparatuses, such as a liquid crystal display (LCD), it is preferable to have high insulation, For example, as a volume resistance (ohm * cm), 10 ⁷ ohm * cm or more is a preferable range. to be.

Also, the CIE brightness L ^* of 10 or less, chromaticity a ^* of -1 or more and 1, chromaticity b ^* of -1 or more and 1 or less, and an optical density of OD value of 3 or more. It is preferable.

The lower the CIE brightness L ^*, the higher the blackness, and in particular, when used as a black matrix of a display device such as a liquid crystal display (LCD), the lower the contrast of the display. Therefore, 10 or less which is a range with favorable display contrast was made into the preferable range.

It is preferable that chromaticity a ^* , b ^* is an achromatic color from the point of display quality, and since absolute value exceeds 1, it has a color, The absolute value which becomes achromatic color is 1 or less, ie, -1 or more and 1 or less.

If the OD value is low, sufficient light shielding properties cannot be obtained, and in order to obtain sufficient light shielding properties with a low OD value film, the film thickness must be increased, and in particular, when used as a black matrix such as a liquid crystal display (LCD), the film thickness As the thickness becomes thicker, display unevenness tends to occur. Therefore, even when film thickness is thin, the range which can obtain sufficient light-shielding property was made into 3 or more.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the cross-sectional structure of the black material of embodiment (1st of this invention) of this invention, and the black fine particles of embodiment (2nd of this invention).

It is a schematic diagram which shows the other example of the cross-sectional structure of the black material of embodiment (1st of this invention) of this invention, and the black fine particle of embodiment (2nd of this invention).

It is a schematic diagram which shows the other example of the cross-sectional structure of the black material of embodiment (1st of this invention) of this invention, and the black fine particle of embodiment (2nd of this invention).

It is a schematic diagram which shows the other example of the cross-sectional structure of the black material of embodiment (1st of this invention) of this invention, and the black fine particle of embodiment (2nd of this invention).

It is a schematic diagram which shows the cross-sectional structure of the black fine particle of embodiment (3rd of this invention) of this invention.

It is a schematic diagram which shows another example of the cross-sectional structure of the black fine particle of embodiment (3rd of this invention) of this invention.

It is a schematic diagram which shows another example of the cross-sectional structure of the black fine particle of embodiment (3rd of this invention) of this invention.

It is a schematic diagram which shows another example of the cross-sectional structure of the black fine particle of embodiment (3rd of this invention) of this invention.

9 is a view showing a powder X-ray diffraction diagram of the powder samples of Examples 1 and 7 of the present invention.

10 is a diagram showing a powder X-ray diffraction diagram of powder samples of Examples 2 and 8 of the present invention.

Fig. 11 is a diagram showing a powder X-ray diffraction diagram of the powder samples of Examples 3 and 9 of the present invention.

12 is a view showing a powder X-ray diffraction diagram of the powder sample of Example 4 of the present invention.

Fig. 13 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 5 of the present invention.

<Description of the code>

1, 11, 21, 31: black material

2: primary particles

3: secondary particles

4: particulate

5: insulation film

12, 23: space part

22: dense outer shell layer

32: nucleus of particle shape

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment (1st of this invention) of this invention is demonstrated more concretely by Examples 1-6 and Comparative Examples 1-3, this invention is not limited by these Examples.

(Example 1)

10 g of tin colloid (average particle diameter: 90 nm, solid content: 30% by weight, manufactured by Sumitomo Osaka Chemical Co., Ltd.) was taken, and pure water was added thereto to obtain A liquid having a total capacity of 300 ml. In addition, 1.5 g of silver nitrate and 33 g of sodium thiosulfate are weighed and mixed, pure water is added thereto to make an aqueous solution, 5 ml of concentrated ammonia water (NH ₃ : 28%) is added to this aqueous solution, and further pure water is added to the total capacity. This 100 ml liquid B was obtained.

Subsequently, these A liquid and B liquid were mixed for 10 minutes using the magnetic stirrer, and it wash | cleaned by centrifugation, and the C liquid whose solid content is 15% was obtained.

When the shape of the particle | grains in this C liquid was observed with the transmission electron microscope (TEM), the particle | grains whose particle diameters are 10-30 nm covered the surface of the particle | grains whose particle diameters are 50-90 nm.

Moreover, the particle | grains were isolate | separated from this C liquid by the filtration method, and it dried after that, the powder sample of Example 1 was produced, and the produced | generated image in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 9 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 1, wherein? Is a diffraction line of tin (Sn), and? Is a diffraction line of an Ag ₄ Sn alloy phase or an Ag ₃ Sn alloy phase. to be.

According to the powder X-ray diffraction diagram and the synthesis procedure described above, it was found that the particles in the C liquid had a core shell structure in which the surface of the Sn particles serving as nuclei was covered with Ag · Sn alloy fine particles.

Subsequently, PVA aqueous solution was added to this C liquid so that it may become volume ratio of solid content in liquid C: PVA = 50: 50, and it disperse | distributes in an ultrasonic disperser (Sonyfire 450: BRANSON ULTRASONICS company), and it is left as it is for 1 hour, and a coating liquid It was made.

Next, this coating liquid was applied onto a glass substrate having a thickness of 1.1 mm by a spin coat method to obtain a black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a coating liquid.

Subsequently, after drying this black film | membrane at room temperature (25 degreeC), the film thickness was measured by the film thickness measuring instrument Tencol (Tencol Co., Ltd.), and the light transmittance of the black film | membrane itself with respect to the light of wavelength of 550nm with a spectroscopic spectrometer. Was measured.

