JP4524151B2 - Substrate with light-shielding film for plasma display and plasma display using the same - Google Patents

Description

  The present invention relates to a plasma display panel (hereinafter also referred to as “PDP”) used for information display terminals, flat-screen televisions, and the like, and more particularly to a substrate with a light-shielding film for plasma display and a plasma display for realizing high contrast. .

The PDP is a display that displays an image by causing a phosphor layer to emit light by ultraviolet rays generated by discharge of a gas sealed between a pair of opposing substrates (a front substrate and a back substrate).
This PDP is classified into a direct current type and an alternating current type according to a discharge type, and is roughly divided into a counter electrode type and a surface discharge type according to the form of an electrode. Among these, the AC surface discharge type is excellent in terms of luminance and luminous efficiency, and is widely used. An example of such a PDP is disclosed as “Plasma Display Panel and Method for Manufacturing the Same” (for example, see Patent Document 1).

  The phosphor used in the PDP is a white powder having a very high reflectance. Accordingly, when indoor or outdoor light (external light) is incident on the panel, the phosphor powder is mainly reflected by about 30% to 50%, and contrast and color purity are significantly impaired. For this reason, there is a method of disposing an ND filter having a transmittance of about 40 to 80% on the panel surface. However, since the panel emits light, the panel brightness is lowered.

  There is a method using a color filter as a method for suppressing reflection of external light without reducing the panel luminance as much as possible. This forms a color filter that transmits red, green, and blue light on the display surface side corresponding to the emission color of each discharge cell of red, green, and blue (hereinafter also referred to as R, G, and B). It is.

  Furthermore, in order to improve contrast, a black light-shielding film is formed between the discharge cells. This serves to reduce external light reflection on the display surface. This light-shielding film is usually formed by thick-film printing a paste made of a metal oxide powder such as iron, chromium, nickel or cobalt and low melting point lead glass. In addition, since there is a disadvantage that the luminance is lowered when a color filter is used, there are some that use only a light shielding film without using a color filter.

  Conventionally, in order to produce a light shielding film having high light shielding properties, it is considered to use a metal. For example, a metal thin film is produced by vapor deposition or sputtering, and a photoresist is applied on the metal thin film, A method of forming by exposing and developing a photoresist layer using a photomask having a pattern for a substrate with a light-shielding film for a display device, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film. (For example, refer nonpatent literature 1).

  Since this method uses a metal thin film, a high light-shielding effect can be obtained even if the film thickness is small, but there is a problem that a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required and the cost is increased. In addition, since it is a metal film, there is a problem that the reflectance is high and the display contrast is low under strong external light. For this, there is a means of using a low-reflective chromium film (such as one composed of two layers of metal chromium and chromium oxide), but it cannot be denied that the cost is further increased. And the chromium used most by this method has the fault that environmental impact is large.

  On the other hand, there is a technique for forming a light-shielding film for a display device using carbon black in order to obtain a substrate with a light-shielding film having a low reflectance (see Patent Document 2). This is one obtained by exposing and developing a photosensitive resin composition containing carbon black applied to a substrate and drying.

  However, since the carbon black has a lower optical density per unit coating amount than the metal fine particles, the film thickness inevitably increases if a high light shielding property and optical density are ensured. For this reason, there is a step in the light shielding film portion, and it is necessary to consider the design so that the step is not affected when assembled in the cell. In addition, when the pixels such as red, blue, and green are formed after the light shielding film is provided, the surface tends to be uneven. In order to eliminate these steps, there are methods such as polishing the substrate surface to ensure smoothness and providing a planarizing layer on the surface, but this increases the cost.

  Further, a method for forming a light shielding film is disclosed in which a metal such as nickel is generated in the film using electroless plating (see Patent Document 3). Since this method also includes a plating step, the environmental burden of manufacturing is large as in the method using a metal sputtered film.

Further, a method for forming a light-shielding film is disclosed in which a metal sulfide such as nickel is generated in the film using electroless plating (see Patent Document 4). Since this method also includes a plating step, the environmental burden of manufacturing is large as in the method using a metal sputtered film.
JP 11-1335023 A JP-A-62-9301 JP-A-5-241016 JP-A-7-218715 “Color TFT LCD”, Kyoritsu Shuppan Co., Ltd., April 10, 1997, pp. 218-220

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a light-shielding film having a low environmental load, a thin layer and high light-shielding properties, and a low reflectance when viewed from the observer side. It is to provide an attached substrate.
Further, the present invention is to provide a substrate with a light-shielding film for a plasma display having a low environmental load, a thin film having a high light-shielding property, and a low reflectance when viewed from the observer side. It is to provide a plasma display using the same.

The above object is achieved by the present invention described below.
<1> A substrate with a light-shielding film for a plasma display having a light-shielding film on at least a part of at least one side of the substrate, the light-shielding film comprising a resin layer containing metal fine particles The light shielding film has an OD of 3 to 20 at a thickness of 555 nm of 3 to 20 , the metal fine particles contain two or more kinds of metal fine particles having different average particle diameters, and the difference between the average particle diameters is 10 nm or more . A substrate with a light-shielding film for a plasma display.

<2><1> Symbol plasma display using a plasma shielding film substrate with a display mounting.

According to the present invention, it is possible to provide a light-shielding film-attached substrate that has a low environmental load, is thin, has high light-shielding properties, and has low reflectance when viewed from the observer side.
In addition, the present invention can provide a substrate with a light-shielding film for a plasma display having a low environmental load, a thin film and high light-shielding properties, and a low reflectance when viewed from the observer side. A plasma display using the plasma display can be provided.

The substrate with a light-shielding film for plasma display of the present invention has a light-shielding film on at least a part of the substrate and at least one side of the substrate, and the light-shielding film includes a resin layer containing metal fine particles. The optical density (OD) per 1 μm thickness at 555 nm of the film is 3 to 20 , the metal fine particles contain two or more kinds of metal fine particles having different average particle diameters, and the difference between the average particle diameters is 10 nm or more . It is characterized by being.

Substrate has a light shielding film includes a resin layer light-shielding film containing metal fine particles is within the above range the optical density (OD) per thickness 1μm in 555nm of the light shielding film, the metal fine particles, average Since it contains two or more types of metal fine particles with different particle diameters and the difference in average particle diameter is 10 nm or more, the environmental load is small, the film is thin and highly light-shielding, and it is reflected when viewed from the observer side It is possible to provide a substrate with a light-shielding film for a plasma display with a low rate.

《Substrate with light shielding film for plasma display》
The substrate with a light-shielding film for a plasma display (hereinafter also referred to as “PD”) of the present invention has a light-shielding film on at least a part of the substrate and at least one side of the substrate.

<Light shielding film>
The light shielding film includes a resin layer containing metal fine particles, but preferably further includes a light absorption layer.
The light shielding film “black matrix (also referred to as BM)” of the present invention is particularly preferably used for a plasma display.
The thickness of the light shielding film is preferably in the range of 0.2 to 0.9 μm, more preferably 0.3 to 0.6 μm, and most preferably 0.4 to 0.5 μm. When the thickness is less than 0.2 μm, the light-shielding property is lowered. When the thickness exceeds 0.9 μm, the surface of red, blue, and green pixels to be subsequently provided may not be smooth and color unevenness may occur.
The optical density (OD) of the light-shielding film in the visible light region is preferably 3.0 or more and 7.0 or less, more preferably 3.5 or more and 6.5 or less, and most preferably 4 or more and 6 or less. When the optical density is less than 3, the contrast is lowered, the display quality is deteriorated, and there is a case where the frame portion is transparent due to the backlight. When the optical density is 7.0 or more, the film thickness may be increased. .

  In order to realize this optical density (OD) range, the optical density (OD) at a wavelength of 555 nm needs to be 3 to 20 per 1 μm thickness, more preferably 4 to 15, most preferably 8 to 12. is there.

  The light-shielding film is required to have performances such as heat resistance, light resistance, chemical resistance, surface smoothness, and hardness generally required for a color filter. Page 189 of "Technology and Chemicals (supervised sequentially by Watanabe, CMC Co., Ltd., published in 1998)" and page 117 of "Next-generation liquid crystal display technology (published by Tatsuo Uchida, Industrial Research Committee, 1994)". The required performance can be controlled by the pigment / binder ratio, binder type, exposure and heat treatment conditions, etc., as in the known light-shielding film.

(Resin layer containing fine metal particles)
Hereinafter, the resin layer containing the metal fine particles will be described.
The resin layer contains a resin together with the metal fine particles. However, unlike the carbon black and the pigment, the resin layer containing the metal fine particles of the present invention realizes a high shielding efficiency by reflecting and shielding light. It is considered a layer. Thereby, the film thickness of the light shielding film can be reduced. The light incident from the substrate side (observer side as a display) reflects the light leaked through the light absorption layer and returns to the substrate side. However, the metal fine particles inside the layer containing the metal fine particles of the present invention Reflection can be reduced by absorption by surface plasmons (absorption coefficient is around 10E7). If the light absorption layer is provided between the substrate and the layer containing metal fine particles, the light leaking through the light absorption layer is reflected back to the substrate side, and the thickness of the light absorption layer is reduced. Can do.
By having both the property of reflecting light and the property of absorbing light in this way, it has a high shielding power even though the reflectivity is lower than the mirror surface of aluminum (99% or more in the visible light range). At the same time, it is considered that reflection of light from the observer side can be suppressed to some extent, and light from the observer side can be prevented from being reflected to a practically acceptable level. Furthermore, a remarkable effect can be obtained by providing a relatively thin light absorption layer.

  In addition, the reflectance of the layer containing the metal fine particles increases as the concentration of the metal fine particles in the film increases with the same metal.

  In addition, since the object of the present invention is to reduce the environmental load, a metal film formed by metal sputtering, ion plating, metal deposition, or the like that requires an etching process as a layer containing metal fine particles. Is inappropriate.

