JP4602106B2 - Light shielding film for display device, production method thereof, composition containing metal fine particles, substrate for display device, and color filter - Google Patents

Description

  The present invention relates to a light-shielding film (hereinafter referred to as “light-shielding film”) provided inside a display device such as a liquid crystal display device, a plasma display device, an EL display device, or a CRT display device.

The light shielding film for a display device is a black edge provided inside a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device, or a black edge portion in a lattice shape or a stripe shape around a pixel ( This is a so-called black matrix), and also a dot-like or linear black pattern for TFT light shielding.
An example of the light shielding film for a display device is a black matrix formed around the red, blue, and green pixels of the color filter in order to prevent a decrease in contrast due to light leakage.
Another example is a light-shielding film provided on a TFT in an active matrix driving type liquid crystal display element using a thin film transistor (TFT) in order to prevent deterioration in image quality due to current leakage due to light from the TFT. These light shielding films are usually required to have a light shielding property with an optical density of 2 or more. The color tone of the light shielding film is preferably black from the viewpoint of display quality of the display device.

Conventionally, in order to produce a light shielding film for a display device having high light shielding properties, it has been 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. And then exposing and developing the photoresist layer using a photomask having a light shielding film pattern for a display device, etching the exposed metal thin film, and finally peeling 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 the cost cannot be denied. 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 light shielding film having a low reflectance (see Patent Document 1). 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. When red, blue and green pixels are formed after the formation of a light shielding film for a display device, there are disadvantages that bubbles are generated and it is difficult to form uniform pixels.
JP-A-62-9301 Published by Kyoritsu Shuppan Co., Ltd. “Color TFT LCD”, pp. 218-220 (April 10, 1997)

The present invention has been made in view of such problems of the, its object is light-shielding film for the dispersion is good display of the fine metal particles, the metal fine particle-containing composition for producing a light-shielding film及beauty the method for manufacturing a barrier light film, and to provide a substrate and a color filter for a display device.

The problems of the present invention are solved by providing the following light shielding film for a display device, a composition containing metal fine particles for producing the light shielding film, a method for producing the light shielding film, a substrate for the display device, and a color filter. Is done.
(1) a metal particulate-containing compositions for making light-blocking film for a display device, a polymeric binder, silver, gold, platinum, palladium, and metal particles selected from the group consisting of tungsten and titanium, thiol group , thioether group, a thioxo group, an amino group, or a compound having at least one imino group and a metal fine particle-containing composition S P value contains 9.0 or more solvents.
(2) The metal fine particle-containing composition as described in (1) above, wherein the metal fine particle-containing composition further contains a polymerizable monomer and a photopolymerization initiator and has photosensitivity.

(3) A light-shielding film for a display device provided on a substrate using the metal fine particle-containing composition according to (1) or (2), wherein the polymer binder is dispersed in the polymer binder. Containing finely divided metal particles selected from the group consisting of silver, gold, platinum, palladium, tungsten and titanium, and a compound having at least one of a thiol group, a thioether group, a thioxo group, an amino group, or an imino group, and having a thickness Is a light-shielding film for a display device, having an optical density of 3.5 or more.
(4) The compound having at least one kind of the thiol group, thioether group, thioxo group, amino group, or imino group is contained in an amount of 1% by mass or more of the metal fine particles. Light shielding film for display device.

( 5 ) The light-shielding film for a display device according to ( 3 ) or ( 4), comprising a step of coating the substrate containing the metal fine particle-containing composition according to ( 1 ) or (2). Manufacturing method.
( 6 ) The method for producing a light-shielding film for a display device according to ( 5 ), wherein the metal fine particle-containing composition has photosensitivity, and the metal fine particle-containing composition coated on the substrate is patterned. .

( 7 ) A light-shielding film for a display device produced by the production method according to ( 5 ) or ( 6) .

(8) the (3), (4), a display device substrate that also includes a display device for shielding film according to (7).
(9) the (3), (4), or a color filter for a display device comprising a display device for shielding film according to (7).