Moreover, in order to evaluate the blackness of this black film, the CIE brightness L ^* of this black film was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE (International Illumination Commission). These measurement results are shown in Table 1.

(Example 2)

Pure water was added to the C solution obtained in Example 1 and diluted 10 times. 100 g of aqueous tartaric acid solution (tinic acid: 5%) was added to the diluted solution and stirred for 10 minutes, followed by washing by centrifugation to obtain a solid content of 15. D solution which is% was obtained.

As a result of observing the shape of particle | grains in this D liquid with the transmission electron microscope (TEM), it turned out that there exist many hollow particle | grains whose particle diameter is 50-90 nm and the space part was formed inside. This hollow particle | grain was the shape which the particle | grains whose particle diameters are 10-30 nm gathered.

Moreover, the particle | grains were isolate | separated from this D liquid by the filtration method, and then dried, the powder sample of Example 2 was produced, and the produced | generated phase in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 10 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 2, wherein? Is a diffraction line of Sn, and? Is a diffraction line of Ag ₄ Sn alloy phase or Ag ₃ Sn alloy phase.

As mentioned above, it turned out that the particle | grains in D liquid are hollow particle | grains comprised from Ag * Sn alloy.

Subsequently, an aqueous solution of PVA was added to this liquid D so that the volume ratio of solid content in liquid D: PVA = 50: 50 was dispersed in an ultrasonic disperser (Sonyfire 450: manufactured by BRANSON ULTRASONICS) and left as it was for 1 hour to obtain a coating liquid. .

Next, this coating liquid was applied onto a glass substrate having a thickness of 1.1 mm by the spin coating method to obtain a black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a coating liquid.

Then, after drying this black film at room temperature (25 degreeC), the film thickness was measured by the film thickness meter Tencol (Tencol Co., Ltd.), and the light transmittance of the black film itself with respect to the light of 550 nm wavelength was measured by the spectral spectrometer. Measured.

In addition, the CIE lightness L ^* of this black film | membrane was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE. These measurement results are shown in Table 1.

(Example 3)

Pure water was added and diluted 10-fold with D liquid obtained in Example 2, and this diluted solution was dispersed for 5 minutes using a sand mill to obtain an E liquid having a solid content of 15%.

As a result of observing the shape of the particle | grains in this E liquid with the transmission electron microscope (TEM), it turned out that the particle | grains whose particle diameters are 10-30 nm aggregate and form the particle | grains whose particle diameters are 50-150 nm.

Moreover, the particle | grains were isolate | separated from this E liquid by the filtration method, and it dried after that, the powder sample of Example 3 was produced, and the produced | generated phase in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 11 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 3, wherein? Indicates a diffraction line of an Ag ₄ Sn alloy phase or an Ag ₃ Sn alloy phase.

As mentioned above, it turned out that the particle | grains in E liquid are particle | grains which Ag-Sn alloy microparticles | fine-particles gathered.

Subsequently, PVA aqueous solution was added to this E liquid so that it may become a volume ratio of solid content: PVA = 50: 50 in E liquid, and it disperse | distributed in an ultrasonic disperser (Sonyfire 450: BRANSON ULTRASONICS Co., Ltd.), and left as it for 1 hour as a coating liquid. .

Next, this coating liquid was applied onto a glass substrate having a thickness of 1.1 mm by the spin coating method to obtain a black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a coating liquid.

Then, after drying this black film at room temperature (25 degreeC), the film thickness was measured by the film thickness meter Tencol (Tencol Co., Ltd.), and the light transmittance of the black film itself with respect to the light of wavelength of 550 nm by a spectroscopic spectrometer. Was measured.

Moreover, CIE lightness L ^* of this black film | membrane was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE. These measurement results are shown in Table 1.

(Example 4)

Water was added to 2.3 g of glucose, 0.2 g of tartaric acid, and 4 g of ethanol to obtain an F liquid having a total weight of 50 g. In addition, 5 ml of concentrated ammonia water (NH ₃ : 28%) was added to 1.5 g of silver nitrate, and pure water was further added to obtain a G liquid having a total weight of 50 g.

Subsequently, these F liquids and G liquids were mixed, and this mixed liquid was added to the A liquid used in Example 1, and this solution was stirred, and 10 g of 0.05-N sodium hydroxide aqueous solution was slowly dropped to this solution. Subsequently, the solution was stirred for 10 minutes using a magnetic stirrer, and then washed by centrifugation to obtain an H liquid having a solid content of 15%.

The shape of the particle | grains in this H liquid was observed with the transmission electron microscope (TEM), and as a result, the surface whose particle diameter is 80-100 nm was smooth particle | grains.

Moreover, the particle | grains were isolate | separated from this H liquid, and it dried after that, the powder sample of Example 4 was produced, and the produced | generated image in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 12 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 4, wherein? Is a diffraction line of Sn, x is a diffraction line of silver (Ag), and? Is an Ag ₄ Sn alloy phase or Diffraction lines of Ag ₃ Sn alloy phase.

As mentioned above, it turned out that the particle | grains in H liquid consist of the dense layer of Ag and Ag. Sn alloy.

Subsequently, PVA aqueous solution was added to this H liquid so that it may become a volume ratio of solid content: PVA = 50: 50 in H liquid, and it disperse | distributes in an ultrasonic disperser (Sonyfire 450: BRANSON ULTRASONIC Co., Ltd.), and it is left as it for 1 hour as a coating liquid. It was.