―Metal fine particles―
The metal fine particles preferably include two or more kinds of metal fine particles having different average particle diameters, and the difference in the average particle diameters is preferably 10 nm or more.
The metal fine particles used in the present invention are not particularly limited, and any fine particles may be used. Here, the term “metal” refers to that described in “Metal” on page 444 of “Iwanami Physical and Chemical Dictionary (5th edition, published by Iwanami Shoten 1998)”.
In the present invention, the metal preferably forms a nanoparticle, and the metal forming the nanoparticle is preferably a metal belonging to Group 3 to Group 13 of the periodic table. Among these, silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, aluminum, tungsten, titanium, or chromium is preferable, and gold, silver, copper, and aluminum are more preferable.
The reflectance of the light-shielding film (metal film) when using silver rises from around 400 nm, and the reflectance is 90% or more at 500 nm. Although the reflectance varies depending on the compound, a material having a high reflectance in the visible light region such as gold, silver, and aluminum is preferably used. In particular, silver for cost and stability is preferred. As silver, colloidal silver is most preferable.
In the production of metal fine particles, two or more of the above metals may be used in combination, or may be used as an alloy.

As the metal fine particles, commercially available ones can be used, and the metal fine particles can be prepared by a chemical reduction method of metal ions (heat-reducible metal fine particles of fatty acid silver), an electroless plating method, a metal evaporation method, or the like.
For example, in the case of silver fine particles (colloidal silver), a conventionally known method, for example, a method of reducing a soluble silver salt with hydroquinone in an aqueous gelatin solution disclosed in US Pat. No. 2,688,601. , A method of reducing a sparingly soluble silver salt described in German Patent 1,096,193 with hydrazine, reduced to silver with tannic acid described in US Pat. No. 2,921,914 A method of chemically reducing silver ions in a solution, a method of forming silver particles by electroless plating described in JP-A-5-134358, and an inert gas such as helium as a bulk metal. It is possible to use a method such as a gas evaporation method in which the solvent is evaporated in the inside and cold trapped with a solvent. Alternatively, a method for preparing yellow colloidal silver by the dextrin reduction method of Carey Le described in Wiley & Sons, New York, 1933, Colloidal Elements by Weiser may be used.

As the metal fine particles in the present invention, it is also preferable to use the heat-reducible metal fine particles of the organometallic compound as a raw material. Here, in this specification, an organometallic compound is a generic name for organic compounds containing metals.
The organometallic compound used is not particularly limited, and any commercially available product can be used. For example, fatty acid metal salts such as oleate, naphthenate, octylate, stearate, benzoate, paratoyl ylate, n-decanoate, metal alkoxides such as izopropoxide and ethoxide, acetylacetone of the above metals Examples include complex salts. Among these, fatty acid metal salts such as oleate, paratoyl ylate, stearate, or n-decanoate, metal ethoxide, metal acetoacetonate, and the like are more preferable, and fatty acid metal salts are more preferable. Straight chain fatty acid metal salts are particularly preferable, and the number of carbon atoms is usually about 6 to 30, and more preferably 10 to 18.
The organometallic compounds can be used alone or in combination of two or more. The metal of the organometallic compound is not particularly limited, and can be appropriately selected according to the use of the final product.

The metal component of the organometallic compound is not particularly limited as long as it is derived from the organometallic compound, but the metal constituting the metal fine particles of the previous period is preferable.
The metal component in the present invention includes all states such as a simple substance of these metals, a mixture of these metals, or an alloy of these metals.
Regarding the metal component of the organometallic compound, for example, when ultrafine particles obtained from it are used for a metal coating film, the metal component forms a metal coating film as many components. May be selected as appropriate.
For example, even an organometallic compound that has sublimation properties and decomposes rapidly can be effectively used by adding a high-boiling solvent to suppress sublimation properties.
In addition, the metal fine particles in the present invention can be prepared as alloy-type ultrafine particles, for example, by mixing in advance an organometallic compound containing two or more kinds of metals.
The form of the organometallic compound as a raw material is not particularly limited, and any form such as powder or liquid may be used.

  The shape of the metal fine particle of the present invention is not particularly limited, and is spherical (cross section is circle, ellipse), indeterminate, plate, needle, regular hexahedron or regular octahedron (nanorod, disk, fiber, ring), etc. Although a polyhedron may be used, a spherical shape is preferable.

The average particle size of the metal fine particles in the present invention is preferably in the range of 1 to 5000 nm, more preferably in the range of 2 to 500 nm, and still more preferably in the range of 2 to 200 nm. Particles having an average particle diameter of 1 nm are difficult to produce, and absorption by metal plasmons is large, so that the absorption is not flat as a whole. A color filter produced using metal fine particles having the average particle diameter has its characteristics. On top, it may be unfavorable in that it looks brown in the field of view. On the other hand, if it exceeds 5000 nm, the stability of the dispersion in which the particles are dispersed may be lowered, and the light shielding property may be deteriorated.
The term “particle size” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area. The “number average particle diameter” refers to the average value of 100 particles obtained from the above-mentioned particle diameters of a large number of particles.

―Formation method of metal fine particles―
There is no restriction | limiting in particular in the formation method of the metal microparticle of this invention. Typical methods include the following.
(1) A method of forming metal compound particles by reduction of an organometallic compound prepared by a known method. (Japanese Patent Laid-Open No. 10-183207)
(2) A known method for evaporating metal such as a gas phase method or a liquid phase method.
In addition, a method for forming metal fine particles is described in, for example, “Latest Trends in Technology and Application of Ultrafine Particles II (issued by Sumibe Techno Research Corporation 2002)”

The light-shielding film in the present invention can be formed by using a coloring composition described later.
When formed with the coloring composition, the optical density per 1 μm of the thickness of the light shielding film needs to be 3 or more and 20 or less.

  Further, when preparing the color filter, considering that the metal fine particles are prevented from being fused during the heating step, the content of the metal fine particles in the colored composition is the same as that of the metal fine particles contained in the formed light shielding film. It is preferable to adjust the content to be about 10 to 90% by mass, preferably about 10 to 80% by mass.

The metal fine particles preferably contain two or more kinds of metal fine particles having a difference in average particle size of 10 nm or more. Here, the average particle diameter means a value obtained by measuring 50 particle diameters by observation with a transmission electron microscope (TEM) and calculating the average. The difference in the average particle diameter is preferably 10 to 500 nm, and more preferably 30 to 250 nm. When three or more kinds of metal fine particles having different average particle diameters are contained, the average particle diameter of the metal fine particles after mixing the two kinds is first converted from the two adjacent average particle diameters and the content ratio, and the remaining one kind The difference from the metal fine particles may be 10 nm or more.
If the difference in average particle diameter is less than 10 nm, it is difficult to obtain black (achromatic color).
From the viewpoint of the optical density (OD) of the light shielding film, the average particle size of the metal fine particles used in the colored composition of the present invention is preferably 1 to 500 nm, particularly preferably 60 to 250 nm, and particularly preferably 70 to 200 nm. preferable.

―Core shell fine particles―
The metal fine particles are preferably core-shell fine particles having a double structure composed of at least a metal and / or a metal compound.
The core and shell of the core-shell particle may be any component, but the surface shell and the inner core component are preferably different, have a shell made of a metal compound on the surface, and have a metal inside. Having a core is preferable in terms of ease of manufacture.

  As the metal fine particles of the present invention, that is, the metal that forms the core inside the nanoparticle, metals of Group 3 to Group 13 of the periodic table are preferable. Among these, silver, nickel, chromium, copper, palladium, gold, platinum, aluminum, tungsten, or titanium is preferable, and silver is particularly preferable from the viewpoint of cost and stability.

The “metal compound” referred to in the present invention is a compound comprising a metal and an element other than the metal. This metal is synonymous with the said metal, and its preferable example is also the same.
Examples of the compound of the metal and other elements include metal oxides, sulfides, sulfates, carbonates, etc. Among them, metal sulfides are particularly preferable because of their color tone and ease of forming fine particles.
Specific examples of the metal compound include copper (II) oxide, manganese oxide, iron sulfide, and silver sulfide. Among these, silver sulfide is particularly preferable from the viewpoints of color tone, ease of fine particle formation, and stability.

  The metal constituting the metal compound forming the shell and the metal forming the core may be of the same type or different types, but the same type is desirable in terms of ease of particle formation.

There is no restriction | limiting in particular in the shape of the core-shell fine particle in this invention. It is not necessarily a true sphere, and may be a spheroid, an indefinite shape, or a polyhedron such as a regular hexahedron or a regular octahedron.
The number average particle size of the core-shell particles in the present invention is preferably in the range of 1 to 5000 nm, more preferably in the range of 2 to 500 nm, and still more preferably in the range of 2 to 200 nm. Particles having an average particle diameter of 1 nm are difficult to produce, and absorption by metal plasmons is large, so that the absorption is not flat as a whole. A color filter produced using metal fine particles having the average particle diameter has its characteristics. On top, it may be unfavorable in that it looks brown in the field of view. On the other hand, if it exceeds 5000 nm, the stability of the dispersion in which the particles are dispersed may be lowered, and the light shielding property may be deteriorated.
The term “particle size” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area. The “number average particle diameter” refers to the average value of 100 particles obtained from the above-mentioned particle diameters of a large number of particles.

There is no restriction | limiting in particular about ratio of the core radius of the core-shell particle of this invention, and the thickness of a shell. The proportion of the shell weight to the particle weight is desirably 0.05 to 0.95, more preferably 0.08 to 0.92. It is preferable that the surface metal compound is 0.2 to 250 mass% with respect to the internal metal.
When the weight ratio of the shell is too large, the light shielding property is deteriorated. On the other hand, when the shell is too small, the light reflectance is undesirably increased.

-Formation method of core-shell particles-
There is no restriction | limiting in particular in the formation method of the said core-shell particle. Typical methods include the following.

(1) A method of forming a metal compound shell on the surface of a metal fine particle produced by a known method by oxidation or sulfuration. For example, there is a method in which metal fine particles are dispersed in a dispersion medium such as water, and sulfides such as sodium sulfide and ammonium sulfide are added. In addition, metal fine particles are contacted with a gas such as hydrogen sulfide or ozone to sulfidize the surface. Or a method of oxidizing. By these methods, the surface of the particles is sulfided or oxidized to form a core shell.

(2) In the process of forming metal fine particles, in order to continuously adjust the amount ratio of the metal compound and the internal metal on the surface, in the case of metal sulfide, a method of controlling the amount of sulfide to be added is preferable.
As the known metal fine particles, the method described in JP-A No. 10-183207, “Latest Trends in Technology and Application of Ultrafine Particles II (issued by Sumibe Techno Research Co., Ltd. 2002)”, etc. can be used. It can be produced by a method such as evaporation of a metal such as a liquid phase method.

