JP5742383B2 - Black film, substrate with black film, and image display device - Google Patents

Description

  The present invention relates to a black material, a black material dispersion using the black material, a black resin composition, a black film, a substrate with a black film, and an image display device.

  Conventionally, black materials include black light-shielding film, black light-shielding glass, black paper, black cloth, black ink, plasma display panel (PDP), liquid crystal display (LCD), and organic electroluminescence (EL) display. It is used as a material that imparts black color or light-shielding properties to black matrix materials, black seal materials, black mask materials, and the like of display elements.

As such a black material, in addition to metal materials such as carbon black, titanium black (low-order titanium oxide or titanium oxynitride), iron oxide, chromium, and inorganic materials, black fine particles made of silver fine particles are known ( For example, see Patent Document 1).
Further, as a black material having high blackness and excellent light-shielding properties, it is composed of particles having an average particle diameter of 1 nm to 300 nm mainly composed of a silver-tin alloy, and the silver content in the silver-tin alloy is preferably 47. Black fine particles of 6 mass% to 90 mass% have been proposed (see, for example, Patent Document 2).

Further, as black materials having low reflection and high shielding power, black fine particles composed of silver tin alloy fine particles and silver fine particles, and the content of silver fine particles is 30% by mass to 90% by mass (for example, Patent Document 3) See also metal particles having a silver-tin alloy part having a silver atom content of 30 mol% or more and 80 mol% or less used as a colorant of a black ink composition (see, for example, Patent Document 4).
Furthermore, as a black material used for a black composition having a high light-shielding property, black fine particles containing silver or tin as a main component and having a silver atom content of 50% by mass to 90% by mass in all particles have been proposed. (For example, refer to Patent Document 5).

JP 2004-240039 A JP 2006-89771 A JP 2009-30096 A Special table 2009-503123 JP 2010-189628 A

However, in a black film in which black fine particles obtained by these known techniques are embedded in a resin, when the black fine particles contain a large amount of simple silver or silver oxide, the black film is in a high temperature state due to the catalytic activity of silver. When this occurs or when a large amount of light energy is received, the resin around the black fine particles may be decomposed, resulting in deterioration of the black film itself or decomposition gas. In addition, due to the generated decomposition gas, there is a problem that, for example, the adhesion with other films formed on the black film is reduced, or the adhesion with the base material of the black film itself is lowered and is easily peeled off. It was. Further, since the decomposition gas diffuses to the surroundings, it may affect not only the black film but also surrounding materials. For example, the black film is shielded from organic electroluminescence (hereinafter referred to as “organic EL”) elements. When used as a film, since the organic EL element has low resistance to gas, there is a problem that the organic EL element itself deteriorates due to gas such as oxygen and water vapor contained in the decomposition gas.
On the other hand, when the black material is a metal fine particle mainly composed of a base metal, although the resin is hardly decomposed, the fine particle itself is likely to be oxidized, and reliability may be impaired.

  The present invention has been made in view of such circumstances, a black material having high blackness, excellent light shielding properties, and low catalytic activity for a resin, a black material dispersion using the black material, and a black resin composition Another object of the present invention is to provide a functional element having a black film and a black film-containing substrate having the black film, and a black member and a functional member using the black material.

The above problems are solved by the present invention described below. That is, the present invention
[1] consisting of metal fine particles including silver fine particles and silver tin alloy fine particles;
A black material having a silver-tin alloy component amount of 50% by mass or more and 90% by mass or less and a silver component amount of 75% by mass or more and 87% by mass or less;
[2] The black material according to [1], wherein the metal fine particles further include composite fine particles composed of a silver part and a silver tin alloy part.
[3] The black material according to [1] or [2], wherein the average primary particle diameter of the metal fine particles is 3 nm or more and 100 nm or less,
[4] A black material dispersion obtained by dispersing the black material according to any one of [1] to [3] in a dispersion medium,
[5] A black resin composition comprising at least the black material according to any one of [1] to [3] and a resin-forming component or a resin component,
[6] A black film comprising at least the black material according to any one of [1] to [3] and a resin component,
[7] The black film according to [6], wherein the volume resistivity is 10 ¹¹ Ω · cm or more,
[8] A substrate with a black film having the black film according to [6] or [7] on the surface of the substrate, and an image display device having the black film according to [9] [6] or [7],
Is to provide.

  According to the present invention, a black material having high blackness, excellent light shielding properties, and low catalytic activity for a resin and the like, a black material dispersion using the black material, a black resin composition, a black film, and the black film A substrate with a black film having a film and an image display device having a black film using the black material can be provided.

Hereinafter, the present invention will be described with reference to embodiments. This embodiment is specifically described in order to better explain the gist of the invention, and does not limit the present invention unless otherwise specified.
<Black material>
The black material of the present embodiment is composed of metal fine particles including silver fine particles and silver tin alloy fine particles, the silver tin alloy component amount is 50% by mass or more and 90% by mass or less, and the silver component amount is 75% by mass or more and 87%. It is below mass%.

The metal fine particles constituting the black material of the present embodiment include silver fine particles and silver tin alloy fine particles as described above. As described above, silver fine particles are useful as black fine particles used in materials that require high blackness, but their glossiness is a problem.
Therefore, the present inventors have attempted to achieve both blackness and low gloss by mixing silver tin alloy fine particles having a lower gloss than silver fine particles, and have obtained results (above In this case, too, the reduction in silver-derived catalytic reactivity was insufficient. Therefore, as a result of further investigation, in the black material containing silver fine particles and silver tin fine particles, by limiting the amount of silver tin alloy component to a specific range and limiting the ratio of silver and tin to a certain range, It was found that metal fine particles having low oxidation catalytic properties while maintaining blackness can be obtained.

The metal fine particles in the present embodiment need only contain silver fine particles and silver tin alloy fine particles, and may contain fine particles such as other metals.
Here, the “silver fine particles” are fine particles consisting essentially of silver containing substantially no tin, and the “silver tin alloy fine particles” are fine particles consisting only of a silver tin alloy part to be described later. .

Furthermore, the fine metal particles in the present embodiment may include composite fine particles composed of a silver part and a silver tin alloy part. This “composite fine particles composed of a silver part and a silver tin alloy part” is different from silver tin fine particles composed only of silver fine particles or silver tin alloy parts which do not substantially contain tin, and part of the silver tin alloy part. Means a fine particle combined with a silver part made of only silver.
Here, the silver part is a part consisting only of silver that does not substantially contain tin, and the “silver tin alloy part” includes an intermetallic compound of silver and tin, that is, silver and tin. In addition, a portion having a crystal structure different from the crystal structure of silver or tin is included, but not only that, but also a portion in which tin is solid-solved in a state where the crystal structure of silver is maintained (tin solid-solution silver) It is. However, for reasons described later, the silver tin alloy part included in the present embodiment is determined to be Ag ₃ Sn.
In this way, the metal fine particles contain silver fine particles and silver parts to maintain blackness, and by reducing the catalytic activity by containing silver tin alloy fine particles and composite fine particles in a certain amount or more, the light shielding property, black It is possible to obtain a good balance between the catalytic activity of fine particles.