Then, this coating liquid was apply | coated on the glass substrate of thickness 1.1mm by the spin coat method, and it was set as the black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a coating liquid.

Subsequently, after drying this black film | membrane at room temperature (25 degreeC), the film thickness was measured by the film thickness meter Tencol (Tencol Co., Ltd.), and the light transmittance of the black film | membrane itself with respect to the light of wavelength of 550 nm was measured by the spectral spectrometer. Measured.

In addition, the CIE lightness L ^* of this black film | membrane was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE. These measurement results are shown in Table 1.

(Example 5)

Pure water was added to the H liquid obtained in Example 4 and diluted 10-fold. 100 g of aqueous tartaric acid solution (tinic acid: 5%) was added to the diluted solution and stirred for 10 minutes, followed by washing by centrifugation, whereby the solid content was 15. I solution which is% was obtained.

As a result of observing the shape of the particles in the liquid I by a transmission electron microscope (TEM), a large number of hollow particles having a particle diameter of 80 to 100 nm exist, and the hollow particles are formed of a dense outer shell layer. I could see that.

Moreover, the particle | grains were isolate | separated from this liquid I, and it dried after that, the powder sample of Example 5 was produced, and the generated image in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 13 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 5, wherein? Is a diffraction line of Sn and? Is a diffraction line of Ag ₄ Sn alloy phase or Ag ₃ Sn alloy phase.

As mentioned above, it turned out that the hollow particle formed from the dense outer shell layer in I liquid is comprised from Ag * Sn alloy.

Subsequently, PVA aqueous solution was added to this liquid I so that it may become volume ratio of solid content in liquid I: PVA = 50: 50, and it disperse | distributes in an ultrasonic disperser (Sonyfire 450: BRANSON ULTRASONICS company), and it is left as it is for 1 hour, and a coating liquid It was made.

Then, this coating liquid was apply | coated on the glass substrate of thickness 1.1mm by the spin coat method, and it was set as the black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a coating liquid.

Subsequently, after drying this black film at room temperature (25 degreeC), the film thickness was measured by the film thickness meter Tencol (Tencol Co., Ltd.), and the spectroscopic spectrometer of the black film itself with respect to the light of the wavelength with respect to the light of 550 nm wavelength was carried out. Light transmittance was measured.

Moreover, CIE lightness L ^* of this black film | membrane was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE. These measurement results are shown in Table 1.

(Example 6)

33.8 ml of an aqueous tin chloride solution containing 1.19 g of nickel chloride powder (NiC1 ₂ · 6H ₂ O) and 100 g of tin chloride (SnC1 ₂ · 2H ₂ O) dissolved in pure water in 100 ml of pure water. To this solution, 9.9 g of potassium pyrophosphate powder, 7.5 g of tartaric acid, and 0.82 g of glycine were further added, followed by stirring for 10 minutes.

Thereafter, 5.0 g of a 1% polyvinylpyrrolidone aqueous solution was added to this solution, a 5N aqueous NaOH solution was further added dropwise, and the pH of the solution was adjusted to 8.5.

Subsequently, in the state which kept this solution at 55 degreeC, the solution obtained by dissolving 1.1 g of sodium borohydride in 50 g of pure water was thrown in at once, and it stirred for 1 hour. Thereafter, washing was performed by centrifugation to obtain a J liquid having a solid content of 10%.

As a result of observing the shape of the particles in the J liquid with a transmission electron microscope (TEM), the particles having a particle diameter of 1 to 10 nm adhered to cover the particle surface having a particle diameter of 20 to 30 nm, and the particle diameter was 30. It turned out that the secondary particle which is -50 nm is formed.

The particles were separated from the liquid J by filtration and then dried to prepare a powder sample of Example 6, and elemental analysis of the powder sample was carried out using an electron probe microanalyzer (EPMA). Trace amounts of B were detected.

As a result of identifying the generated image in the powder sample using an X-ray diffraction apparatus, diffraction lines of Ni and Sn were detected.

From the powder X-ray diffraction diagram and the synthesis procedure described above, it was found that the particles in the J liquid had a core shell structure in which the surfaces of Ni particles serving as nuclei were covered with Sn fine particles.

Subsequently, PVA aqueous solution was added to this J liquid so that it may become a volume ratio of solid content: PVA = 50: 50 in J liquid, and it disperse | distributes in an ultrasonic disperser (Sonyfire 450: BRANSON ULTRASONICS Co., Ltd.), and keeps it for 1 hour as a coating liquid. It was.

Then, this coating liquid was apply | coated on the glass substrate of thickness 1.1mm by the spin coat method, and it was set as the black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a coating liquid.

Subsequently, after drying this black film | membrane at room temperature (25 degreeC), the film thickness is measured by the film thickness meter Tencol (Tencol Co., Ltd.), and the light transmittance of the black film | membrane itself with respect to the light of wavelength of 550nm is measured by the spectral spectrometer. It was.

In addition, in order to evaluate the blackness of this black film, the CIE brightness L ^* of this black film was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE (International Illumination Commission). These measurement results are shown in Table 1.

(Comparative Example 1)

An aqueous solution of PVA was added to carbon black (HA3, manufactured by Tokai Carbon Co., Ltd.) in the same manner as in Example 1 so as to have a volume ratio of carbon black: PVA = 50: 50, and dispersion treatment and adjustment of the amount of water in the coating liquid in the same manner as in Example 1, Coating on the glass substrate was performed, and the black coating film of thickness 0.5micrometer was produced.