  In the present invention, it is desirable that the metal fine particles are dispersed. Although the presence state is not particularly limited, it is preferable that the metal fine particles exist in a stable dispersed state, for example, a colloidal state is more preferable. In the colloid state, for example, it is preferable that the metal fine particles are dispersed in a substantially spherical fine particle state.

Here, as the dispersant, a thiol group-containing compound, an amino acid or a derivative thereof, a peptide compound, a polysaccharide, a natural polymer derived from a polysaccharide, a synthetic polymer, a gel derived from these, or the like can be used.
The kind of the thiol group-containing compound used here is not particularly limited and may be any compound as long as it has one or more thiol groups.

  Examples of the thiol group-containing compound include alkyl thiols (eg, methyl mercaptan, ethyl mercaptan, etc.), aryl thiols (eg, thiophenol, thionaphthol, benzyl mercaptan, etc.), amino acids or derivatives thereof (eg, cysteine, glutathione). Etc.), peptide compounds (eg, dipeptide compounds containing cysteine residues, tripeptide compounds, tetrapeptide compounds, oligopeptide compounds containing 5 or more amino acid residues), or proteins (eg, metallothionein or cysteine residues) And the like, but are not limited thereto.

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

-Core shell metal fine particle dispersion composition-
The core-shell particles can be used for the production of a light-shielding film as a core-shell metal fine particle dispersion composition in which core-shell fine particles are dispersed (hereinafter also referred to as “particle dispersion composition”).
The dispersion medium of the particle dispersion composition is not particularly limited, and various materials such as water, toluene, xylene, methyl isobutyl ketone, acetone, methyl alcohol, n-propyl alcohol, i-propyl alcohol can be used. .

The core-shell particle concentration in the particle dispersion composition is preferably 0.01 to 70% by mass, more preferably 0.1 to 30% by mass. If the concentration is less than 0.01% by mass, the amount of the composition for obtaining the necessary particles increases, which is disadvantageous. On the other hand, if the concentration exceeds 70% by mass, the stability of the composition decreases.
In addition to the core-shell particles and the dispersion medium, a dispersant, a surfactant and the like may be added to the particle dispersion composition of the present invention.

―Sinterable particles―
When the metal fine particles used in the present invention have a certain particle size, the particles can be fused to each other at a certain ratio in the heat treatment process, and these particle groups are close to the metal film and reflect light. Thus, light can be shielded efficiently. In addition, a certain degree of metal film-like reflection can be obtained without heat treatment such as when the particle size is distributed or when ultrafine particles of 10 nm or less are used.
For this reason, the metal fine particles in the present invention are preferably sinterable particles exhibiting the above properties.
That is, with the sinterable particles, the phenomenon of melting point drop due to the particle size being in the nanometer unit is generally known as the Kubo effect. The particles used this time are not exceptions, and are particles that cause a phenomenon in which the metal fine particles and the metal fine particles are fused with each other due to the melting point drop of the surface by becoming metal fine particles of around 10 nm.
Moreover, the higher the melting point of the bulk metal, the larger the sintered particle diameter, which is disadvantageous. Gold or silver has a melting point of around 1000 ° C. and can be preferably used.
Thus, it is considered that when the particles are sintered, the electron transfer distance of the free electrons in the metal becomes longer, so that the bulk property is changed and the reflectance is increased (approaching the bulk metal).

The volume fraction of the metal fine particles in the layer containing the metal fine particles in the present invention is slightly different depending on the metal, but is determined by “(metal volume / layer volume) × 100 = metal volume ratio (%)”. For example, the volume ratio of the metal fine particles in the layer containing the metal fine particles is a ratio obtained by obtaining the volume of metal silver with a specific gravity of 10.5 and dividing by the total volume of the layer containing the metal fine particles.
The volume fraction (%) of the metal fine particles in the layer containing the metal fine particles is slightly different depending on the metal, but is preferably 30 to 95%, more preferably 40 to 94%, and most preferably 50 to 93%. When the volume ratio is less than 30%, the necessary reflectance (reflectance necessary for light shielding) in the layer containing metal fine particles cannot be obtained, and further. If it exceeds 90%, the developability during photolithography tends to be poor, the coating film becomes brittle, and pinhole failure or scratch failure tends to occur. Also, 30% to 95% is preferable from the aim of reducing the overall film thickness or from the purpose of promoting fusion between particles.

―Coloring composition for light shielding film production―
It is preferable that the colored composition for preparing a light shielding film contains the metal fine particles, and additionally contains a dispersant and a dispersion medium. Furthermore, the composition preferably has photosensitivity. The metal fine particles are preferably used as the core-shell fine particle dispersion composition.
In order to impart photosensitivity, a photosensitive resin composition is added to the colored composition. Hereinafter, the colored composition may refer to a state containing a photosensitive resin composition.
The photosensitive resin composition means a photosensitive resin composition that does not contain fine metal particles. An alkali-soluble binder polymer, a monomer that undergoes addition polymerization upon irradiation with light having an ethylenically unsaturated double bond, photopolymerization initiation It can be produced by containing an agent or the like.

Photosensitive resin compositions include those that can be developed with an aqueous alkali solution and those that can be developed with an organic solvent, but those that can be developed with an aqueous alkaline solution are preferred in terms of safety and the cost of the developer.
The photosensitive resin used may be either a negative type in which a part that receives radiation such as light or an electron beam is cured, or a positive type in which a radiation non-accepting part is cured.

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

Examples of the negative photosensitive resin include a photosensitive resin composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. It is done.
Among them, a photosensitive resin containing a photopolymerization initiator, a photopolymerizable monomer, and a binder as basic components is particularly preferable.
For the photosensitive resin layer, "polymerizable compound B", "polymerization initiator C", "surfactant", "adhesion aid" described in JP-A-11-133600, and other compositions can be used.
For example, a negative photosensitive resin that can be developed in an aqueous alkali solution can be subjected to addition polymerization by irradiation with light with a binder containing a carboxylic acid group as a main component (such as the aforementioned alkali-soluble thermoplastic resin). It contains an ethylenically unsaturated double bond-containing monomer and a photopolymerization initiator.

The substrate with a light-shielding film of the present invention can be produced by applying a colored composition for producing a light-shielding film (hereinafter referred to as a colored composition) on the substrate.
The particle concentration of the metal fine particles in the coloring composition is desirably in the range of 0.01 to 70% by mass, more preferably 0.1 to 40% by mass. When the concentration is less than 0.01% by mass, the amount of the photosensitive resin composition used to obtain the required coating amount of the particles increases, and there may be problems such as being unable to apply uniformly and applying a drying load. On the other hand, when the concentration exceeds 70% by mass, the storage stability of the photosensitive resin composition may be lowered.

    In addition to the solvent, a dispersant, a surfactant and the like may be added to the photosensitive resin composition in the present invention.

As the dispersant, known dispersants such as polyvinyl alcohol, acrylamide, sodium polyacrylate, sodium alginate, acrylamide / acrylic acid copolymer, styrene / maleic anhydride copolymer can be used. In addition, aliphatic silver compounds such as silver stearate can also be used publicly. The dispersant is described in, for example, “Pigment Dispersion Technology, Technical Information Association Co., Ltd.” (issued in 1999).
As the surfactant, known anionic, cationic, nonionic or betaine surfactants can be used, and among these, anionic surfactants are preferred from the viewpoint of stability.
Examples of preferable anionic surfactants include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dioctylsulfosuccinate, sodium oleate and the like. Surfactants are described in, for example, “New Edition Surfactant Handbook (Tokiyuki Yoshida, Shinichi Shindo, Tadayoshi Ogaki, Kazuyoshi Yamanaka, Optical Book Co., Ltd., published in 1987)”. Further, as a surfactant, C ₈ F ₁₅ SO ₂ N (C ₂ H ₅ ) (CH ₂ O) ₁₄ H, C ₈ F ₁₇ SO ₃ Li, C ₇ F ₁₅ COONH ₄ , C ₈ F ₁₇ SO ₂ (C _{2 H 5) C 2 H 4} OPO (OH) 2, F110, F113, F176PF, F117, F780 ( both produced by Dainippon Ink & Chemicals Co. oligomers fluoropolymer surfactant) fluorinated surfactants, such as Is also preferable

―Pigment fine particles―
Since the light-shielding film of the present invention is required to absorb light, it can further contain fine pigment particles.
Examples of the pigment fine particles include light absorbing substances (black pigments, pigments, dyes). Examples thereof preferably include carbon black, a mixture of pigments, and an oxide composite compound containing at least one metal element of manganese, cobalt, iron and copper. More preferred are carbon black, oxide composite compounds containing at least one metal element of manganese, cobalt, iron and copper, and most preferred is carbon black. Carbon black is used after being appropriately surface-treated.

As the reflectance, the reflectance at 555 nm near the peak wavelength of eye sensitivity is used in the present invention.
The specific measurement method is that light is incident from a direction inclined by 5 ° with respect to the normal, and the intensity of the light is measured in the reflection direction opposite to the normal (5 ° with respect to the angle normal). It is calculated from the ratio “(I / I ₀ ) × 100 (%)” of I ₀ and reflection intensity I. However, when there is an influence of the reflection on the substrate surface, the value obtained by subtracting the reflection of the substrate is measured in advance. The reflectance of the layer containing metal fine particles is measured from the side opposite to the substrate after being formed alone on the substrate.
The reflectance of the layer containing metal fine particles tends to increase as the metal fine particles come close to each other or can contact each other. For example, in a small and uniform particle size (10 nm), the particles are fused to each other even at a relatively low heat treatment temperature of about 200 ° C., and the reflectance is high. Further, in a mixture of various sizes (2 to 80 nm), the particles tend to approach or come into contact with each other at the stage of film formation and have a high reflectance.
The reflectance of the layer containing fine metal particles in the present invention is preferably 30% to 90%, more preferably 40% to 80%, and most preferably 50% to 70% at a wavelength of 555 nm. Below this range, sufficient shielding power may not be obtained, and above this range, the amount of metal particles added may increase so that patterning by photolithography may be difficult.
When measured from the substrate side of the light-shielding film in the present invention, the reflectance at a wavelength of 555 nm is preferably 0.01 to 6%, more preferably 0.1 to 1.5% from the viewpoint of increasing bright room contrast. 0.7 to 1.0% is preferable.