Here, what can be considered as a silver-tin alloy part is as follows, referring to a silver-tin phase diagram (Binary Alloy Phase Diagram, p. 94-97).
That is, as a range of X when the silver tin alloy is represented by the chemical formula Ag _1-X Sn _X , (Ag) phase (space group represented by the following formula (1)), 0 <X ≦ 0.115, 0 ≦ 118 ≦ X ≦ 0.2285 (space group P6 ₃ / mmc) and ε phase (space group Pmmn) of 0.237 ≦ X ≦ 0.25. Comparing the composition and space group of these phases with the X-ray diffraction ICDD card (JCPDS card), the (Ag) phase is a solid solution of tin in a state where the crystal structure of silver is maintained in silver. Since some of the silver atoms in the silver crystal are substituted with tin atoms, it is considered equivalent to Ag (IDCC 86-2265, cubic system), and the X-ray diffraction data of the ζ phase is Ag ₄ Sn (IDCC 29-1151, hexagonal system) and ε-phase X-ray diffraction data are considered to correspond to Ag ₃ Sn (IDCC 71-0530, orthorhombic system). Of these, the (Ag) phase has a silver crystal structure as described above, while Ag ₃ Sn and Ag ₄ Sn have a silver tin intermetallic compound crystal structure.

Here, considering the stability of these three phases ((Ag), Ag ₄ Sn, Ag ₃ Sn), it is considered that Ag ₃ Sn has the highest stability. Further, as shown in the production method described later, the metal fine particles of the present embodiment are formed by reducing silver ions with a tin colloid to form a silver-tin alloy, and the tin colloid is added in excess compared to the silver ions. Therefore, it is appropriate to consider that Ag ₃ Sn having the largest amount of tin among these three phases is generated. From these things, the silver tin alloy part in this embodiment was supposed to be made of Ag ₃ Sn.
Further, according to the phase diagram of silver-tin, there is no specific phase when the amount of tin is larger than the ε phase (Ag ₃ Sn). Therefore, what is obtained by the manufacturing method of the silver tin alloy of this embodiment is a mixture of Ag ₃ Sn and tin, and it is appropriate to consider that Ag ₃ Sn remains by dissolving tin in the acid in the subsequent acid treatment. It is. This is also the reason for judging that the silver-tin alloy part is made of Ag ₃ Sn.

  In the present embodiment, by utilizing tin having a lower catalytic activity than silver, it was possible to simultaneously realize the characteristic of low oxidation catalytic activity while maintaining the light shielding property and the blackness. The content range of the silver tin alloy in the metal fine particles determined from this viewpoint is the first requirement.

That is, in this embodiment, it is necessary that the content of silver tin alloy (silver tin component amount) in the metal fine particles forming the black material is 50% by mass or more and 90% by mass or less.
When the content of the silver-tin alloy in the metal fine particles is less than 50% by mass, the amount of silver fine particles and silver parts in the black material, that is, the amount of a single silver component increases. The activity cannot be kept low. On the other hand, when the content of the silver-tin alloy in the metal fine particles exceeds 90% by mass, the black fineness and the silver portion are reduced in the black material, so that the blackness is lowered and sufficient light shielding properties cannot be obtained.
55 mass% or more and 85 mass% or less are preferable, and, as for content of the silver tin alloy in a black material, 60 mass% or more and 85 mass% or less are more preferable.

As a second requirement, in this embodiment, the silver element content (silver component amount) in the metal fine particles forming the black material needs to be 75 mass% or more and 87 mass% or less.
When the silver element content in the metal fine particles is less than 75% by mass, the blackness of the black material is lowered and sufficient light shielding properties cannot be obtained. On the other hand, if the content of silver element in the metal fine particles exceeds 87% by mass, the reflectivity becomes high due to silver element, and sufficient blackness cannot be obtained or natural black cannot be obtained. End up.
The content of the silver element in the black material is preferably 77% by mass or more and 85% by mass or less, and more preferably 77% by mass or more and 83% by mass or less.

The content of the silver and tin elements in the black material may be obtained by performing a quantitative analysis such as ICP emission analysis on a solution in which the black material is dissolved with an acid or the like. Since it contains only light element and tin, it can be measured by EPMA (electron beam microanalyzer) analysis using a green compact.
In addition, when the metal element which is a main component of the black material of this embodiment is only silver and tin, the content (%) of the silver element in the metal fine particles is expressed by the following formula (2) from the measured value of EPMA. The tin element content (%) is the remaining amount of the silver element content.
Content of silver element (%) = [mass of silver element / (mass of silver element + mass of tin element)] × 100 (2)
Note that the denominator in the formula (2) does not include elements other than metals such as carbon resulting from a dispersant or the like adhering to the periphery of the metal fine particles or oxygen due to oxidation of the surface of the metal fine particles. .

Further, as described above, since the silver-tin alloy part in the present embodiment is made of Ag ₃ Sn, the content of the silver-tin alloy in the black material is determined from the content of the silver element and tin element obtained above. It is obtained by proportional calculation.

  In this embodiment, it is preferable that the average primary particle diameter corresponding to the circular diameter of the metal fine particles in the black material is 3 nm or more and 100 nm or less. By setting the average primary particle diameter within this range, a desired black shielding film can be easily formed in the black film described later. That is, when the average primary particle diameter is less than 3 nm, the transmitted light amount increases and the desired blackness may not be obtained because it is too small compared to the wavelength of visible light. On the other hand, when the average primary particle size exceeds 100 nm, scattering occurs, metal characteristics as a bulk body, that is, metallic luster, is exhibited, and it becomes difficult to obtain a desired blackness, or unevenness on the surface of the black light shielding film. It may become bigger.

The average primary particle size is more preferably 3 nm to 60 nm, more preferably 5 nm to 60 nm, and still more preferably 5 nm to 40 nm.
In addition, the average primary particle diameter corresponding to the circle diameter in the present embodiment means that the metal fine particles having various shapes are observed with a TEM (transmission electron microscope) as described later, and the area is the same as the confirmed fine particles. The diameter corresponding to such a circle.

The method for producing the black material of the present embodiment is not particularly limited as long as it is a method capable of obtaining metal fine particles exhibiting black color by adjusting the composition and particle diameter as described above. Conventional metal fine particle synthesis methods such as a thermal decomposition method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method can be applied.
Among these, the liquid phase reaction method is used because it is easy to form silver fine particles and silver tin fine particles, and composite fine particles composed of a silver portion and a silver tin alloy portion, and it is easy to control the composition and shape of the particles according to the synthesis conditions. It is preferable to use it. Conventionally, there has been no method for producing an alloy of tin and silver having greatly different oxidation-reduction potentials while controlling the composition of the metal fine particles, the crystal system accompanying the composition, the particle diameter, the particle shape, etc. In the form, a silver-tin alloy can be generated while controlling the composition, the crystal system accompanying it, the particle size, the particle shape, etc. by strictly controlling the reaction conditions such as reaction temperature, pH, and stirring efficiency as described later. It has become possible.

As an example of the liquid phase reaction method, for example, a predetermined amount of a reducing agent is added to a silver compound solution, a part of silver ions in the silver compound solution is reduced to form silver fine particles, and then a colloidal tin dispersion A method of adding silver and reducing the remaining silver ions with tin to alloy tin with silver to form silver tin alloy fine particles can be exemplified.
In this production method, by appropriately adjusting the reaction conditions (for example, the type and amount of the reducing agent, the ratio of tin and silver ions, the pH of the reaction solution, the reaction temperature, the reaction time, etc.), The silver element content and the ratio of silver fine particles to silver tin alloy fine particles can be arbitrarily controlled.