Subsequently, the black film was dried, the film thickness was measured, the light transmittance was measured, and the CIE brightness L ^* was measured in the same manner as in Example 1. These measurement results are shown in Table 1.

(Comparative Example 2)

PVA aqueous solution was added to titanium black (13M, manufactured by Gemco Co., Ltd.) in the same manner as in Example 1 so as to have a volume ratio of titanium black: PVA = 50: 50, and dispersion treatment and adjustment of the amount of water in the coating liquid were performed in the same manner as in Example 1. Application | coating to the glass substrate was performed and the black coating film whose thickness is 0.5 micrometer was produced.

Then, in the same manner as in Example 1, drying of the black film, measurement of the film thickness, measurement of light transmittance, and measurement of CIE brightness L ^* were performed. These measurement results are shown in Table 1.

(Comparative Example 3)

To the silver nanoparticles (manufactured by Sumitomo Osaka Cement Co., Ltd.), an aqueous solution of PVA was added so as to have a volume ratio of silver nanoparticles: PVA = 50: 50 in the same manner as in Example 1, and the dispersion treatment and the amount of water in the coating liquid were performed in the same manner as in Example 1. Adjustment was carried out and coating on the glass substrate was made to produce a black coating film having a thickness of 0.5 µm.

Subsequently, drying of this black film | membrane, the measurement of a film thickness, the measurement of light transmittance, and the measurement of CIE brightness L ^* were performed similarly to Example 1. These measurement results are shown in Table 1.

Structure of particles Film thickness (㎛) Light transmittance (%) CIE Brightness L ^* Example 1 Sn-Ag fine particles 0.51 0.00 4.3 Example 2 Sn · Ag alloy hollow particles 0.50 0.00 3.5 Example 3 Sn · Ag alloy assembly particle 0.52 0.00 3.9 Example 4 Sn-Ag Dense Shell Particles 0.51 0.00 4.4 Example 5 Sn · Ag dense shell hollow particles 0.53 0.00 4.0 Example 6 Ni · Sn Fine Particles 0.55 0.00 4.7 Comparative Example 1 Carbon black 0.55 0.32 5.1 Comparative Example 2 Titanium black 0.53 1.05 8.6 Comparative Example 3 Ag nanoparticles 0.52 0.01 24

According to this Table 1, it was confirmed that the black films of Examples 1 to 6 had a lower light transmittance, an excellent CIE brightness L ^* , and excellent light shielding properties and blackness than Comparative Examples 1 to 3.

On the other hand, it was found that the black films of Comparative Examples 1 and 2 had high light transmittance and were inferior in light shielding properties as compared with the black films of Examples 1 to 5.

In addition, although the black film | membrane of the comparative example 3 can obtain substantially the same light-shielding properties as Examples 1-6, the film | membrane color is gray and there existed a problem in the point of color tone.

EMBODIMENT OF THE INVENTION Next, although embodiment 7 of this invention (2nd of this invention) demonstrates this invention concretely by Examples 7-10 and Comparative Examples 4-6, this invention is limited by these Examples. no.

(Example 7)

Take 20 g of tin (Sn) colloid (particle diameter 20-80 nm, average particle diameter: 30 nm, solid content: 15 weight%, Sumitomo Osaka Chemical Co., Ltd.), and this polyvinylpyrrolidone (PVP) (k15: Tokyo Kasei Co., Ltd. make). ) Was added to 0.15 g of dissolved pure water to obtain an A liquid having a total volume of 300 ml.

In addition, 1.5 g of silver nitrate and 33 g of sodium thiosulfate are weighed and mixed, pure water is added thereto to make an aqueous solution, 5 ml of concentrated ammonia water (NH ₃ : 28%) is added to this aqueous solution, and further pure water is added to the total capacity. This l00 ml liquid B was obtained.

Subsequently, these A liquid and B liquid were mixed for 10 minutes using the magnetic stirrer, and then it wash | cleaned by centrifugation and obtained C liquid whose solid content is 15%.

Subsequently, PVA aqueous solution was added to this C liquid so that it may become a volume ratio of solid content: PVA = 50: 50 in C liquid, and it disperse | distributes in an ultrasonic disperser (Sonyfire 450: BRANS0N ULTRAS0NICS company), and it leaves black for 1 hour. It was set as the fine particle dispersion.

Subsequently, this black fine particle dispersion was apply | coated on the glass substrate of thickness 1.1mm by the spin coat method, and it was set as the black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a dispersion liquid.

Then, after drying this glass substrate with a coating film at room temperature (25 degreeC), the glass substrate with a black light shielding film was obtained.

Then, the film thickness of this black light shielding film was measured by the film thickness measuring instrument Tencol (Tencol Co., Ltd.).

Next, the light transmittance of this glass substrate with a black light shielding film was measured. Here, the light transmittance of the black light shielding film itself with respect to the light of wavelength 550nm was measured with the spectral spectrometer.

In addition, in order to evaluate the blackness of this black shading film, the CIE lightness L ^* , chromaticity, b ^* of this black shading film was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE (International Lighting Commission). .

Moreover, the OD value which is the optical density of this black light shielding film was measured using the transmission density meter. These measurement results are shown in Table 2.

Moreover, when the shape of the particle | grains in said C liquid was observed with the transmission electron microscope (TEM), it was a shape which the particle | grains with an average particle diameter of 5-30 nm cover the surface of the particle whose average particle diameter is 20-80 nm.