(Light absorption layer)
It is preferable that the light shielding film is composed of at least two resin layers, at least one of the resin layers is a layer containing the metal fine particles, and at least one of the resin layers is a light absorption layer. .
When the layer containing the metal fine particles (hereinafter also referred to as “light reflecting layer”) has a reflectance of 30 to 90% at a wavelength of 555 nm, the optical density (OD) of the light absorbing layer at a wavelength of 555 nm is 0.3. It is preferable that it is -3.0.

The light absorption layer in the present invention is a layer having a light absorption function and reducing the reflection when observed from the substrate side.
When the light absorption layer is provided on the most substrate side of the entire resin layer, reflection at the substrate-resin layer interface is also suppressed. For this light absorption layer, a low reflection black film or a homogeneous composite low reflection black film is used.
The thickness of the homogeneous composition film is preferably 0.05 to 0.6 μm, and more preferably 0.1 to 0.3 μm from the viewpoint of the total film thickness. If it is thinner than 0.05 μm, the light absorption effect may be lost, and if it is thicker than 0.6 μm, there is a possibility that trouble may occur when forming a color filter.
The optical density (OD) is in the range of 0.3 to 3.0, preferably 0.5 to 1.2, and most preferably in the range of 0.6 to 1.0.
For this purpose, the light absorbing layer in the present invention preferably contains a light absorbing substance (black pigment, pigment, dye).

  Examples of the light absorbing material preferably include carbon black, a mixture of pigments, and an oxide composite compound containing at least one metal element of manganese, cobalt, iron, and copper. More preferred are carbon black, oxide composite compounds containing at least one metal element of manganese, cobalt, iron and copper, and most preferred is carbon black. Carbon black is used after being appropriately surface-treated.

The light-absorbing substance (coloring material) used in the light-absorbing layer of the present invention is preferably substantially uniformly dispersed in the resin layer, and preferably has a particle size of 5 μm or less, preferably 1 μm or less. It is. In producing a color filter, a particle size of 0.5 μm or less is particularly preferable.
Examples of preferred black pigments (black pigments) or dyes are as follows. Monolite First Black B (CI Pigment Black 1) and carbon black, manganese and cobalt oxides Mn ₃ O ₄ and Co ₃ O ₄ , and metal oxides such as iron and copper .

  The disperser used when dispersing these pigments is not particularly limited, and examples thereof include known dispersers such as a kneader, roll mill, atrider, super mill, dissolver, homomixer, and sand mill.

  The optical density of the light absorption layer is determined by the balance with the light reflection layer density. The light absorption layer has both an effect of preventing reflection of reflected light from the light reflection layer and an effect of light absorption. However, since the light absorption layer absorbs external light twice, it is more than a normal single layer film. There is an advantage of being thin. Usually, the optical density of the light absorbing layer is preferably 3 or less. As a particularly preferable aspect, the optical density of the light absorption layer is set low by setting the metal fine particle concentration of the layer containing the metal fine particles to 70% or more and the light reflectivity to 70% or more in the range of 400 nm to 800 nm. It becomes possible.

  The light absorption layer in the present invention needs to be formed in a pattern by a method having a small environmental load such as photolithography, and is formed by a composition containing a resin component necessary for this. This resin component will be described later.

When the light absorption layer in the present invention is formed on the side closest to the substrate by a transfer method, the transfer material for forming the light absorption layer in the present invention is softened or tacky at a temperature of 150 ° C. or less. And is preferably thermoplastic.
Most of the layers using known photopolymerizable compositions have this property, but some of the known layers can be further modified by the addition of thermoplastic binders or compatible plasticizers. .

―Resin component―
As the material for the light absorption layer in the present invention, all known photosensitive resins described in, for example, JP-A-3-282404 can be used.
Specific examples include a photosensitive resin layer composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Among these, a photopolymerizable resin is particularly preferable. The photopolymerizable resin preferably contains a photopolymerization initiator, a photopolymerizable monomer or oligomer, and a binder as basic components.
Moreover, the resin component described here is preferable in the sense that the coating film is stably adhered to the substrate even when the photosensitive resin composition is directly applied to the substrate.
Furthermore, the resin component described here can also be used for a layer containing metal fine particles of the present invention and an auxiliary layer.
Since the light absorption layer is formed for the purpose of suppressing reflection when viewed from the viewer side, the light absorption layer is provided so as to be positioned on the viewer side with respect to the layer containing metal fine particles. If provided in reverse, this purpose cannot be achieved.

(Auxiliary layer)
The auxiliary layer in the present invention is a layer having one or more functions described below, and is preferably provided in the light-shielding image layer from the viewpoint of impact resistance, chemical resistance, and solvent resistance.
The light-shielding film may be patterned by a photolithographic method using a photosensitive auxiliary layer to form a light-shielding film on at least a part of the substrate, but the wavelength dependence on the absorption of metal fine particles by surface plasmons By using a wavelength region with relatively weak light shielding power as an exposure wavelength, it is possible to include a photopolymerization system in the layer containing metal fine particles and pattern it by a photolithographic method. is there.
More specifically, for example, in the case of a photocuring system using an absorption region of 365 nm, the light reflectance is required to be low in the vicinity thereof. In the case of silver, since the reflectance near 300 nm is 50% or less, it is suitably used for a photocuring system using an absorption region of 365 nm.
Since this reflection characteristic varies depending on the type of metal, the type of metal is appropriately selected according to the exposure wavelength.

1. 1. A layer formed at this interface in order to increase the adhesion between the substrate and the resin layer (light absorbing layer) in the present invention. 2. Layer which is provided between the substrate and the resin layer in the present invention or between the resin layer in the present invention and another resin layer in the present invention to prevent reflection at the interface 3. A layer provided at this interface in order to increase the adhesion between the light reflecting layer and the light absorbing layer. 4. Layer provided for protecting the resin layer on the present invention. Layer provided for patterning the resin layer in the present invention by photolithography

  Examples of a specific layer configuration using the auxiliary layer in the present invention include, from the substrate side, a light absorbing layer / light reflecting layer / auxiliary layer, a light absorbing layer / auxiliary layer / light reflecting layer / auxiliary layer, an auxiliary layer / Examples of the light absorbing layer / light reflecting layer / auxiliary layer include, but are not particularly limited to.

<Transfer material>
The transfer material in the present invention is a material having at least one transfer layer on a temporary support. The transfer material of the present invention may further be provided with a thermoplastic resin layer, an intermediate layer, an intermediate layer, a release layer, etc., if necessary. In particular, the thermoplastic resin layer and the intermediate layer are effective for improving the transferability and sensitivity of the transfer layer.
The transfer layer is preferably at least two resin layers, and the resin layer preferably includes at least one layer containing metal fine particles (light reflecting layer) and at least one light absorbing layer.
The transfer material will be described in detail.

(Temporary support)
As the temporary support, a known temporary support such as polyester or polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of strength, dimensional stability, chemical resistance, and cost. The thickness of the temporary support is desirably 15 to 200 μm, more preferably 30 to 150 μm. If the thickness is too large, it is disadvantageous in terms of cost. If the thickness is too small, there is a disadvantage that the temporary support is deformed by the heat of the drying process or lamination process after coating.
Further, it is necessary to be flexible and not to cause significant deformation, contraction or elongation even under pressure or under pressure and heating. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Transfer layer)
The transfer layer of the transfer material in the present invention is preferably formed from the above-described coloring composition for forming a light-shielding film, and is preferably a photosensitive resin composition. If necessary, a polymer, a monomer, and a polymerization start It is obtained by applying a coating liquid obtained by adding an agent, a polymerization inhibitor, a surfactant, a pigment and the like to a temporary support.
The transfer layer of the present invention preferably has a photosensitivity.
The transfer layer can be developed with an aqueous alkali solution, and can be developed with an organic solvent. In view of safety and the cost of the developer, the transfer layer is preferably an aqueous alkaline solution developable. The photopolymerizable composition that can be developed in an alkaline aqueous solution contains a carboxylic acid group-containing binder, a polyfunctional acrylic monomer, and a photopolymerization initiator as main components.

-Multifunctional acrylic monomer-
Polyfunctional acrylic monomers used in the present invention include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene (Meth) acrylates such as glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-hexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Are preferred.

-binder-
As the carboxylic acid group-containing binder, a copolymer of an unsaturated organic acid compound such as acrylic acid or methacrylic acid and an unsaturated organic acid ester compound such as methyl acrylate, ethyl acrylate or benzyl methacrylate is preferable.

-Photopolymerization initiator-
As a photoinitiator, the composition containing a halomethyl oxadiazole type compound or a halomethyl-s-triazine type compound can be mentioned.

-solvent-
The photosensitive resin composition in the present invention preferably contains a solvent. This solvent is not particularly limited, and water, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, acetone, methyl alcohol, n-propyl alcohol, i-propyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexane Various things such as hexanol, ethyl lactate, methyl lactate, caprolactam can be used.

(Thermoplastic resin layer)
The transfer material of the present invention can be provided with a thermoplastic resin layer.
Examples of the resin constituting the thermoplastic resin layer include acrylic resins, polystyrene resins, polyesters, polyurethanes, rubber resins, vinyl acetate resins, polyolefin resins, and copolymers thereof.
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

  These resins are preferably used by mixing two types (resin A and resin B) as follows. The resin A has a weight average molecular weight of 50,000 to 500,000 and a glass transition temperature (Tg) in the range of 0 to 140 ° C., more preferably a weight average molecular weight of 60,000 to 200,000, and a glass transition temperature (Tg). ) Is preferably in the range of 30 to 110 ° C. Specific examples of these resins include methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymers described in JP-A-63-147159.

  The resin B has a weight average molecular weight of 3,000 to 30,000 and a glass transition temperature (Tg) in the range of 30 to 170 ° C., more preferably a weight average molecular weight of 4,000 to 20,000 and a glass transition temperature (Tg). ) Is preferably in the range of 60 to 140 ° C. Preferable specific examples include styrene / (meth) acrylic acid copolymers described in JP-A-5-241340.