In such a liquid phase reaction, since the synthesis is completed by the reaction in the liquid phase, there is no need to recover the black material, and the black material dispersion described later can be easily obtained as it is or through a simple process. It is also possible.
Moreover, when producing a black film using this black material, the water dispersion system may be changed to the organic solvent dispersion system in consideration of dispersibility with the resin component. When changing to an organic solvent dispersion system, solvent replacement may be performed while maintaining the liquid phase state, but in order to reduce the water content in the organic solvent dispersion system, cake-like aggregates recovered from the liquid phase It is preferable to use a method in which the powder is once mechanically pulverized to form a powder and then dispersed in an organic solvent using a wet mixer such as a ball mill or a bead mill.

<Black material dispersion>
The black material dispersion of this embodiment is a dispersion in which the black material of this embodiment is dispersed in a dispersion medium.
The black material content in the dispersion is preferably 1% by mass to 80% by mass, more preferably 5% by mass to 50% by mass, and still more preferably 10% by mass to 40% by mass. Here, the reason why the content of the black material is preferably 1% by mass or more and 80% by mass or less is that this range is a range in which the black material can take a good dispersion state, and the content is less than 1% by mass. This is because the effect as a black material may be reduced, and if it exceeds 80% by mass, the concentration of the black material becomes too high and a paste is formed, and the characteristics as a dispersion may be lost. .

(Dispersion medium)
The dispersion medium basically contains at least one of water and an organic solvent.
Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol, butanol, and octanol; diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol mono -N-propyl ether, ethylene glycol mono-n-butyl ether (butyl cellosolve), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- (poly) alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;
(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n formate -Pentyl, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Le, other esters such as γ- butyrolactone;
Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferably used. Among these solvents, 1 Species or two or more can be used.

Among the above, the water content in the dispersion when a water-insoluble organic solvent is used is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less.
When the water content of the dispersion exceeds 5% by mass, the dispersion is caused when the black material dispersion in which the black material is dispersed is mixed with a non-aqueous resin component or resin-forming component for the purpose of forming a black resin composition such as paint. The liquid and the resin component or the resin-forming component are easily separated, and it may be difficult to obtain a stable mixture (paint or the like). That is, by setting the water content of the dispersion to 5% by mass or less, it is possible to appropriately select a non-aqueous resin component or a resin-forming component suitable for desired characteristics from among many types. There is no restriction in the resin composition (paint) or coating film, and the degree of freedom in designing can be expanded.

(Other ingredients)
In the dispersion liquid of the present embodiment, it is preferable to use a dispersant and / or a dispersion aid or a surface treatment agent in combination in order to improve the dispersibility of the black material and the dispersion stability. Among these, it is particularly preferable to use a polymer dispersant as the dispersant because the dispersion stability over time is excellent. Here, the dispersant is a polymer having a completely different structure from the black material for ensuring the dispersion stability of the black material, and the dispersion aid is a pigment derivative for enhancing the dispersibility of the black material. Say.

  In general, the classification of polymer dispersants includes, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants. , Aliphatic modified polyester dispersants, polycarboxylates, polyalkyl sulfates, polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide and the like. Of these, urethane dispersants are preferred in view of compatibility with ionizing radiation curable resins, thermosetting resins and thermoplastic resins used as resins, and compatibility with organic solvents.

In addition, when the polymer dispersant is classified by the structure depending on the production method, there are a random copolymer, a comb copolymer, an ABA block copolymer, a BAB block copolymer, a hydrophilic group-containing polymer at one end, a hydrophilic group-containing polymer at one end, etc. . Among these, a random copolymer and a comb polymer are preferable in consideration of compatibility with an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin used as a resin, and compatibility with an organic solvent.
Specific examples of the dispersant satisfying these conditions include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), and SOLPERSE (manufactured by Geneca). Moreover, these dispersing agents can be used 1 type or in mixture of 2 or more types.

  Moreover, it is preferable that the addition amount with respect to the black material of the said dispersing agent is 5 to 50 mass parts when black material is 100 parts. When the amount of the dispersant added is less than 5 parts by mass, the amount of the dispersant necessary for dispersing the black fine particles is insufficient, so that the dispersibility of the dispersion cannot be maintained. The average particle size inside may not be satisfied. Further, when the amount of the added dispersant exceeds 50 parts by mass, the amount of the dispersant becomes excessive with respect to the black material, and the dispersibility of the dispersion cannot be maintained due to the interaction between the dispersants. The dispersed particle size, 90% cumulative volume particle size may not be satisfied.

In the black material dispersion liquid of the present embodiment, the average dispersed particle diameter of the metal fine particles (black material) dispersed in the solvent is preferably 5 nm or more and 100 nm or less. Since the average primary particle diameter of the metal fine particles in this embodiment is 3 nm or more, it is difficult to obtain a dispersion having an average dispersed particle diameter of less than 5 nm. If the average dispersed particle diameter exceeds 100 nm, the dispersion of the fine particles in the black material dispersion is not sufficient, and the light-shielding property may be lowered or the appearance may become whitish due to the scattering of the fine particles, and the blackness may be lowered.
The average dispersed particle size is more preferably 5 nm or more and 80 nm or less, and further preferably 5 nm or more and 50 nm or less.

The 90% cumulative volume particle size of the metal fine particles (black material) dispersed in the solvent of the black material dispersion is preferably 1 μm or less. If the 90% cumulative volume particle diameter exceeds 1 μm, the dispersion of the fine particles in the black material dispersion is not sufficient and coarse particles are present, so that the light-shielding property is deteriorated or the appearance is caused by the scattering of the fine particles. It may become whitish and the blackness may decrease.
The 90% cumulative number particle size is more preferably 0.6 μm or less.

Regarding the method of measuring the average dispersed particle size and 90% cumulative volume particle size in the above dispersion, the particle size distribution of this dispersion is measured using a particle size distribution measuring apparatus by a dynamic light scattering method, and the fine particles in the dispersion are measured. When the cumulative curve was determined with the total volume of 100% as the total volume, the particle size at the point where the cumulative curve was 50% was the average dispersed particle size, and the particle size at the point where the cumulative curve was 90% was the 90% cumulative volume particle size.
Moreover, the average dispersed particle diameter and 90% cumulative volume particle diameter in the black resin composition described later were also determined by the same measurement method.

The black material dispersion of this embodiment can be prepared by mixing and dispersing a black material and components such as a dispersant and a dispersion aid as required in addition to a dispersion medium. The mixed dispersion method may be selected from known dispersion treatment methods such as an ultrasonic disperser, a paint shaker, a ball mill, a bead mill, an Eiger mill, etc., but a bead mill is preferable from the viewpoint of dispersibility. . A plurality of dispersion methods may be used in combination.
For example, when the above bead mill is used, the ratio of (mass of beads) / (mass of dispersion) in the dispersion chamber in a batch type bead mill is 0.5 to 15 and the rotation speed is 1000 rpm to 4000 rpm. It is preferable to disperse for about 1 hour to 10 hours.
As preferable dispersion conditions, for example, a ratio of (mass of beads) / (mass of dispersion) is set to 3.5, and dispersion is performed at 2500 rpm for about 2 hours.