Moreover, the particle | grains were isolate | separated from the said C liquid by the filtration method, and it dried after that, the powder sample of Example 1 was produced, and the produced | generated image in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 9 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 7, wherein? Is a diffraction line of tin (Sn), and? Is a diffraction line of an Ag ₄ Sn alloy phase or an Ag ₃ Sn alloy phase. to be.

Thereby, it turned out that the particle | grains in C liquid are core-shell structure which covered the surface of Sn particle used as a nucleus with Ag * Sn alloy microparticles | fine-particles.

(Example 8)

Pure water was added to the C solution obtained in Example 7 and diluted 10-fold. 100 g of aqueous hydrochloric acid solution (4.5% hydrochloric acid) was added to the diluted solution, followed by stirring for 10 minutes, followed by washing by centrifugation to obtain a solid. D solution which was 15% was obtained.

Subsequently, an aqueous solution of PVA was added to this liquid D so as to have a volume ratio of solid content in liquid D: PVA = 50: 50, dispersed in an ultrasonic disperser (Sony Fire 450: manufactured by BRANS0N ULTRAS0NICS), and then left as it was for 1 hour to give black fine particles. It was set as the dispersion liquid.

Next, this black fine particle dispersion was apply | coated on the glass substrate of thickness 1.1mm by the spin coat method, and it was set as the black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a dispersion liquid.

Then, after drying this glass substrate with a coating film at room temperature (25 degreeC), the glass substrate with a black light shielding film was obtained.

Subsequently, in the same manner as in Example 7, the film thickness of the black light shielding film, the light transmittance, the CIE brightness L ^* , the chromaticities a ^* , b ^* , and the 0D value were measured. These measurement results are shown in Table 1.

In addition, when the shape of the particles in the liquid D was observed with a transmission electron microscope (TEM), it was found that the average particle diameter was 20 to 80 nm, and there were a large number of completely hollow particles having a space therein. . At the same time, some of the hollow particles were insufficient or some particles were broken up. These hollow particles were secondary particles in which primary particles having an average particle diameter of 5 to 30 nm were collected.

Moreover, the particle | grains were isolate | separated from the said D liquid by the filtration method, and it dried after that, the powder sample of Example 8 was produced, and the produced | generated image in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 10 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 8, wherein? Is a diffraction line of tin (Sn), and? Is a diffraction line of an Ag ₄ Sn alloy phase or an Ag ₃ Sn alloy phase; to be.

Thereby, it turned out that the particle | grains in D liquid are the particle | grains which fell short or some part of the hollow particle | grains comprised from Ag * Sn alloy, and the hollow shape particle | grains.

(Example 9)

Pure water was added and diluted 10-fold with D liquid obtained in Example 8, and this diluted solution was dispersed for 5 minutes using a sand mill to obtain an E liquid having a solid content of 15%.

Then, PVA aqueous solution was added to this E liquid so that it may become a volume ratio of solid content: PVA = 50: 50 in E liquid, and it disperse | distributes in an ultrasonic disperser (Sonyfire 450: BRANS0N ULTRAS0NICS company), and it leaves black for 1 hour. It was set as the fine particle dispersion.

Subsequently, this black fine particle dispersion was apply | coated on the glass substrate of thickness 1.1mm by the spin coat method, and it was set as the black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a dispersion liquid.

Then, after drying this glass substrate with a coating film at room temperature (25 degreeC), the glass substrate with a black light shielding film was obtained.

Subsequently, in the same manner as in Example 7, the film thickness of the black light shielding film, the light transmittance were measured, the CIE brightness L ^* , the chromaticity a ^* , b ^* , and the 0D value were measured. These measurement results are shown in Table 2.

In addition, when the shape of the particle | grains in said E liquid was observed with the transmission electron microscope (TEM), the particle | grains with an average particle diameter of 5-30 nm gather and form the secondary particle whose average particle diameter is 30-150 nm. I could see that.

Moreover, the particle | grains were isolate | separated from this E liquid by the filtration method, and then dried, the powder sample of Example 9 was produced, and the produced | generated image in this powder sample was identified using the X-ray diffraction apparatus.

Fig. 11 is a diagram showing a powder X-ray diffraction diagram of the powder sample of Example 9, wherein? Denotes diffraction lines of an Ag ₄ Sn alloy phase or an Ag ₃ Sn alloy phase.

Thereby, it turned out that the particle | grains in E liquid are particle | grains which Ag-Sn alloy microparticles | fine-particles gathered.

(Example 10)

33.8 ml of an aqueous tin chloride solution containing 1.19 g of nickel chloride powder (NiCl ₂ · 6H ₂ O) and 100 g of tin chloride (SnCl ₂ · 2H ₂ O) in 100 ml of pure water to a total capacity of 1 liter (L) To this solution, 9.9 g of potassium pyrophosphate powder, 7.5 g of tartaric acid, and 0.82 g of glycine were further added, followed by stirring for 10 minutes.

Thereafter, 5.0 g of a 1% polyvinylpyrrolidone (PVP) aqueous solution was added to the solution, and the pH of the solution was adjusted to 8.5 by further dropping a 5N aqueous Na0H solution.

Subsequently, the solution obtained by dissolving 1.1 g of sodium borohydride in 50 g of pure water while maintaining the solution at 55 ° C. was added at once, stirred for 1 hour, and then washed by centrifugation to obtain a solid content of 10%. F solution was obtained.