When the weight average molecular weight of the resin A constituting the thermoplastic resin layer is less than 50,000 or the glass transition temperature (Tg) is less than 0 ° C., the thermoplastic resin protrudes to the surroundings during the occurrence of reticulation or transfer. Contaminates the support. When the weight average molecular weight of the resin A exceeds 500,000 or the glass transition temperature (Tg) exceeds 140 ° C., the suitability for lamination deteriorates.
The thickness of the thermoplastic resin is desirably 1 to 50 μm, more preferably 2 to 20 μm. When the thickness is less than 1 μm, the suitability for lamination is deteriorated, and when it exceeds 50 μm, it is not preferable from the viewpoint of cost and production suitability.
The coating liquid for the thermoplastic resin layer of the present invention can be used without particular limitation as long as the resin constituting this layer is dissolved, and for example, methyl ethyl ketone, n-propanol, i-propanol and the like can be used.

(Intermediate layer <oxygen barrier layer>)
In the transfer material of the present invention, an alkali-soluble intermediate layer (hereinafter also referred to as “oxygen barrier layer”) for preventing layer mixing of both layers during coating is provided between the thermoplastic resin layer and the transfer layer. It is preferable to provide it.
The resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble. Examples of such resins include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins and copolymers thereof. it can. Further, a resin which is made alkali-soluble by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin which is not usually alkali-soluble, such as polyester, can also be used.
Of these, polyvinyl alcohol is preferred. The polyvinyl alcohol preferably has a saponification degree of 80% or more, more preferably 83 to 98%.

  It is preferable to use a mixture of two or more resins constituting the intermediate layer, and it is particularly preferable to use a mixture of polyvinyl alcohol and polyvinyl pyrrolidone. The mass ratio of the two is preferably polyvinylpyrrolidone / polyvinyl alcohol = 1/99 to 75/25, more preferably in the range of 10/90 to 50/50. If the mass ratio is less than 1/99, problems such as deterioration of the surface state of the intermediate layer and poor adhesion with the light absorption layer coated on the intermediate layer may occur. Moreover, when the said mass ratio exceeds 75/25, the oxygen barrier property of an intermediate | middle layer falls and a sensitivity may fall.

  The thickness of the intermediate layer is preferably from 0.1 to 5 μm, more preferably from 0.5 to 3 μm. If the thickness is less than 0.1 μm, the oxygen barrier property may be lowered. If the thickness exceeds 5 μm, the intermediate layer removal time during development increases.

  The application solvent for the intermediate layer is not particularly limited as long as it can dissolve the above-mentioned resin, but water is preferably used, and a mixed solvent obtained by mixing the above-mentioned water-miscible organic solvent with water is also preferable. Specific examples of preferable coating solvents for the intermediate layer include the following. Water, water / methanol = 90/10, water / methanol 70/30, water / methanol = 55/45, water / ethanol = 70/30, water / 1-propanol = 70/30, water / acetone = 90/10 Water / methyl ethyl ketone = 95/5. These ratios represent mass ratios.

(Method for producing photosensitive resin transfer material)
In the photosensitive resin transfer material in the present invention, a thermoplastic resin layer is provided by applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support, followed by drying. Then, an intermediate layer material solution made of a solvent that does not dissolve the thermoplastic resin layer is applied on the thermoplastic resin layer and dried, and then the photosensitive resin layer is applied and dried with a solvent that does not dissolve the intermediate layer. Can be produced.
In addition, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are also prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

(Protective film)
The photosensitive resin layer can have a thin cover sheet on the side facing the temporary support to protect against contamination and damage during storage. The cover sheet may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. As the covering sheet material, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable. The thickness of the covering sheet is preferably about 5 to 100 μm. Particularly preferred is a polyethylene or polypropylene film having a thickness of 10 to 30 μm.

(Coating, drying)
In order to apply the colored composition in the present invention, it can be performed by a known coating apparatus or the like.
There is no restriction | limiting in particular as a coating method. For example, a spin coating method described in JP-A-5-224011, a die coating method described in JP-A-9-323472, or the like can be used. Further, for example, a method described in “Coating Engineering (Yuji Harasaki, Asakura Shoten, published in 1972)” can also be used.
Among these, in this invention, it is preferable to carry out by the coating device (slit coater) using the slit-shaped nozzle which has a slit-shaped hole in the part which discharges a liquid.
Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Application Laid-Open No. 2001-310147 and the like are preferably used.
By applying the coloring composition to a temporary support or a substrate with these nozzles or coaters, a transfer layer can be formed on the temporary support, and a photosensitive resin layer can be formed on the substrate.
The film thickness after drying is desirably 0.2 to 0.9 μm, more preferably 0.3 to 0.6 μm, and most preferably 0.4 to 0.5 μm. When the thickness is less than 0.2 μm, the light shielding property of the formed light shielding film is deteriorated. When the thickness exceeds 0.9 μm, the surface of red, blue, and green pixels provided after the light shielding film is formed is not smooth and color unevenness occurs. appear.

<< Method of manufacturing substrate with light-shielding film >>
<Method for producing substrate with light-shielding film using transfer material>
The substrate with a light-shielding film of the present invention is formed by laminating a transfer material provided with a transfer layer (light-shielding layer) on a temporary support so that the transfer layer (light-shielding layer) is in contact with the substrate, and a laminate of the transfer material and the substrate. The temporary support is peeled from the substrate, and then the photosensitive light-shielding layer is exposed and developed through a photomask for a light-shielding film.
Hereinafter, a method for transferring the transfer material (photosensitive resin transfer material) in the present invention to the substrate will be described in detail.

In this step, the transfer layer having at least two resin layers on the temporary support is transferred to the substrate.
The transfer is preferably performed by laminating the transfer layer (light reflection layer and / or light absorption layer) and the substrate in close contact. A known method can be used for laminating. For example, a laminator, a vacuum laminator or the like can be used at a temperature of about 60 to 150 ° C., a pressure of about 0.2 to 20 Pa, and a line speed of about 0.05 to 10 m / min. In the present invention, it is preferable to peel off the temporary support after lamination.

(Formation of other colors)
Further, in order to form a color filter according to the present invention, it can be produced by a known method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated by the number of colors. If necessary, the boundary may be divided by a light shielding film.
In the above production method, the method for forming the photosensitive resin layer on the substrate includes: (a) a method of applying each of the colored photosensitive resin compositions by a known coating apparatus; and (b) the above-described method. Examples thereof include a method of using a photosensitive resin transfer material and affixing with a laminator.

-Pasting with a laminator-
Using the above-mentioned photosensitive resin transfer material, the photosensitive resin layer formed in a film shape can be attached by pressure bonding or thermocompression bonding with a roller or flat plate heated and / or pressurized on a substrate described later. . Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575.

(substrate)
As a substrate used in the present invention, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, or a plastic A film etc. can be mentioned.
Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring composition or a photosensitive resin transfer material by performing a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used.

(Intermediate layer, oxygen barrier layer)
In carrying out the present invention, the exposure can be carried out in a state in which an intermediate layer having an oxygen blocking function is further provided on the photosensitive resin layer. Thereby, exposure sensitivity can be improved. Examples of the material include those already described in the section of (Interlayer) of <Photosensitive resin transfer material>.

(Pattern exposure)
The exposure in the production of the light shielding film of the present invention is preferably performed as follows.
The light source used for exposure is selected according to the photosensitivity of the light-shielding transfer layer. For example, a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or an argon laser can be used. As described in JP-A-6-59119, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used in combination.
The exposure method may be batch exposure in which the entire surface of the substrate is exposed at once, or may be divided exposure in which the substrate is divided and exposed in several times. Furthermore, the exposure method performed while scanning the substrate surface using a laser may be used.

(developing)
In this step, the resin layer (transfer layer) after the pattern exposure is developed and unexposed portions are removed.
As the developer, a dilute aqueous solution of an alkaline substance is used, but a developer added with a small amount of an organic solvent miscible with water may also be used. Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Mention may be made of morpholine, tetraalkylammonium hydroxides (for example tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01 to 30% by mass, and the pH is preferably 8 to 14. Further, according to the properties such as oxidation of the transfer layer, for example, the pH of the developer can be changed to adjust the transfer layer so that the development by the film-like detachment can be performed.
Suitable organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of the water-miscible organic solvent is generally 0.1 to 30% by mass.

A known surfactant can be further added to the developer. The concentration of the surfactant is preferably from 0.01 to 10% by mass.
The developer can be used as a bath solution or a spray solution. In order to remove the uncured portion of the transfer layer in a solid form (preferably a film form), use a method such as rubbing with a rotating brush or wet sponge in the developer, or spray pressure when the developer is sprayed. Is preferred. The temperature of the developer is usually preferably in the range of about room temperature to 40 ° C. It is also possible to put a water washing step after the development processing.
The processing solution for the thermoplastic resin layer and the developing solution for the photosensitive resin layer do not need to be the same, and the formulations may be different.

(Bake)
You may heat-process as needed after a image development process. By this treatment, the photosensitive light-shielding film cured by exposure can be heated to proceed with curing, and the solvent resistance and alkali resistance can be enhanced. Examples of the heating method include a method of heating the substrate after development in an electric furnace, a drier, etc., a method of heating with an infrared lamp, and the like. The heating temperature and heating time depend on the composition and thickness of the photosensitive light-shielding film, but are preferably in the range of 120 to 250 ° C. for 10 to 300 minutes, more preferably 180 to 240 ° C. for 30 to 200 minutes.

(Post exposure)
In addition, after the development step and before the heat treatment, exposure may be performed to accelerate curing. This exposure can also be performed by the same method as the first exposure described above.

(Patterning)
In the present invention, obtaining the shape of the pixel is called patterning and is performed by exposure and development of the photosensitive resin layer as described above. Such a patterning method is called photolithography or photolithography.

<Method for producing light-shielding film using colored composition (including photosensitive resin composition)>
A method for producing a light-shielding film using the colored composition (including the photosensitive resin composition) in the present invention will be described.
First, the colored composition (including the photosensitive resin composition) is applied onto a substrate and dried to form a resin layer. Subsequently, the resin layer is exposed to an image pattern using an exposure mask. The exposed resin layer of the image pattern is developed to remove the unexposed portions, and a light shielding film is formed on the substrate.
Here, the substrate, exposure, development, and the like are the same as those described when the transfer material is used. Moreover, about the application | coating and drying, the conditions in the manufacturing method of a transfer material are employable.
The photosensitive resin composition contained in the colored composition in the present invention is used for various purposes depending on the purpose, and preferably the light shielding film, the substrate with the light shielding film, the transfer material, a color filter described later, and Used for BM in a display device.