<Black resin composition>
The black resin composition of the present embodiment includes at least the black material of the present embodiment and a resin forming component or a resin component, and includes a paint and the like. The resin component is the same as the resin component in the black film described later, and the resin forming component is a component for forming the resin component in the black film described later.
Here, the main components for constituting the black resin composition are the following five types [A] to [E]. Note that [B] and [E] are different.
[A] Black material [B] Black material dispersion medium [C] Resin forming component [D] Resin component [E] Resin forming component or solvent of resin component

The black resin composition is mainly composed of a combination of these five components, and the combinations are as follows (1) to (7). In order to disperse the metal fine particles constituting the black material in the black resin composition, the black material is preferably treated with a dispersant. However, since the dispersant is an additional component, the description here Is omitted. Furthermore, description of components other than [A] to [E] that can be added as necessary, that is, a dispersant, a dispersion aid, and a surface treatment agent is omitted here.
(1): [A] + [C]
It is a two-component system that is a minimum combination, and can be regarded as a dispersion of a black material in a liquid resin-forming component. In this case, [C] needs to be liquid.
(2): [A] + [B] + [C]
It is a three-component system and can be regarded as a mixture of the “black material dispersion” and a resin-forming component. In general, [C] needs to be liquid, but when [C] is soluble in [B], [C] may be solid.
(3): [A] + [C] + [E]
It can be regarded as a three-component system in which a black material is dispersed in a resin-forming component dissolved in a solvent. Since [C] is dissolved in [E], it may be liquid or solid.
(4): [A] + [D] + [E]
It is a three-component system and can be considered as a black material dispersed in a resin component dissolved in a solvent. Since [D] is a solid, [E] is indispensable as long as [D] is present.
(5): [A] + [B] + [D]
This is a combination that is possible only when [D] is soluble in [B], and can be considered as a resin component dissolved in the “black material dispersion”. Only in this case, [E] is exceptionally unnecessary.
(6): [A] + [B] + [C] + [E]
(7): [A] + [B] + [D] + [E]
It is a four-component system, and can be regarded as a mixture of a resin forming component or a solution in which a resin component is dissolved in the “black material dispersion”. In this case, [B] and [E] must be highly compatible. When the compatibility between the two is low, even if the “black material dispersion liquid” and the “resin-forming component or solution in which the resin component is dissolved” exist stably, the phase separation and the particle component will occur when both are mixed. This is not preferable because aggregation of the liquid occurs. When [B] and [E] are the same, (6) is included in (2) or (3), and (7) is included in (4) or (5).

  Of the above black material [A], black material dispersion medium [B], resin forming component [C], resin component [D], resin forming component or resin component solvent [E], black material, black material dispersion Since the medium has been described above, the resin component, the resin forming component, the resin forming component, or the solvent of the resin component will be described here.

(Resin forming component, resin component)
The resin forming component is a component for forming a resin component in a black film, which will be described later, and usually includes a resin component monomer, oligomer, or prepolymer. That is, as the resin component, various kinds of ionizing radiation curable resins, thermosetting resins, thermoplastic resins, and the like can be used, and therefore at least any of monomers, oligomers, and prepolymers of these resins is included.

  When an ionizing radiation curable resin is selected as the resin component, the ionizing radiation polymerizable monomer (monomer) that is the resin forming component is a polyfunctional compound that is a polymerizable monomer having a radical polymerizable functional group in the molecule ( (Meth) acrylates are preferred, specifically ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. Examples of the monomer having a cationic polymerizable functional group include alicyclic epoxides such as 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, and glycidyl ethers such as bisphenol A diglycidyl ether. , Vinyl ethers such as 4-hydroxybutyl vinyl ether, and oxetanes such as 3-ethyl-3-hydroxymethyloxetane. These ionizing radiation polymerizable monomers may be used singly or in combination of two or more, or may be used in combination with an ionizing radiation polymerizable prepolymer described later.

  Examples of the ionizing radiation polymerizable prepolymer (including oligomers) include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyol (meth) acrylate, and silicone (meth). Cationic polymerization in molecules such as polymerizable oligomers having radical polymerizable functional groups in molecules such as acrylates and unsaturated polyesters, or epoxy resins such as novolac epoxy resin prepolymers and aromatic vinyl ether resin prepolymers And polymerizable oligomers having a functional functional group. These ionizing radiation polymerizable prepolymers may be used singly or in combination of two or more. Here, “(meth) acrylate” means “acrylate or methacrylate”.

Moreover, phenol resin, phenol-formalin resin, urea resin, urea-formalin resin, melamine resin, polyester-melamine resin, melamine-formalin resin, alkyd resin, epoxy resin, epoxy-melamine resin which are thermosetting resins as resin components When selecting an unsaturated polyester resin, polyimide resin, acrylic resin, polysiloxane resin, polyurethane resin, general-purpose two-component curable acrylic resin (acrylic polyol cured product), etc., these thermosetting resins are used as the resin-forming component. And a raw material compound for forming a monomer, a monomer, an oligomer and a prepolymer of a polymerizable resin.
In addition, when a polyester resin, alkyd resin, polyurethane, polyvinyl pyrrolidone, polyvinyl alcohol, or the like, which is a thermoplastic resin, is selected as the resin component, the resin-forming component includes a raw material compound for forming these thermoplastic resins, , Polymerizable monomers, oligomers, and prepolymers.

  Furthermore, a reactant, a reaction initiator, a polymerization agent, a polymerization initiator, and the like, which are added to form a resin from these raw material compounds, polymerizable resin monomers, oligomers and prepolymers, are included in the resin forming component. Also good.

Here, the content of the resin forming component in the total solid content in the black resin composition is preferably 5% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 50% by mass or less.
If there are too many resin-forming components than this range, when a black film is formed, there may be insufficient black material existing in the unit volume of the resin component, so that sufficient light-shielding properties may not be ensured. If the amount is too small, a preferable shape as a black film may not be formed, for example, a uniform film body may not be formed or a necessary film thickness may not be obtained.

(Resin-forming component or resin component solvent)
The resin-forming component or the solvent for the resin component (hereinafter sometimes referred to as “resin solvent”) is a liquid in which the resin-forming component or the resin component is highly soluble. It is selected from one type or two or more types.
As the resin solvent, in addition to the high solubility of the resin-forming component or resin component, the dispersibility of the black material is high, the compatibility with the black material dispersion is high, and when mixed with the black material dispersion The condition that the dispersibility of the black material and the solubility of the resin component and the resin-forming component are not lowered is necessary. When these conditions are not satisfied, even if the “black material dispersion liquid” and the “resin forming component or the solution in which the resin component is dissolved” exist stably, both are mixed to form a black paint. At this time, phase separation, aggregation and sedimentation of the black material, precipitation of the resin-forming component or resin component, etc. occur, which is not preferable because a good black paint cannot be obtained. Here, it is preferable that the same or similar solvent can be selected as the resin solvent and the black material dispersion because such problems can be avoided.
In addition, as an organic solvent, the organic solvent used for the above-mentioned black material dispersion liquid can be used similarly.

Also in the black resin composition of the present embodiment, a dispersant and / or a dispersion aid and a surface treatment agent are added to improve the dispersibility and dispersion stability of the black material as in the black material dispersion. It is preferable to use together. Among these, it is particularly preferable to use a polymer dispersant as the dispersant because the dispersion stability over time is excellent. Since the dispersant and the dispersion aid are the same as those described in the black material dispersion, the details are omitted.
In addition, when a dispersion containing a dispersant and / or a dispersion aid or a surface treatment agent is selected as the black material dispersion of this embodiment, and this black material dispersion is used as a raw material for a black paint, the dispersion Dispersants, dispersion aids and surface treatment agents already contained in the liquid may be used as they are. The reason for this is that the dispersant, dispersion aid and surface treatment agent are substances that modify the surface of the black material so that the surface of the black material has an affinity for the dispersion medium and solvent. This is because it is not necessary to treat with another type of dispersant or dispersion aid if the characteristics are not different from those of the medium or solvent.