Subsequently, PVA aqueous solution was added to this F liquid so that it may become a volume ratio of solid content: PVA = 50: 50 in F liquid, and it disperse | distributes in an ultrasonic disperser (Sonyfire 450: BRANS0N ULTRAS0NICS company), it is left for 1 hour, and it is a black fine particle dispersion It was made.

Subsequently, this black fine particle dispersion was apply | coated on the glass substrate of thickness 1.1mm by the spin coat method, and it was set as the black coating film. Here, the thickness of the coating film was 0.5 micrometer by adjusting the moisture content in a dispersion liquid.

Then, after drying this glass substrate with a coating film at room temperature (25 degreeC), the glass substrate with a black light shielding film was obtained.

Then, in the same manner as in Example 7, the film thickness of the black light shielding film, the measurement of the light transmittance, the measurement of the CIE brightness L ^* , the chromaticities a ^* , b ^* , and the 0D value were measured. These measurement results are shown in Table 2.

In addition, as a result of observing the shape of the particles in the F liquid by a transmission electron microscope (TEM), particles having an average particle diameter of 1 to 10 nm adhered to cover the surface of particles having an average particle diameter of 20 to 30 nm. It turned out that the secondary particle whose average particle diameter is 30-50 nm is formed.

In addition, the particles were separated from the F liquid by filtration and then dried to prepare a powder sample of Example 10, and elemental analysis of the powder sample was performed using an electron probe microanalyzer (EPMA). And trace amounts of B were detected.

As a result of identifying the generated image in the powder sample using an X-ray diffraction apparatus, diffraction lines of Ni and Sn were detected.

Thereby, it turned out that the particle | grains in F liquid are core-shell structure in which the surface of Ni particle used as a nucleus was covered with Sn microparticles | fine-particles.

(Comparative Example 4)

To the carbon black (HA3, manufactured by Tokai Carbon Co., Ltd.), an aqueous solution of PVA was added in the same manner as in Example 7 so as to have a volume ratio of carbon black: PVA = 50: 50, and dispersion treatment and adjustment of the amount of water in the dispersion liquid were carried out in the same manner as in Example 7. Coating on the glass substrate by the spin coat method was performed, and the black coating film of thickness 0.5micrometer was produced.

Next, this glass substrate with a coating film was dried at room temperature (25 degreeC), and the glass substrate with a black light shielding film was obtained.

Subsequently, in the same manner as in Example 7, the film thickness of the black light shielding film, the light transmittance, the CIE brightness L ^* , the chromaticities a ^* , b ^* , and the 0D value were measured. These measurement results are shown in Table 1.

(Comparative Example 5)

To titanium black (13M, manufactured by Gemco Co., Ltd.), an aqueous solution of PVA was added so as to have a volume ratio of titanium black: PVA = 50: 50 in the same manner as in Example 7, and the dispersion treatment, adjustment of the amount of water in the dispersion liquid and spin were carried out in the same manner as in Example 7. Application | coating to the glass substrate by the coating method was performed, and the black coating film whose thickness is 0.5 micrometer was produced.

Next, this glass substrate with a coating film was dried at room temperature (25 degreeC), and the glass substrate with a black light shielding film was obtained.

Subsequently, in the same manner as in Example 7, the film thickness of the black light shielding film, the light transmittance, the CIE brightness L ^* , the chromaticities a ^* , b ^* , and the 0D value were measured. These measurement results are shown in Table 2.

(Comparative Example 6)

To the silver nanoparticles (manufactured by Sumitomo Osaka Cement Co., Ltd.), an aqueous solution of PVA was added so as to have a volume ratio of silver nanoparticles: PVA = 50: 50 in the same manner as in Example 7, and the dispersion treatment and adjustment of the amount of water in the dispersion liquid were carried out in the same manner as in Example 7. The coating was applied onto a glass substrate by a spin coating method to produce a black coating film having a thickness of 0.5 µm.

Next, this glass substrate with a coating film was dried at room temperature (25 degreeC), and the glass substrate with a black light shielding film was obtained.

Then, in the same manner as in Example 7, the film thickness of the black light shielding film, the measurement of the light transmittance, the measurement of the CIE brightness L ^* , the chromaticities a ^* , b ^* , and the 0D value were measured. These measurement results are shown in Table 2.

Structure of particles Film thickness (㎛) Light transmittance (%) OD value CIE Brightness L ^* Chromaticity a ^* Chromaticity b ^* Example 7 Sn-Ag core-shell aggregated particles 0.51 0.00 > 4 4.5 -0.49 0.15 Example 8 Sn · Ag hollow aggregated particles 0.50 0.00 > 4 3.6 -0.13 -0.30 Example 9 Sn · Ag aggregate particles 0.50 0.00 > 4 3.9 -0.04 0.33 Example 10 Ni · Sn Core Shell Type Aggregate Particles 0.53 0.00 > 4 4.7 -0.99 0.67 Comparative Example 4 Carbon black 0.51 0.35 2.45 5.0 1.25 -2.30 Comparative Example 5 Titanium black 0.50 1.02 1.99 8.6 1.23 1.45 Comparative Example 6 Ag nanoparticles 0.52 0.01 4.00 21.3 -0.89 8.86

According to this Table 2, the black light shielding films of Examples 7 to 10 had lower light transmittance, lower CIE brightness, L ^*, and lower absolute values of chromaticities a ^* and b ^* than those of Comparative Examples 4-6. It was confirmed that the blackness was excellent.