"Color filter"
The color filter according to the present invention is preferably composed of a colored layer on a substrate, having two or more pixel groups exhibiting different colors, and each pixel constituting the pixel group is isolated from each other by the light shielding film. .
The substrate is preferably a light transmissive substrate, as described above.
The color filter is preferably formed using the PD light-shielding film-coated substrate, and the light-shielding film is preferably formed using the colored composition or the transfer material.
The color filter layer in the present invention preferably uses at least one of a blue filter, a green filter, and a red filter. In the case of the three-color independent light emitting type, it is not necessary to provide it.
The color filter is preferably a color filter used in a plasma display (PD).
The color filter layer may be a color filter used in liquid crystal displays, but if the characteristics of the color filter are adjusted according to the light emitted by the phosphor and the extraction efficiency and color purity are optimized. Good. Further, it is preferable to use a color filter that can cut light having a short wavelength that absorbs light.
In order to obtain a full color display using such a color filter, the color after passing through the color filter may be adjusted to the NTSC standard or the chromaticity coordinates of the current CRT. Such chromaticity coordinates can be measured using a general chromaticity coordinate measuring instrument, such as SR-1 manufactured by Topcon Corporation.

<Plasma display (PD)>
The plasma display of the present invention is manufactured based on a method for manufacturing a plasma display described in, for example, Japanese Patent Application Laid-Open Nos. 2003-203575 and 9-283030.
The plasma display in the present invention may have only a light shielding film or a color filter layer provided with the light shielding film.

EXAMPLES Hereinafter, although an Example , a reference example, and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples at all. Unless otherwise specified, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Example 1
Production of substrate with light-shielding film (production of silver-dispersed slurry)
3,488 g of distilled water was added to 112 g of gelatin, and the resulting mixture was heated to about 47 ° C. to dissolve the gelatin. To this, 4.0 g of calcium acetate and 2.0 g of potassium borohydride were added. Immediately thereafter, 6.0 g of silver nitrate dissolved in 1.0 L of distilled water was added with rapid stirring. Distilled water was added to adjust the final weight to 5.0 kg. The product was then cooled to near the gelation temperature and passed through a small hole into the cooled water, thereby forming a very fine noodle. These noodles (linear slurries) were supplied as amplification catalysts for producing blue silver on site. For convenience and to prevent the noodle from forming a molten mass, the noodle was diluted with water to make a noodle slurry of water 1 to noodle 3.
6.5 g of potassium hydroquinone monosulfonate and 0.29 g of KCl dissolved in 81 g of distilled water were added to 650 g of borohydride-reduced silver nuclei. The noodle slurry was cooled to about 6 ° C. The following two types of solutions A and B were prepared in separate containers.

A Sodium sulfite (anhydrous) 19.5 parts Sodium bisulfite (anhydrous) 0.98 parts Distilled water 122.0 parts

B Silver nitrate 9.75 parts Distilled aqueous solution 122.0 parts

The above A and B were mixed, and a white precipitate disappearing when stirring was continued. Immediately, this mixture was then added to the noodle slurry with rapid stirring in a short time (within 5 minutes). The temperature was maintained at 10 ° C. and amplification was allowed to proceed for about 80 minutes until all soluble silver salt was reduced onto the nuclei. The resulting blue slurry particulates were passed through the slurry in a nylon mesh bag through the slurry and washed for about 30 minutes with the wash water passing through the bag, so all the salt was washed away.
The washed blue silver dispersed in the gel slurry was dewatered until the weight of the product was 412 g so that when melted, a blue silver dispersion having a concentration of 1.5 wt% silver was obtained.

(Preparation of silver fine particles)
To 5000 g of the silver dispersion slurry obtained as described above, 25 g of a dispersant (Lapisol B-90, manufactured by NOF Corporation) and 1000 g of a papain 5% by weight aqueous solution were added and stored at 37 ° C. for 24 hours.
This solution was centrifuged at 2000 rpm for 5 minutes to precipitate silver fine particles. After removing the supernatant, it was washed with distilled water to remove the gelatin degradation product decomposed by the enzyme.
Next, the silver fine particle precipitate was washed with methyl alcohol and then dried. An aggregate of about 85 g of silver fine particles was obtained. 73.5 g of this aggregate and 1.05 g of Solsperse 20000 (dispersant manufactured by Avicia Co., Ltd.) and 16.4 g of methyl ethyl ketone were mixed. This was used to obtain a silver fine particle dispersion A-1 having an average particle diameter of 100 nm using a bead disperser (zirconia beads 0.3 mm).

  A silver fine particle dispersion A-2 having an average particle size of 90 nm was obtained in the same manner.

(Preparation of temporary support)
On a polyethylene terephthalate film temporary support having a thickness of 75 μm, a thermoplastic resin layer coating solution having the following formulation C is applied using a slit nozzle so that the dry thickness is 5 μm. Let dry for minutes.
Next, an intermediate layer coating solution having the following formulation D was applied on the thermoplastic resin layer prepared above so as to have a dry thickness of 1.5 μm, and dried at 100 ° C. for 3 minutes.

C: Thermoplastic resin layer coating solution formulation Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid = 54/12/5/29 copolymer (number average molecular weight 80,000) 58 parts Styrene / acrylic acid = 70/30 Copolymer (number average molecular weight 7000) 136 parts BPE-500 (polyfunctional acrylate made by Shin-Nakamura Chemical Co., Ltd.) 90 parts F780F (fluorine surfactant 20% made by Dainippon Ink & Chemicals, Inc.) 1 part methyl ethyl ketone 541 1-methoxy-2-propanol 63 parts methyl alcohol 111 parts

D: Prescription of coating solution for intermediate layer (protective layer) Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd.) 3.0 parts Polyvinylpyrrolidone (PVP-K30 manufactured by GAF Corporation) 1.3 parts Distilled water 50.7 parts Methyl Alcohol 45.0 parts

(Production of transfer material)
On the temporary support obtained above, the coating solution obtained from the following formula E is applied on the intermediate layer prepared as described above so that the film thickness becomes 0.6 μm, and at 100 ° C. for 3 minutes. It dried and produced the transfer material.

E: Formulation of photosensitive resin layer coating solution Silver fine particle dispersion A-1 (100 nm) 20.0 parts Silver fine particle dispersion A-2 (90 nm) 20.0 parts Propylene glycol monomethyl ether acetate 28.6 parts
Methyl ethyl ketone 37.6 parts Surfactant (F176PF (20%)) 0.2 parts Hydroquinone monomethyl ether 0.001 part benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, molecular weight 30000) 2.1 parts di Pentaerythritol hexaacrylate Added bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl so that the sum of the volume fractions of the metal fine particles is 0.126 ] Phenyl] sebacate 0.1 part

(Production of substrate with light-shielding film by transfer using transfer material)
A substrate with a light shielding film was produced by the following method using the transfer material.
(Transcription)
The photosensitive resin layer surface of the transfer material is attached to a transparent glass substrate (thickness 1.1 mm) by applying pressure (0.8 Pa) and heating (130 ° C.) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.). Subsequently, peeling was performed at the interface between the temporary support and the thermoplastic resin layer, and only the temporary support was removed. When the transfer material has a protective sheet, the operation is performed after the sheet is peeled off.

(exposure)
Subsequently, a substrate and a mask (quartz exposure mask having an image pattern) were vertically set on the transfer material obtained above by a proximity type exposure machine (manufactured by Hitachi Electronics Engineering) having an ultrahigh pressure mercury lamp. In this state, the distance between the exposure mask surface and the photosensitive material was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² from the coated surface side. The vertically standing state means that the thermoplastic resin layer surface of the photosensitive material stands vertically in parallel with the mask so as to be on the mask side.

(developing)
The thermoplastic resin and the intermediate layer were removed with a 1% triethanolamine aqueous solution. At this time, the photosensitive resin layer was not substantially developed.
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the resin layer, and then a KOH developer (KOH, containing nonionic surfactant, product names: CDK-1, Fuji Film Arch) ) At 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa for shower development to obtain a patterning image.
Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, thereby obtaining a light shielding film. Then, it heat-processed for 40 minutes at 220 degreeC, and obtained the board | substrate with a light shielding film.

(Examples 2 to 5)
It carried out like Example 1 except having used the liquid mixture of the silver fine particle dispersion shown in Table 1 instead of the silver fine particle dispersion of Example 1.

(Example 6)
Instead of the silver fine particle dispersion A-2 (90 nm) of Example 1, a gold fine particle dispersion (90 nm) prepared by treating the water surface of a chloroauric acid aqueous solution with a burner flame was used. It carried out similarly.

(Example 7)
It implemented similarly to Example 1 except having used palladium fine particle dispersion (90 nm) instead of silver fine particle dispersion A-2 (90 nm) of Example 1. FIG.

(Examples 8 to 14)
A photosensitive layer coating solution and a protective layer coating solution (same as the formulation of the intermediate layer coating solution) were prepared in the same manner as in Examples 1-7.
(Production of photosensitive material)
A photosensitive layer coating solution having the above formulation E was applied to a glass substrate using a spin coater so as to have a film thickness of 0.6 μm, and dried at 100 ° C. for 5 minutes. Next, a protective layer coating solution having the above-mentioned formulation D was applied onto this using a spin coater so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 5 minutes.
(Preparation of substrate with light-shielding film by liquid registration using photosensitive material)
The photosensitive material obtained above was exposed and developed in the same manner as in Example 1 to obtain a substrate with a light-shielding film.

(Examples 15 to 21)
Without a protective layer in Example 8 to 14, and except that the exposure amount was changed 500 mJ / cm ² from 70 mJ / cm ² was performed in the same manner as in Example 8-14. As a result, the same results as in Examples 8 to 14 were obtained.