For the black resin composition described above, at least the black material and the resin-forming component and / or resin component are selected, and if necessary, a black material dispersion medium, a resin-forming component or a resin component solvent is added, and photopolymerization is further performed. It can be prepared by adding an initiator, a dispersant and other components and mixing and dispersing. Among these, the black material, the black material dispersion medium, the resin forming component, the resin component, the resin forming component, or the combination of the resin component solvents are as described above.
In this case, a black paint may be prepared by preparing a black material dispersion in advance, and adding and dissolving a resin-forming component or the like or a photopolymerization initiator. Moreover, it can also prepare by mixing the black material dispersion liquid prepared previously, and the solution which melt | dissolved components, such as a resin formation component and a photoinitiator.
The mixed dispersion method may be selected from known dispersion treatment methods such as an ultrasonic disperser, a paint shaker, a ball mill, a bead mill, an Eiger mill, etc., as a mixed liquid in which black materials and resin forming components are mixed. To bead mills are preferred. A plurality of dispersion methods may be used in combination. When a black material dispersion prepared in advance is used, the black material dispersion and the solution in which the resin-forming components are dissolved are sufficiently mixed and stirred without performing the above-described dispersion treatment method when the black resin composition is produced. There are cases where it may be sufficient.

<Black film>
The black film of the present embodiment includes at least the black material of the present embodiment and a resin component.
As the resin component in the present embodiment, a resin component that cures in a state where the metal fine particles exhibiting black, which is a black material, are uniformly dispersed, and that is suitable for the characteristics required for the formed black film should be selected. That's fine. As this resin component, various kinds of ionizing radiation curable resins, thermosetting resins, thermoplastic resins, etc. described in the above black resin composition can be used.

  The black film of the present embodiment can be obtained by forming a film body by various known coating methods using a black paint that is one of the black resin compositions described above. For example, the black film is formed by applying the above black paint on one main surface of a substrate, roll coating method, spin coating method, dip coating method, spray coating method, bar coating method, slit coating method, slit & spin coating method. It can be easily obtained by forming the coating film by various coating methods such as, removing the solvent from the coating film by volatilization, etc., and performing a curing treatment if necessary.

This curing treatment is usually a process in which a resin-forming component in the coating film is reacted by polymerization or the like to form a resin component. When an ionizing radiation curable resin is used as the resin-forming component, ultraviolet rays, electron beams, X-rays are used. In the case of using a heat-reactive resin such as a thermoplastic resin material to which a thermal polymerization catalyst is added as a resin-forming component. Includes a heat treatment.
Further, in the case where the component in the black paint is a resin component dissolved in a solvent, the curing process is a step of removing the solvent from the resin component in the coating film, and the heat treatment is performed under atmospheric pressure or reduced pressure. Can be mentioned. In this case, since the resin component cured by solvent removal may be swollen and dissolved again by exposure to the same solvent, it is preferable to remove the solvent completely by tightening the heat treatment conditions. . Here, when an ionizing radiation curable resin is used as the resin component, the resin component may be completely cured by applying radiation such as ultraviolet rays, electron beams, and X-rays after the solvent is removed, and further by performing a heat treatment. When a heat-reactive resin is used, the curing reaction may be completed by heat treatment after removing the solvent.

  As a black film using black paint, a film body patterned into a specific shape, for example, a black matrix of an image display device, a partition between elements in a self-luminous display device such as a plasma display display device or an organic EL display device In the case of (light-shielding partition), etc., a black paint containing an alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound, etc. is used, and light (ultraviolet rays) is applied to the coating film formed by applying the black paint. It is desirable to have photosensitivity. If the coating film has photosensitivity, the coating film is exposed to a specific pattern using a photomask or the like, then developed and cured to obtain a black color having a specific shape such as a black matrix or a partition. A film can be easily obtained.

The alkali-soluble resin is not particularly limited as long as it contains a carboxyl group or a hydroxyl group. For example, epoxy acrylate resin, novolac resin, polyvinyl phenol resin, acrylic resin, carboxyl group-containing epoxy resin, carboxyl group-containing urethane Among these, epoxy acrylate resins, novolac resins, and acrylic resins are preferable, and resins having an aromatic ring structure are particularly preferable in that they provide high volume resistivity and low dielectric constant.
In this case, the ratio of the alkali-soluble resin to the total solid content in the black paint is preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 50% by mass or less. If the proportion of the alkali-soluble resin is more than this range, sufficient sensitivity may not be secured when forming a pattern such as a black matrix or a partition, and the necessary light-shielding property may not be secured. In some cases, a preferable shape such as a wall or a partition wall may not be formed.

The photopolymerization initiator is a compound capable of generating radicals that polymerize ethylenically unsaturated groups by ultraviolet rays or heat.
As the photopolymerization initiator, oxime derivatives (oxime compounds) are particularly effective in terms of sensitivity, and when the light-shielding property is increased or an alkali-soluble resin containing a phenolic hydroxyl group is used, the sensitivity point is increased. In particular, such oxime derivatives (oxime compounds) having excellent sensitivity are useful. In this embodiment, the said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
When the resin black matrix is formed, the ratio of the photopolymerization initiator in the dispersion is preferably 0.4% by mass or more and 15% by mass or less, more preferably 0.5% by mass with respect to the total solid content. It is 10 mass% or less. If the proportion of the photopolymerization initiator is too much above this range, the development speed may be too slow, whereas if it is too small, sufficient sensitivity may not be obtained, and a preferable resin black matrix shape or partition shape may not be formed. .

  The ethylenically unsaturated compound means a compound having one or more ethylenically unsaturated bonds in the molecule, but the difference in the solubility of the developer in the exposed portion and the non-exposed portion due to polymerizability, crosslinkability, and the accompanying properties. From the viewpoint of being able to expand, a compound having two or more ethylenically unsaturated bonds in the molecule is preferable, and a (meth) acrylate compound in which the unsaturated bond is derived from a (meth) acryloyloxy group is further provided. preferable. Furthermore, the use of a compound having three or more ethylenically unsaturated bonds in the molecule is preferable for the electrical properties such as volume resistivity and relative dielectric constant of the formed film.

Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.
Examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

The black film of this embodiment preferably has an optical density (OD value) of 1 or more per 1 μm thickness. If the optical density per 1 μm is less than 1, sufficient light shielding properties cannot be obtained if the thickness of the black film is about several μm, and the film thickness must be increased to obtain sufficient light shielding properties. For this reason, particularly when used as a black matrix, a partition wall, or the like, the thickness of the film is increased, so that disconnection of wiring, display unevenness, and the like easily occur. Therefore, it is preferable to set the optical density per 1 μm to 1 or more as a range in which sufficient light shielding properties can be obtained without increasing the film thickness more than necessary.
The optical density per 1 μm is more preferably 1.2 or more, and further preferably 1.5 or more.
Here, since the black material of the present embodiment has a high blackness and is excellent in dispersibility in the resin, the black film of the present embodiment can be obtained by increasing the amount of the black material. The optical density per 1 μm can be easily set to 2 or more, and can also be set to 3 or more while avoiding adverse effects due to an increase in film thickness, for example, a decrease in film strength and a decrease in blackness due to aggregation of black materials. Therefore, a high light shielding property can be obtained without increasing the thickness of the black film. The higher the optical density per 1 μm, the better, but the upper limit is about 10 due to measurement limitations.
Furthermore, the lower the reflectance of the black film, the higher the blackness of the black film is preferable. When the reflectance is high, the black film looks white and the quality of the film deteriorates. The average reflectance of visible light obtained by averaging the reflectances from 380 nm to 800 nm is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less.