On the other hand, it was found that the black light shielding films of Comparative Examples 4 and 5 had high light transmittance and were inferior in light shielding properties as compared with the black light shielding films of Examples 7 to 10.

Moreover, although the black light shielding film of the comparative example 6 can obtain substantially the same light shielding properties as Examples 7-10, the color of a film is gray and there existed a problem in the point of color tone.

EMBODIMENT OF THE INVENTION Next, although Example 11-12 and Comparative Examples 7-9 are demonstrated about embodiment (3 of this invention) of this invention, this invention is not limited by these Examples.

`` Preparation of black fine particles ''

Black fine particles were prepared as follows.

(1) Silica Coating Silver Tin Alloy Assembly Particles A

Aqueous dispersion of black silver tin alloy aggregate particles forming secondary particles having an average particle diameter of 20 to 150 nm, in which primary particles having an average particle diameter of 5 to 20 nm are collected (concentration of 15% by weight of solid content, manufactured by Sumitomo Osaka Cement Co., Ltd.). ) 750 g of 0.1% by weight aqueous solution of 3-aminopropyltrimethoxysilane (APS) was added to the solution diluted 10-fold with pure water to make A solution.

On the other hand, 100 g of a solution (3% in terms of SiO ₂ ) diluted with water glass was prepared using a cation exchange resin to prepare a pH of 10.5 to be B solution.

Subsequently, pH was adjusted to 9.5 by Na0H aqueous solution (0.1N) in said A liquid, and the said B liquid was slowly dripped at this A liquid, and it stirred for 1 hour. Subsequently, ultrafiltration was used to remove unreacted water glass, APS, ions, and the like from this solution, and then concentrated to obtain a dispersion.

Subsequently, the solution and fine particles were separated from this dispersion by centrifugation, freeze dry, and the like, and dried to obtain silica coated silver tin alloy aggregate particles A.

(2) silica coating silver tin alloy assembly particle B

Aqueous dispersion of black silver tin alloy aggregate particles forming secondary particles having an average particle diameter of 20 to 150 nm, in which primary particles having an average particle diameter of 5 to 20 nm are collected (concentration of 15% by weight of solid content, manufactured by Sumitomo Osaka Chemical Co., Ltd.). ) The pH was adjusted to 4.8 by adding acetic acid to a solution diluted 100-fold with 100 g of pure water.

Subsequently, 200 g of aqueous solution containing 1 weight% of tetraethoxysilane was dripped at this solution, and it stirred at 60 degreeC for 2 hours. Subsequently, unreacted tetraethoxysilane, acetic acid, and the like were removed from this solution using ultrafiltration, and then concentrated to obtain a dispersion.

Subsequently, a silica-coated silver tin alloy aggregate particle B was obtained by drying etc. by separating and drying a solution and microparticles | fine-particles from this dispersion liquid by centrifugation, freeze drying, etc.

"Preparation of a black fine particle dispersion and a black light shielding film" (Example 11)

To 100 g of silica coated silver tin alloy aggregate particles A, 2 g of a dispersant (Solpas 24000: manufactured by Avicia Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate are added, and dispersed using a bead mill to disperse the silica coated silver tin alloy aggregate. A particle dispersion was obtained. To this dispersion was added 50 g of a binder consisting of benzyl methacrylate / methacrylic acid copolymer: 64 parts by weight, dipentaerythritol hexaacrylate: 26 parts by weight, and Irgacure 907: 9 parts by weight, followed by mixing to obtain a coating solution. . This coating liquid was applied onto a glass substrate by a spin coater, dried at room temperature (25 ° C.), and then irradiated with ultraviolet (UV) to form a black film having a thickness of 0.6 μm.

(Example 12)

In Example 11, the black film of Example 12 was formed like Example 11 except having used the silica coating silver tin alloy assembly particle B instead of the silica coating silver tin alloy aggregate particle A.

(Comparative Example 7)

A black film was formed in the same manner as in Example 11 except that the silver tin alloy aggregate particles not coated with silica were used.

(Comparative Example 8)

A black film was formed in the same manner as in Example 11 except that silica coated carbon black was used.

(Comparative Example 9)

A black film was formed in the same manner as in Example 11 except that silica coated titanium black was used.

`` Evaluation of black film ''

The volume resistivity of each of the black films of Examples 11-12 and Comparative Examples 7-9 was measured. The measurement was measured by the 4-terminal method based on Japanese Industrial Standard JIS C2103-1991 "Volume resistivity test."

Moreover, the 0D value which is the optical density of this black film | membrane was measured using the transmission density meter.

In addition, in order to evaluate the blackness of this black film, the CIE lightness L ^* , chromaticity a ^* , b ^* of this black film was measured based on the L ^* a ^* b ^* colorimeter standardized by CIE (International Illumination Commission).

These results are shown in Table 3.

Volume resistivity (Ωcm) OD value CIE Brightness L ^* Chromaticity a ^* Chromaticity b ^* Example 11 > 10 ¹⁰ 4.2 4.51 -0.13 0.17 Example 12 > 10 ¹⁰ 4.1 4.66 -0.04 0.33 Comparative Example 7 1.2 × 10 ⁶ 4.1 4.53 -0.18 0.25 Comparative Example 8 > 10 ¹⁰ 2.0 5.19 1.12 -2.03 Comparative Example 9 > 10 ¹⁰ 1.8 5.63 1.51 1.66

According to this Table 3, the black films of Examples 11 and 12 had a volume resistivity of more than 10 ¹⁰ cm 3, a 0D value of 4 or more, a low CIE lightness L ^* and a low absolute value of chromaticities a ^* , b ^* . It was confirmed that it was excellent in insulation, light shielding property, and blackness.