( Reference Example 1 )
(Preparation of core-shell silver fine particle dispersion / acetone)
Polymer P-1 (vinyl pyrrolidone / vinyl acetate = 60/40 (mass ratio) copolymer, weight average molecular weight 5000) was added to 200 g of an acetone dispersion of silver fine particles (average particle size 30 nm, concentration 2.5 mass%). 0.95 g was added and stirred for 30 minutes.
Next, with stirring, an aqueous sodium sulfide solution having a concentration of 7.2% by mass was added so that the sulfidation rate of the metal was 10%. After addition of the aqueous sodium sulfide solution, stirring was continued for 30 minutes. In this way, silver core-shell fine particles having a silver sulfide shell were produced.
The “sulfidation rate” here is the ratio of metal fine particles that are sulfided, the sulfurization rate of 0% is not sulfided at all, and 100% is the state that the entire particle is completely sulfided. Represents. In addition, the liquid temperature at the time of sodium sulfide aqueous solution addition was 23 degreeC.

These core-shell fine particles were evaluated by the following method.
[Average particle size measurement]
100 fine particles were photographed with FE-SEM (F-900 manufactured by Hitachi, Ltd.). In each photographed image having a magnification of 30000 times, a salt diameter equal to this was determined and used as the particle diameter. The diameters obtained for 100 particles were averaged to obtain the average particle diameter (average diameter) of the particles.

[Shell weight ratio]
The weight ratio of the shell in the particles was calculated from the number of moles of silver and sulfur in the particles. The number of moles of both was determined by fluorescent X-ray analysis using a fluorescent X-ray analyzer Type 3370E (manufactured by Rigaku Corporation) on a sample obtained by spin-coating a particle dispersion on a polyethylene terephthalate temporary support. If the number of moles of sulfur and silver is ms and mA, respectively, the number of moles of Ag ₂ S in the shell is ms, and the number of moles of Ag in the core is mA-2 ms.
Therefore, the weight ratio of the shell to the core is (ms / 247.8) :( mA-2 ms / 107.9).

(Preparation of photosensitive transfer coating solution)
An additive comprising the following formulation F was added to the silver fine particle dispersion prepared above to prepare a photosensitive transfer layer coating solution.

F: Prescription fine particle dispersion of photosensitive coating liquid 159.6 parts Polymer P-2 0.19 part F780F (Dainippon Ink & Chemicals, Inc., 20% fluorine-based surfactant) 0.03 parts hydroquinone monomethyl ether 0 .0001 parts dipentaerythritol hexaacrylate 0.19 parts bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.001 part (Polymer P-2: benzyl methacrylate / methacrylic acid = 60/40 (wt / wt), number average molecular weight (35000)

(Production of substrate with light-shielding film by transfer using transfer material)
On the temporary support produced by the same method as in Example 1, the photosensitive coating solution obtained from the above formula F was applied using a slit coater so that the optical density was 3.8. The transfer material was produced by drying for a minute.
Subsequently, transfer, exposure, and development processes were performed in the same manner as in Example 1 to obtain a substrate with a light shielding film.

( Reference Example 2 )
Except for changing the sulfide ratio 30% was likewise actual subjected Reference Example 1.

( Reference Example 3 )
Except for changing the sulfide ratio of 50% was likewise actual subjected Reference Example 1.

( Reference Example 4 )
Except for changing the sulfide ratio 70%, it was similarly actual subjected Reference Example 1.

( Reference Examples 5 to 8 )
Instead of the silver particles, palladium fine particles except for using (average particle diameter 15 mm, density 10 wt%) was subjected Real similarly in the same manner as in Example 1-4.

( Reference Examples 9 to 16 )
(Production of photosensitive material)
Using a spin coater, a photosensitive coating solution having the same formulation as in Reference Examples 1 to 8 was applied to a glass substrate so that the optical density (OD) was 3.8, and dried at 100 ° C. for 3 minutes. Next, an intermediate layer coating solution composed of the above-mentioned formulation D was coated thereon so as to have a dry film thickness of 1.5 μm and dried at 100 ° C. for 3 minutes.

(Preparation of substrate with light-shielding film by liquid registration using photosensitive material)
The photosensitive material obtained above was exposed and developed in the same manner as in Example 1 to obtain a substrate with a light-shielding film.

( Reference Example 17 )
Production of substrate with light-shielding film A temporary support was produced in the same manner as in Example 1, and the optical density of the layer coating solution containing metal fine particles obtained from the following formulation G was 3.4 on the temporary support. As described above, a slit coater was applied on the intermediate layer produced in the same manner as in Example 1, and a light absorption layer obtained from the following formulation H was further applied thereon so that the optical density was 0.6. It was applied and dried at 100 ° C. for 3 minutes.
In this way, a film in which the temporary support, the thermoplastic resin layer, the oxygen barrier film, the layer containing metal fine particles and the light absorption layer are integrated is prepared, and a protective film (polypropylene film having a thickness of 12 μm) is pressure-bonded thereon. A photosensitive resin transfer material was obtained. A substrate with a light-shielding film was obtained in the same manner as in Example 1 except that the exposure amount was changed to 300 mJ / cm ² using this.

G: Formulation of layer coating solution containing fine metal particles G-1 solution * 10 parts dipentaerythritol hexaacrylate (2.5% toluene diluted solution) 0.19 parts bis [4- [N- [4- (4 6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate (0.2% toluene diluted solution) 0.1 part F780F (Dainippon Ink & Chemicals, Inc. fluorine-based surfactant) 20%) 0.2% toluene diluted solution 0.14 parts benzyl methacrylate / methacrylic acid = 60/40 (wt / wt), number average molecular weight 35000, 2.5% MEK diluted solution 0.4 parts

* G-1 solution is a heptane dispersion containing silver particles having a silver particle concentration of 30 wt% obtained by thermal reduction of silver stearate (average particle size 30 nm, distribution 5 to 50 nm, NAG manufactured by Daiken Chemical Co., Ltd. -09), 4 times the amount of toluene was added and stirred for 30 minutes. The volume (ratio) which metal silver occupies with respect to solid content of G-1 liquid at this time is 60%.

H: Formulation of coating solution for light absorption layer Benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, viscosity = 0.12, weight average molecular weight 38000) 37.9 parts pentaerythritol tetraacrylate 29.1 parts
Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 1.7 parts carbon black (black) (NIPX35, manufactured by Degussa) 30.1 parts methyl cellosolve acetate 560 parts methyl ethyl ketone 280 parts

( Reference Example 18 )
In Reference Example 17 , a substrate with a light-shielding film was produced in the same formulation and process except that the film thickness was changed so that the optical density of the light absorption layer was 1.2.

( Reference Example 19 )
In Reference Example 17 , with the same formulation and process except that the metal volume fraction of formulation G was changed to 90% by changing to a formulation that does not contain binder, monomer, and initiator of the layer containing metal fine particles. A substrate was produced.

( Reference Example 20 )
In Reference Example 17 , a substrate with a light-shielding film was produced in the same formulation and process except that the pigment carbon black (black) of the formulation H in the production of the light absorption layer was changed to nanotech Mn oxide (manufactured by C-I Kasei Co., Ltd.).

( Reference Example 21 )
In Reference Example 17 , a substrate with a light-shielding film was produced in the same formulation and process except that the intermediate layer coating solution was not applied.

( Reference Example 22 )
In Reference Example 17 , an auxiliary layer coating solution having the following formulation I was applied on a 12 μm polypropylene film using a slit coater to the prepared substrate with a light-shielding film, and the film thickness was adjusted to an optical density of 0.6. The film dried for 3 minutes at 100 ° C. was bonded using a laminator.
Using this, exposure and development were performed in the same manner as in Reference Example 17 to produce a substrate with a light shielding film with an auxiliary layer.

I: Prescription of coating liquid for auxiliary layer benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, viscosity = 0.12)
37.9 parts dipentaerythritol hexaacrylate 29.1 parts bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 1.7 Parts carbon black (black) 30.1 parts methyl cellosolve acetate 560 parts methyl ethyl ketone 280 parts

( Reference Example 23 )
In Reference Example 17 , in the same manner as in Reference Example 19 , except that the metal volume ratio of the light reflecting layer consisting of the prescription G was 90%, and the film thickness was changed so that the optical density was 4.4. A substrate with a light-shielding film was prepared by the same formulation and process.

( Reference Example 24 )
In Reference Example 17 , NAG-09 manufactured by Daiken Chemical Co., Ltd. in Formula G was changed to Ag nanometal ink Ag1T (manufactured by Vacuum Metallurgical Co., Ltd., 30 wt%, average particle size 5 nm, distribution 2 to 10 nm). In addition, the silver layer had a yellowish brown color before baking, and a silver mirror was generated after baking. Therefore, the reflectance was measured after baking. Other than that, a substrate with a light-shielding film was prepared in the same formulation and process.

( Reference Example 25 )
(Production of photosensitive material)
In Reference Example 17 , the coating method was changed. A layer coating solution containing metal fine particles composed of the above-mentioned prescription G is applied to a glass substrate using a slit coater so that the dry film thickness becomes 0.2 μm, and the light composed of the above-mentioned prescription H is applied thereon. The absorbent layer coating solution was applied and dried at 100 ° C. for 5 minutes. Next, an intermediate layer coating solution composed of the above-mentioned formulation D was coated thereon so as to have a dry film thickness of 1.6 and dried at 100 ° C. for 5 minutes.

(Preparation of substrate with light-shielding film by liquid registration using photosensitive material)
The light-sensitive material obtained above was subjected to the same exposure and development treatment as in Reference Example 17 to obtain a substrate with a light-shielding film.

(Comparative Example 1)
Comparative Example 1 was carried out in the same manner as in Example 1 except that the photosensitive layer coating solution formulation of Example 1 was changed to the following black resist coating solution, but the OD was extremely low and it was not durable.
Black resist coating solution:
-CFP-FF-775B (CI PB15: 6 dispersion manufactured by Fuji Film Orin Co., Ltd.) 4.50 parts-CFP-FF-293Y (CI PY139 dispersion liquid manufactured by Fuji Film Orin Co., Ltd.) 3.37 parts CFP-FF-802V (CI. PV23 dispersion manufactured by Fujifilm Aurin Co., Ltd.) 4.16 parts CFP-FF-949K (carbon black dispersion manufactured by Fujifilm Olin Co., Ltd.) 11 .9 parts MMPG-AC (propylene glycol monomethyl ether acetate)
18.9 parts, methyl ethyl ketone 52.0 parts, hydroquinone monomethyl ether 0.0022 parts, dipentaerythritol hexaacrylate 4.85 parts, bis [4- [N- [4- (4,6-bistrichloromethyl-s- Triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.238 parts, the following copolymer (methyl isobutyl ketone 30 wt% solution) 0.065 parts

( Reference Example 26 )
Although, except for using the fine silver particle dispersion liquid A-5 (93nm) instead of the silver particle dispersion liquid A-2 in the photosensitive layer coating liquid formulation of Example 1 was subjected real in the same manner as in Example 1, the hue of the black matrix Changed to blue, and there was a hue shift to the extent that it would be an obstacle to practical use.