Here, the optical density per 1 μm thickness can be determined as follows.
The sample is formed into a film on a transparent substrate for measurement of transmission. While measuring the optical density of this film-like sample with a transmission densitometer, measuring the film thickness using a stylus type surface shape measuring instrument, etc., and dividing the optical density value of the obtained sample by the film thickness, The optical density per 1 μm thickness can be determined. In addition, it is preferable that the optical density of the film-like sample is about 4.0 or less because a decrease in measurement accuracy can be prevented.

The volume resistivity of the black film of this embodiment is preferably 10 ¹¹ Ω · cm or more. This is because, in a COA type or BOA type liquid crystal display element or a self-luminous display device, the element driving wiring contacts the black matrix or the partition wall, or the element driving wiring is provided directly on the black matrix or partition wall. Since the structure has become mainstream, if the volume resistivity of the black matrix or partition formed using the black film is less than 10 ¹¹ Ω · cm, the wiring is likely to be short-circuited, and the liquid crystal This is to cause malfunction of the driving element and the light emitting element. Also, in the IPS drive type liquid crystal, if the black matrix formed using the black film has conductivity, an unnecessary electric field is generated in a direction different from the electric field for driving the liquid crystal, and the image is disturbed. It is.
The volume resistivity of the black film is more preferably 10 ¹² Ω · cm or more, and further preferably 10 ¹³ Ω · cm or more. The higher the volume resistivity of the black film, the better. The upper limit is not particularly limited, but it is usually 10 ¹⁸ Ω · cm or less.
The volume resistivity can be measured by using a commercially available volume resistivity meter, for example, by a four-probe method.
Here, since the black material of the present embodiment has high blackness, the content in the black film can be reduced compared to the conventional black material, and the dispersibility in the resin is also excellent. In addition, a conductive path formed by agglomeration so that the black material particles are continuous is not generated. Therefore, even if the optical density per 1 μm is increased as described above, the volume resistivity can be maintained at a high value.

  Moreover, since the black material of this embodiment has reduced the catalytic activity (decomposition activity of organic substance) derived from silver, when the black film containing the black material and the resin component is in a high temperature state or a large amount Even when receiving light energy, decomposition of the resin component around the black fine particles can be suppressed. Therefore, the film loss of the black film can be suppressed, and the deterioration of the black film can be prevented.

<Base material with black film>
The base material with a black film of the present embodiment is configured by providing the black film of the present embodiment described above on a base material. Specifically, for example, a layer formed as described above using a black paint that is one of the black resin compositions described above is patterned on a light-transmitting substrate as necessary. Is done.

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

The material of the glass substrate is not particularly limited, but can be appropriately selected from soda glass, alkali glass, non-alkali glass, and the like.
The material of the plastic substrate is not particularly limited, and examples thereof include cellulose acetate, polystyrene (PS), polyethylene terephthalate (PET), polyether, polyimide, epoxy resin, phenoxy resin, polycarbonate (PC), and polyfluoride. It can be appropriately selected from vinylidene chloride, triacetylcellulose, polyethersulfone (PES), polyacrylate, and the like based on the application and use conditions.

Further, the method of patterning the layer formed using the black paint is not particularly limited, and as described above, an alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound is included in the black paint, Applying this black paint to form a coating film with light (ultraviolet) photosensitivity, exposing the coating film to a pattern and developing it to form a black film, Accordingly, other processes such as post exposure and post bake can be provided.
For patterning processes such as exposure and development, known methods can be used. For example, when applied as a black matrix for an image display device, the methods described in paragraph numbers 0096 to 0106 of JP-A-2006-251095. Alternatively, the method for forming a light-shielded image described in paragraph numbers 0116 to 0126 of JP-A-2006-251237 can also be suitably used in this embodiment.

There is also a method for producing a black film in which a pattern is directly formed on a substrate using the black paint and using an inkjet method. In this case, it is not necessary to give photosensitivity to the black paint film, but the black paint is excellent in dischargeability (discharge volume and stability in the discharge direction) from a minute ink jet nozzle and is not discharged. The paint adhering to the material must be in a highly viscous state so that it does not flow out or deform. For this reason, methods such as adjusting the viscosity of the black paint or adding an auxiliary agent for giving thixotropy are used.
Although a known method can be used for this step, for example, when it is applied as a black matrix for an image display device, the method described in paragraph numbers 0029 to 0031 of JP-A-2008-116895 can be used.

<Image display device>
The image display apparatus of the present embodiment is configured by providing the black film of the present embodiment described above in the apparatus. Specific examples include a self-luminous display device such as a plasma display device and an organic EL display device, a CRT display device, a liquid crystal display device, and the like, particularly when used in a liquid crystal display device and an organic EL display device. The effect of the black film of this embodiment is remarkably exhibited. Here, examples of the liquid crystal display device include STN, TN, VA, IPS, OCS, and R-OCB.

The black film of the present embodiment exhibits high light blocking properties (not transmitting light) and blackness (low light reflectivity) in a wide range of visible light region. Therefore, the black film of this embodiment can be suitably used as a member for an image display device that utilizes light shielding properties and blackness. These members include a black matrix in a liquid crystal display element and a self-luminous display device, a color filter and a black stripe using the black matrix, a light-shielding partition that separates pixels of each color in the liquid crystal display device and the self-luminous display device, and liquid crystal A functional member such as a spacer between substrates filled with liquid crystal in the display device can be given.
In addition, since these black matrices, light-shielding partition walls, spacers, and the like are usually formed on a substrate, it can be said that the image display device of this embodiment has the substrate with the black film of this embodiment.

The black film of this embodiment has a high light-shielding property and blackness, and a high light-shielding property can be obtained even if the black material has a smaller volume fraction than a black film using a black material such as existing carbon black. As a result, for example, in application to a black matrix and a color filter using the same, the thickness of the black matrix can be reduced due to high blackness, and the flatness of the resulting color filter can be increased. Therefore, in the liquid crystal display device provided with this color filter, the cell gap unevenness does not occur between the color filter and the substrate, and the occurrence of display defects such as color unevenness is improved.
That is, the film thickness of the black film is preferably 0.2 μm or more and 5.0 μm or less, and particularly preferably 0.2 μm or more and 4.0 μm or less when the substrate with black film of the present embodiment is a black matrix substrate. Thus, since the black film of this embodiment is used as the black film in the black matrix substrate, even a thin film has a high optical density.

In addition, the black film of this embodiment can obtain a high light-shielding property even if the volume fraction of the black material is small, and is excellent in the dispersibility of the black material. It is difficult to occur, the volume resistivity of the film can be increased, and both high light shielding properties and high volume resistivity of the film can be achieved.
As a result, even when the black matrix and the pixel driving wiring are in contact with each other as in the case of a COA-type or BOA-type liquid crystal display element or a self-luminous display device, there is a risk of causing a driving failure of the element due to a short circuit of the wiring. There is no.

  In addition, when applied to a light shielding wall or a spacer, since the volume resistivity is high, there is no possibility that the wiring between the pixels is short-circuited, and therefore, the device does not fail to drive. Furthermore, since the blackness is high, the thickness of the light shielding wall can be reduced, and the contrast can be improved by expanding the light emitting region in each pixel, or the density of the light emitting elements can be increased due to the decrease in the pixel spacing. .