On the other hand, the black film of Comparative Example 7 had a 0D value of 4 or more, a low CIE brightness L ^* and an absolute value of chromaticities a ^* and b ^* , but a volume resistivity of 1.2 × 10 ⁶ Ωcm and a low insulating property. I knew it was.

In addition, although the black films of Comparative Examples 8 and 9 had a volume resistivity of more than 10 ¹⁰ μm, the CIE brightness L ^* was high, the 0D value was small before and after 2, and the absolute values of chromaticities a ^* and b ^* exceeded 1. As compared with the black films of Examples 11 and 12, it was found that the blackness and the light shielding property were both separated.

Since the first black material of the present invention is excellent in blackness, light shielding properties, and is inexpensive, it is applicable to all articles requiring blackness or light shielding properties, or blackness and light shielding properties. For example, black light shielding film, black light shielding glass, black paper, black cloth, black ink, black matrix material for display devices such as plasma display (PDP) or liquid crystal display (LCD), black seal material, black mask material It can also be used.

The second black fine particle dispersion of the present invention is excellent in blackness and light shielding properties, further excellent in heat resistance, and can be used as a material for inexpensive black light shielding films. It is possible. For example, black matrix material, black seal material, black mask for display devices, such as a black light-shielding film, black light-shielding glass, black paper, black cloth, black ink, a plasma display (PDP) or a liquid crystal display (LCD), etc. It can also be used as a material.

The third black fine particles of the present invention are excellent in blackness, light shielding properties, and insulation properties, and can be used as materials for inexpensive black light shielding films. For example, black matrix material, black seal material, black mask material, etc. for display devices, such as a liquid crystal display (LCD), a plasma display (PDP), an electroluminescent display (ELD), an electrochromic display (ECD), etc. In addition, it can be used also as a black light-shielding film, black light-shielding glass, black paper, black cloth, black ink, etc.

Claims (21)

It consists of the secondary particle which the primary particle which consists of a metal and / or a metal oxide whose particle diameter is 1 nm or more and 200 nm or less, The particle diameter of this secondary particle is 5 nm or more and 300 nm or less, The outermost layers of these secondary particles are gold (Au), platinum (Pt), palladium (Pd), silver (Ag), ruthenium (Ru), copper (Cu), silicon (Si), titanium (Ti), tin ( A black material comprising at least 50% by weight of one or two or more elements selected from Sn), nickel (Ni) or these oxides. The method of claim 1, The secondary material is a black material, characterized in that a space portion is formed therein. The method of claim 1, The secondary material is a black material, characterized in that a space portion is formed inside the outer shell layer composed of a plurality of layers including the outermost layer or the outermost layer. The method of claim 1, And the secondary particles have a core shell shape formed by covering an outer surface of a material serving as a nucleus with an outermost layer or an outer shell layer including a plurality of layers including the outermost layer. The method according to claim 3 or 4, The outer shell layer is a black material, characterized in that dense. Black, characterized in that it comprises secondary particles and a polymer dispersant having an average particle diameter of 5 nm or more and 300 nm or less, in which primary particles of fine particles composed of metals and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less are collected. Particulate dispersion. The method of claim 6, The fine particles dispersion liquid black, characterized in that the fine particles contain one or two or more selected from the group consisting of silver, tin and nickel. The method of claim 6, The black fine particle dispersion, characterized in that the polymer dispersing agent is contained 1% by weight or more and 10% by weight or less with respect to the total weight of the fine particles. The method of claim 6, The black fine particle dispersion, characterized in that the polymer dispersant is polyvinylpyrrolidone. The method of claim 6, The black particulate dispersion according to claim 2, wherein the secondary particles have a space formed therein. The method of claim 6, The secondary particle is a black fine particle dispersion, characterized in that a space portion is formed inside the outer shell layer consisting of the outermost layer or a plurality of layers including the outermost layer. The method of claim 6, And the secondary particles have a core shell shape formed by covering an outer surface of a substance serving as a nucleus with an outermost layer or an outer shell layer including a plurality of layers including the outermost layer. The black shading film | membrane formed by apply | coating the black fine particle dispersion of any one of Claims 6-12. The base material with a black light shielding film provided with the black light shielding film of Claim 13 on one main surface of a base material. The method of claim 14, The black light shielding film has a CIE lightness L ^* of 10 or less, a chromaticity a ^* of -1 or more and 1 or less, a chromaticity b ^* of -1 or more and 1 or less, and a 0D value of 3 or more. The surface of the secondary particles having an average particle diameter of 5 nm or more and 300 nm or less, wherein the primary particles of the fine particles composed of metals and / or metal oxides having an average particle diameter of 1 nm or more and 200 nm or less, are covered with an insulating film. Black fine particles. The method of claim 16, The black fine particles, characterized in that the insulating film is a metal oxide or an organic polymer compound. The method of claim 16, The fine particles are black, characterized in that made of one or two or more selected from the group of silver, tin and nickel. The black fine particle dispersion containing the black fine particle of Claim 16. The black shading film | membrane formed by apply | coating the black fine particle dispersion of Claim 19. The base material with a black light shielding film provided with the black light shielding film of Claim 20 on one main surface of a base material.

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