( Reference Example 27 )
In Reference Example 1 , a substrate with a light-shielding film was produced in the same formulation and process as Reference Example 1 except that the sulfurization rate was changed to 0%.

( Reference Example 28 )
In Reference Example 1 , a substrate with a light-shielding film was produced by the same formulation and process as Reference Example 1 , except that the sulfidation rate was changed to 100%.

( Reference Example 29 )
In Reference Example 1 , a light-shielding film was prepared in the same formulation and process as Reference Example 1 , except that palladium particles (average particle size 15 mm, concentration 10% by mass) were used instead of silver particles, and the sulfide ratio was changed to 0%. A substrate was prepared.

( Reference Example 30 )
In Reference Example 1 , instead of silver particles, palladium particles (average particle size 15 mm, concentration 10% by mass) were used, and the light shielding film was prepared in the same formulation and process as Reference Example 1 except that the sulfurization rate was changed to 100%. A substrate was prepared.

(Reference Examples 31 to 34)
A substrate with a light-shielding film was produced in the same manner as in Reference Examples 26 to 27 , except that the coating method of Reference Examples 26 to 27 was changed to the same method as in Reference Examples 9 to 16 .

(Comparative Example 2)
In Reference Example 17 , a substrate with a light-shielding film was produced in the same formulation and process except that a layer containing metal fine particles was not produced.

( Reference Example 35 )
In Reference Example 17 , a substrate with a light-shielding film was produced in the same formulation and process except that no light absorption layer was produced.

<Evaluation>
About 58 pieces of samples obtained by the above was subjected to the following evaluation. The results are shown in Tables 1 to 3 and Tables 5 to 7.

<Film thickness measurement>
The film thickness was measured using a non-contact type surface roughness meter P-10 (manufactured by TENCOR).

<Optical density measurement>
The optical density of the film was measured by the following method. The optical density of the light-shielding film coated on the glass substrate was measured using a spectrophotometer (Shimadzu Corporation, UV-2100) (OD). Separately, the optical density of the glass substrate was measured by the same method (OD ₀ ). The value obtained by subtracting OD ₀ from OD was defined as the optical density of the film.

<Color tone measurement>
The sample was visually observed from the glass substrate side (the side opposite to the surface on which the coating film was formed).

<Reflectance measurement>
Using an absolute reflectance measuring device ARV-474 manufactured by JASCO Corporation in combination with a spectrophotometer V-560 manufactured by JASCO Corporation. Absolute reflectance was measured. The measurement angle is 5 degrees and the wavelength is 555 nm. The reflectance may be measured before and after baking except for Reference Example 24 .

<Silver volume fraction measurement>
The silver volume was calculated assuming that the specific gravity of silver was 10.5, and the calculation was performed by (silver volume / total volume) * 100 = silver volume%.

(Example 22 )
(Production of color filter: transfer method)
A substrate with a light-shielding film was produced by the same method as in Example 1, and a color filter with a light-shielding film was produced by the following method.
Four temporary supports were prepared in the same manner as in Example 1. On these temporary supports, three coating solutions for photosensitive resin layers of red, blue and green having the composition shown in Table 4 below were prepared. It apply | coated on the intermediate | middle layer of a respectively different temporary support body, and it dried and formed the photosensitive resin layer with a dry layer thickness of 2.0 micrometers.
Further, a protective sheet of polypropylene (thickness: 12 μm) was pressure-bonded on the photosensitive resin layer to prepare red, blue, and green photosensitive transfer materials.
Using this photosensitive transfer material, a color filter with a light shielding film was produced by the following method.
The protective sheet of the red photosensitive transfer material is peeled off, and the photosensitive resin layer surface is pressurized to a transparent glass substrate (thickness: 1.1 mm) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.) (0.8 kg / cm2) and heating (130 ° C.) for bonding, followed by peeling at the interface between the temporary support and the thermoplastic resin layer, and the temporary support was removed. Next, it exposed through the predetermined photomask, and removed the thermoplastic resin layer and the intermediate | middle layer with 1% triethanolamine aqueous solution. At this time, the photosensitive resin layer was not substantially developed. Next, the photosensitive resin layer was developed with a 1% aqueous sodium carbonate solution to remove unnecessary portions, and a red pixel pattern was formed on the glass substrate. Next, a green photosensitive transfer material was bonded to the glass substrate on which the red pixel pattern was formed in the same manner as described above, and peeling, exposure, and development were performed to form a green pixel pattern. The same process was repeated with the blue photosensitive transfer material to form a color filter on the substrate with the light shielding film.
In these steps, the temporary support exhibited satisfactory peelability from the thermoplastic resin layer, and the resulting color filter had no missing pixels, good adhesion to the ground, and no stains.

(Example 23 )
(Production of color filter: Liquid cash register method)
A substrate with a light-shielding film for a color filter was produced by the same method as in Example 1, and a color filter with a light-shielding film was produced by the following method.
On the substrate with a light shielding film, a red photosensitive resin composition having the formulation shown in Table 4 below was applied to the substrate with a light shielding film and dried at 100 ° C. for 3 minutes.
Subsequently, exposure and development were performed in the same manner as in Example 1 to produce a red pattern image.
Further, except for using the green photosensitive resin composition in the following Table 4 instead of the red photosensitive resin composition, the same operation as that for the red pattern image is repeated, and the red pattern image is formed on the red pattern image. A green pattern image was produced.
Subsequently, in place of the red photosensitive resin composition, the same operation as that for the red pattern image was repeated except that the blue photosensitive resin composition shown in Table 4 below was used. A blue pattern image was prepared.

(Example 24 )
<Production of plasma display>
A plasma display as disclosed in Japanese Patent Application Laid-Open No. 2003-203575 was produced using the substrate with a light-shielding film produced in Example 1.
A lower glass substrate and an insulating layer were formed on the lower glass substrate. Address electrodes were formed on predetermined portions on the insulating layer. A lower dielectric layer was formed on the entire surface of the address electrode and the insulating layer. Further, in order to separate each discharge cell, barrier ribs formed at a predetermined interval on the lower dielectric layer, and a light-shielding film prepared in Example 1 were formed on the barrier ribs.
Fluorescent layers were formed on the side surfaces of the light-shielding films and the barrier ribs and on the upper surface of the lower dielectric layer to have a predetermined thickness and emit visible light of red, green, and blue when ultraviolet light is applied. An upper glass substrate was attached in parallel to the lower glass substrate at a predetermined interval above each partition wall. Further, a sustain electrode was formed on a predetermined portion on the upper glass substrate so as to be orthogonal to the address electrode. Bus electrodes were formed on predetermined portions on the sustain electrodes, and upper dielectric layers were formed on all surfaces of the bus electrodes, the sustain electrodes, and the upper glass substrate. In addition, in order to protect the upper dielectric layer, a protective layer was formed on all surfaces on the upper dielectric layer to produce a plasma display.
As a result, the contrast of the PD display device was improved and the resolution was improved, so that a high-definition image could be obtained.

(Example 25 )
<Production of plasma display>
A plasma display as disclosed in JP-A-2001-325887 was produced using the color filter with a light-shielding film produced in Example 22 .
First, a scanning electrode and a common electrode were formed on a front substrate made of a soda lime glass transparent substrate. At this time, the scanning electrodes and the common electrodes were arranged alternately and in parallel in the row direction of the screen. The scan electrode and the common electrode are made of silver metal electrodes a and b and ITO (Indium Tin Oxide) transparent electrodes a and b. The scan electrode and the common electrode are dielectric layers made of zinc-containing frit glass, respectively. Covered.
The dielectric layer was covered with a color filter with a light-shielding film produced in Example 22 , and the dielectric layer was covered with a protective layer made of MgO (magnesium oxide).
The back substrate is made of a transparent substrate of soda lime glass like the front substrate, and a protrusion made of zinc-containing frit glass is formed at the center of the unit cell on the back substrate, and further made of silver. The data electrodes were arranged on and between the protrusions along the screen column direction so as to be orthogonal to the scan electrodes and the common electrode. The data electrode was covered with a dielectric layer made of zinc-containing frit glass, and a corrugated partition wall made of lead-containing frit glass was formed on the dielectric layer between adjacent protrusions along the column direction of the screen. Here, the unit cells are alternately arranged in the row direction of the screen in the column direction of the screen, and one unit pixel is constituted by three unit cells in the row direction.
Thereafter, phosphors R, G, and B capable of emitting light of three primary colors of red, green, and blue were alternately applied to the surface of the dielectric layer and the side surface of the wavy partition wall. (Y, Ga) BO ₃ : Eu was used as the red phosphor, Zn ₂ SiO ₄ : Mn was used as the green phosphor, and BaMgAl ₁₄ O ₂₃ : Eu was used as the blue phosphor.
The front substrate and the rear substrate are integrally assembled so that the scanning electrode, the common electrode, and the data electrode are orthogonal to each other, and the light shielding film and the corrugated barrier ribs overlap each other. A plasma display was prepared by enclosing an ultraviolet ray generating gas that generates ultraviolet rays by electric discharge. As the ultraviolet ray generating gas, a mixed gas of Ne and Xe was used.
As a result of observation, a clear image could be displayed, and the color reproducibility was improved and the contrast was improved.

Claims (2)

  A substrate with a light-shielding film for a plasma display having a light-shielding film on at least a part of at least one side of the substrate, the light-shielding film including a resin layer containing metal fine particles, The OD per 1 μm thickness at 555 nm of the film is 3 to 20, the metal fine particles contain two or more kinds of metal fine particles having different average particle diameters, and the difference between the average particle diameters is 10 nm or more A substrate with a light-shielding film for a plasma display. The plasma display using the board | substrate with the light shielding film for plasma displays of Claim 1 .