  Furthermore, the black film of this embodiment uses the black material of this embodiment in which the catalytic activity (decomposition activity of organic matter) derived from silver is reduced, so that the black film is in a high temperature state or a large amount. Even when light energy is received, the decomposition of the resin component in the black film can be suppressed, and the reduction or deterioration of the black film can be prevented. Therefore, it is possible to prevent film loss and deterioration of functional members such as black matrix, light shielding partition walls, spacers between substrates provided in various image display elements, and to prevent peeling of these functional members from the substrate, Furthermore, it is possible to suppress a decrease in adhesion with wirings, protective films, and the like provided on these functional members.

Furthermore, since decomposition of the resin component in the black film is suppressed, almost no generation of decomposition gas occurs, and the decomposition gas does not diffuse to the surroundings, so that the surrounding materials and the like are not affected. . Therefore, the black film of the present embodiment can be suitably used for an image display device using a material having low resistance to water vapor, oxygen, etc. contained in the decomposition gas, such as an organic EL element. .
In the case of an organic EL element, the material constituting the element itself is deteriorated by the decomposition gas, but even if there is no material deterioration, the characteristics change due to the decomposition gas adhering to the material surface and the surface state changing. The black film of the present embodiment can be preferably used even for an element using such a material.

  Furthermore, it can be applied to a contrast enhancement film or the like by utilizing high light absorption.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
<Measurement and evaluation methods>
Below, each measurement or evaluation method, such as the characteristic of a material and a sheet | seat employ | adopted in the Example or the comparative example, is shown.

-Black material Particles were separated from an aqueous dispersion of black fine particles, which will be described later, and dried to obtain a powder sample, which was evaluated as follows.
(Identification of contained fine particle species)
For a powder sample, the crystal phase is identified by an X-ray diffractometer (XRD), and the green compact is analyzed by qualitative and quantitative analysis using an electron beam microanalyzer (EPMA) to obtain the crystal phase and composition ratio (content ratio). From this result, the metal particle species included was determined.
[Identification of crystal phase by XRD measurement]
The powder sample was packed in a glass sample holder and measured using CuKα rays with an X-ray diffractometer (manufactured by PANalytical, X′Pert PRO). In the obtained XRD profile, the peaks at diffraction angles 2θ = 38 ° and 44 ° are silver crystal structures (single silver and / or tin solid solution silver), 2θ = 34.7 ° and 39.7 °. By identifying the silver tin intermetallic compound crystal structure (Ag ₃ Sn and / or Ag ₄ Sn), the peaks around 2θ = 30.7 ° and around 32 ° as tin crystal phase peaks, The crystal phase of was confirmed.
[Qualitative and quantitative analysis by EPMA measurement]
The presence of silver and tin in the powder by analyzing the green compact powder using an electron beam microanalyzer (EPMA, JEOL Ltd., JXA8800) and qualitative and quantitative analysis using a wavelength dispersive X-ray spectrometer. In addition, the content ratio (mass ratio) of silver and tin was measured.

[Identification of particulate species and calculation of abundance]
From the confirmed crystal phase of the metal particle species and the content ratio of silver and tin, the presence of silver and silver-tin alloy was confirmed as follows, and the respective content rates were determined.
The silver-tin alloy component (silver-tin alloy fine particles) was obtained from the quantitative analysis in EPMA after confirming the crystal phase of the silver-tin intermetallic compound crystal structure by XRD and confirming the absence of simple tin. The total amount of was calculated as forming Ag ₃ Sn, and the amount was determined. The reason that the total amount is Ag ₃ Sn is as described above.
In order to form Ag ₃ Sn from the total amount of silver obtained from quantitative analysis in EPMA after confirming the presence of the silver component (silver fine particles) by confirming the crystal phase of the silver crystal structure by XRD. The required amount of silver was subtracted to calculate the amount.
[Confirmation of composite particles]
A sample obtained by diluting a black material dispersion prepared from a black material powder was used as a sample, and this sample was placed on a sample stage and dried, and a field emission transmission electron microscope (FE-TEM: manufactured by JEOL, JEM-2100F) ) And an attached energy dispersive X-ray analyzer (EDX). Surface analysis of silver and tin was performed, and it was confirmed that composite particles were formed by confirming the presence of portions having different abundance ratios of silver and tin in one particle.
Further, the crystallite diameters of silver and silver tin alloy are calculated from the half width of the peak in the XRD profile, and it is confirmed that the crystallite diameter is about 1/2 to 1/3 of the actual average particle diameter described later. It was also confirmed that composite particles were formed.

(Average primary particle diameter and particle shape of metal fine particles)
A sample obtained by diluting a black material dispersion prepared from a black material powder was used as a sample, and the sample taken on a sample stage and dried was observed with a transmission electron microscope (TEM: manufactured by Hitachi, Ltd., H-800). . Arbitrary 50 to 100 particles were selected from the observation field, each particle image was approximated by a circle, and the diameter of the circle was defined as the particle diameter of the particle (particle diameter corresponding to the circle diameter). The cumulative number distribution of particle diameters was obtained from the obtained results, and the particle diameter (median diameter) corresponding to the cumulative value of 50% was taken as the average primary particle diameter of the black material in the film.

・ Black film (optical density (film shading))
About the glass substrate in which the black film was formed, the optical density (OD value: Optical Density) in the visible light region was measured using a transmittance densitometer (manufactured by TECHKON, RT-120), and the glass substrate alone measured in the same manner ( By using the measured value of “without film” as a reference value, the OD value of the black film itself was obtained.
(Film thickness)
The film thickness of the black film was measured by observing the cross section with a transmission electron microscope (TEM).
(Volume resistivity of black film)
A glass substrate having an ITO film formed on the surface by sputtering is selected as the deposition substrate, and an insulation resistance meter (manufactured by ADC, ultrahigh resistance / microammeter R8340A, Volume resistivity was measured using a product of ADC. The volume resistivity measurement was performed at DC 5V.

・ Catalytic activity of black material (reduction rate of black film)
The black film after the film thickness measurement is exposed in the atmosphere at 230 ° C. for 5 hours, and the film thickness after the exposure is obtained again by TEM observation of the cross section, and the reduction rate of the film thickness from before the exposure is obtained. It was. The catalytic activity in the black material was evaluated based on the film thickness reduction amount.

<Example 1>
(Preparation of black material dispersion)
The silver nitrate 56g was melt | dissolved in the pure water, and 1500 g of silver nitrate aqueous solution (A liquid) was prepared. In addition, 314 g of trisodium citrate dihydrate and 360 g of polyvinylpyrrolidone diluted to 1% by mass were dissolved in pure water to prepare 2500 g of a trisodium citrate aqueous solution (solution B). Next, after liquid A was dropped into and mixed with liquid B, 500 g of an aqueous solution in which 7 g of sodium borohydride was dissolved in pure water was dropped and mixed to obtain liquid C.
Subsequently, the said C liquid was dripped and mixed in the 4000 g tin fine particle dispersion liquid which mixed the tin colloid A (average particle diameter: 20 nm, solid content: 10 mass%, Sumitomo Osaka Cement Co., Ltd.) 200g and pure water. Further, an aqueous solution in which 180 g of tartaric acid was dissolved in 2000 g of pure water was dropped into a mixed liquid of the tin fine particle dispersion and the C liquid and stirred to dissolve excess tin colloid. Thereafter, washing was performed by centrifugation to prepare an aqueous dispersion of black fine particles (liquid D, solid content: 25% by mass).

Thereafter, 100 g of the above solution D, 3.75 g of a comb urethane polymer dispersant and 34 g of methyl ethyl ketone were mixed, and then water and methyl ethyl ketone were evaporated from the mixture using an evaporator to obtain a dry powder (E powder).
Next, 29 g of the above E powder and 71 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed and dispersed using a bead mill to obtain a black material dispersion (liquid F, solid content: 25% by mass).

(Production of black film)
A black material dispersion (liquid F), a resist (dispersion medium: PGMEA) containing polyfunctional acrylate as a resin-forming component, and PGMEA as a solvent so that the solid content volume ratio (black fine particles: resist) is 10:90. And dispersed by sonication to obtain a black paint. In addition, the said solid content volume ratio is a preparation ratio.
Next, the prepared black paint was applied onto a 0.7 mm thick glass substrate using a spin coater, pre-baked on a hot plate at 120 ° C. for 2 minutes, and further post-baked at 230 ° C. for 30 minutes, A glass substrate with a black film was obtained. The film thickness of the black film was 1 μm.

(Evaluation)
About the black material obtained above, according to the said conditions, identification of the metal microparticle in black material and the fixed_quantity | quantitative_assay of the composition were performed. Moreover, about the obtained black film, optical density, a film thickness reduction rate, etc. were measured.
The results are summarized in Table 1. The presence or absence of single silver in the table was determined by the presence or absence of a silver peak in the XRD profile.

<Example 2>
In the preparation of the black material dispersion of Example 1, the black material dispersion was the same as Example 1 except that the amount of sodium borohydride was 5 g and the amount of trisodium citrate dihydrate was 157 g. A liquid and a black paint were prepared, a black film was prepared, and the same evaluation was performed.
These results are summarized in Table 1.

<Example 3>
In the preparation of the black material dispersion of Example 1, Example 1 and Example 1, except that the amount of colloidal tin A was 250 g, the amount of sodium borohydride was 4 g, and the amount of trisodium citrate dihydrate was 157 g. Similarly, a black material dispersion and a black paint were prepared and a black film was prepared, and the same evaluation was performed.
These results are summarized in Table 1.

<Example 4>
In the preparation of the black material dispersion of Example 1, the same procedure as in Example 1 except that the amount of tin colloid charged was 250 g, the amount of sodium borohydride was 2 g, and the amount of trisodium citrate dihydrate was 157 g. Then, a black material dispersion and a black paint were prepared, a black film was prepared, and the same evaluation was performed.
These results are summarized in Table 1.

<Example 5>
Liquid A and liquid B were prepared in the same manner as in Example 1. Subsequently, A liquid was dripped and mixed in B liquid, and G liquid was obtained.
Subsequently, the said G liquid was dripped and mixed in the 4000 g tin fine particle dispersion liquid which mixed the tin colloid A (average particle diameter: 20 nm, solid content: 10 mass%, Sumitomo Osaka Cement Co., Ltd.) and pure water. Further, an aqueous solution in which 180 g of tartaric acid was dissolved in 2000 g of pure water was dropped and stirred into a mixture of the tin fine particle dispersion and the G liquid to dissolve excess tin colloid, and then washed by centrifugation to obtain a dispersion (H Liquid). 85 g of silver colloid (average particle size: 20 nm, solid content: 25% by mass, manufactured by Sumitomo Osaka Cement Co., Ltd.) is added to and mixed with liquid H, and an aqueous dispersion of black fine particles (liquid I, solid content: 25% by mass). ) Was prepared.
Thereafter, a black material dispersion and a black paint were prepared and a black film was prepared in the same manner as in Example 1 except that the liquid I was used instead of the liquid D as the black fine particle aqueous dispersion. Evaluation was performed.
These results are summarized in Table 1.

<Comparative Example 1>
Liquid A and liquid B were prepared in the same manner as in Example 1. Next, after liquid A was dropped into and mixed with liquid B, 500 g of an aqueous solution in which 20 g of sodium borohydride was dissolved in pure water was dropped and mixed. Then, washing | cleaning was performed by centrifugation and the silver particle aqueous dispersion (solid content: 25 mass%) was prepared.
Thereafter, the black fine particle dispersion and the black paint were prepared in the same manner as in Example 1 except that the silver fine particle aqueous dispersion was used in place of the D liquid as the black fine particle aqueous dispersion. The same evaluation was performed.
These results are summarized in Table 1.

<Comparative Example 2>
Preparation of black material dispersion and black paint in the same manner as in Example 1 except that the amount of tin colloid A was 150 g and the amount of sodium borohydride was 9 g in the preparation of the black material dispersion of Example 1. A black film was prepared and evaluated in the same manner.
These results are summarized in Table 1.

<Comparative Example 3>
Example 1 except that the amount of tin colloid A was 400 g, the amount of sodium borohydride was 0.1 g, and the amount of trisodium citrate dihydrate was 79 g in the preparation of the black material dispersion of Example 1. In the same manner as in Example 1, a black material dispersion and a black paint were prepared and a black film was prepared, and the same evaluation was performed.
These results are summarized in Table 1.

  In Table 1, “alloy” in the metal particle type column of * 1 means “silver tin alloy fine particles (silver tin intermetallic compound)”, and “composite” means “composite fine particles (tin solid solution silver + silver). Solid solution tin) ".

As shown in Table 1, the black light-shielding films of the examples had high OD values and excellent light-shielding properties, and satisfied the performance required for black films, such as high light-shielding properties and blackness.
In addition, since the film thickness reduction rate after exposure under high temperature conditions is relatively small, the catalytic activity of the black material is reduced, and it is understood that the deterioration of the black film itself and the generation of decomposition gas are suppressed. It was. Therefore, for example, it was judged that the adhesion of the black film itself to the base material is suppressed from being lowered, and can be applied to a light shielding film of an organic EL element.
On the other hand, Comparative Example 1 was not only low in light shielding properties, but also had a large film thickness reduction rate after exposure under high temperature conditions. In Comparative Example 2, the light-shielding property was sufficient, but the film thickness reduction rate after exposure under high temperature conditions was large. Since these Comparative Examples 1 and 2 have a large amount of silver single component, the catalytic activity of the black material is high, and it is considered that the film thickness reduction rate is high.
Furthermore, although the comparative example 3 had a small film thickness reduction rate, it could not be said that the light-shielding property was sufficient. This is presumably because the amount of a single silver component in the black material is too small, so that the catalytic activity is low, but the light shielding property is insufficient.

  The black film of the present invention and the substrate with the black film using the same can be suitably used in a display element typified by a liquid crystal display element and an organic EL element, and an image display apparatus using the same. In addition, the black material of the present invention, the black material dispersion using the black material, and the black resin composition can effectively provide the black film or the substrate with the black film.

Claims (5)

It consists of metal fine particles containing silver fine particles and silver tin alloy fine particles, the amount of silver tin alloy component in the metal fine particles is 50% by mass or more and 90% by mass or less, and the amount of silver component in the metal fine particles is 75% by mass. A black material of 87% by mass or less ;
Including at least a resin component,
A black film having a volume resistivity of 10 ¹¹ Ω · cm or more . The fine metal particles are further black film according to claim 1 comprising a composite fine particles comprising silver portion and a silver-tin alloy. The average primary particle diameter of the fine metal particles, black film according to claim 1 or 2 is 3nm or more 100nm or less. The base material with a black film which has the black film of any one of Claims 1 thru | or 3 on a base-material surface. The image display apparatus which has a black film of any one of Claims 1 thru | or 3 .