  Since the composition containing metal fine particles of the present invention contains a specific compound, the dispersion stability of the metal fine particles is good and the storage stability of the coating liquid is high. Moreover, by producing a light-shielding film using such a coating solution, the dispersibility of the metal fine particles in the light-shielding film is good, the film thickness for obtaining the required optical density is thin, and the color tone is excellent. A light-shielding film can be obtained. Moreover, the light-shielding film of the present invention has a small environmental load during production.

[Light-shielding film]
The light shielding film for display device in the present invention refers to a light shielding film provided inside a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. Examples thereof include black edges provided at the periphery, black edges (so-called black matrix) provided around the pixels, such as grids and stripes, dots for shielding light from the TFT, and linear black patterns.
The light-shielding film for a display device of the present invention includes both those patterned and those not patterned.
The light-shielding film contains a polymer binder, metal fine particles dispersed in the polymer binder, and a compound having at least one sulfur atom and / or nitrogen atom.

(Metal fine particles)
In the present invention, the term “metal” refers to “metal” (page 444) described in “Iwanami Physical and Chemical Dictionary (5th edition)” (published by Iwanami Shoten in 1998).
As the metal of the metal fine particles used in the present invention, silver, gold, platinum, palladium, tungsten, titanium, copper or alloys thereof are preferable from the viewpoint of safety and environmental load. Among these , fine metal particles selected from the group consisting of silver, gold, platinum, palladium, tungsten and titanium , and silver is preferable from the viewpoint of chemical stability and cost.
The metal fine particles used in the present invention may have a uniform composition or a non-uniform composition. As an example of the non-uniform composition, there can be mentioned a coating layer having a composition different from the inside on the surface. The shape of the metal fine particles used in the present invention is not particularly limited, and various shapes such as a sphere, an indeterminate shape, a plate shape, a cube, a regular octahedron, and a column shape can be used.

The average particle size of the metal fine particles used in the present invention is preferably from 3 to 3000 nm, particularly preferably from 60 to 250 nm. When the average particle size is less than 1 nm, the absorption wavelength is short, and those exceeding 3000 nm are not preferable because they may give rise to color or optical density.
There are no particular restrictions on the particle size distribution of the metal fine particles.

There are no particular restrictions on the method for producing the metal fine particles used in the present invention, and a known production method, for example, a vapor phase method such as an evaporation aggregation method or a gas phase reduction method, or a liquid phase method such as a liquid phase reduction method is employed. can do. The details are described in "Latest Trends in Technology and Application of Ultrafine Particles II" (issued by Sumibe Techno Research Co., Ltd., 2002).
Further, for example, in the case of silver fine particles (colloidal silver), a soluble silver salt is reduced with hydroquinone in a conventionally known method, for example, 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, a silver with tannic acid described in US Pat. No. 2,921,914 A method of chemically reducing silver ions in a solution, such as a method of reducing silver ions in a solution, a method of forming silver particles by electroless plating described in JP-A-5-134358, It is also possible to use a method such as an in-gas evaporation method that evaporates in an active gas and cold traps with a solvent.

(Polymer binder)
The following can be used as the polymer binder contained in the light shielding film of the present invention.
In the case of producing a light-shielding film using a non-photosensitive metal fine particle-containing composition described later, it is preferable to use a water-soluble polymer binder or an alkali-soluble polymer binder. For example, (meth) acrylic acid- (meta) containing a cellulosic polymer binder such as polyvinyl alcohol, gelatin, methylcellulose, acrylic acid and / or methacrylic acid, and further copolymerized with methyl methacrylate, ethyl acrylate, benzyl acrylate, styrene, and the like. ) Acrylate copolymers and styrene- (meth) acrylic acid copolymers are preferred.
A polymer binder comprising an alkali-soluble (meth) acrylic acid- (meth) acrylate copolymer or styrene- (meth) acrylic copolymer containing acrylic acid and / or methacrylic acid as a component, This is preferable because it can be patterned by alkali development.
The total content of acrylic acid and / or methacrylic acid in these copolymers is 10 to 60% by mass, more preferably 20 to 50% by mass.
Specific examples of these copolymers include benzyl methacrylate / methacrylic acid = (60/40), methyl methacrylate / styrene / methacrylic acid = (10/60/30), methyl methacrylate / styrene / acrylic acid / methacrylic acid = ( 20/50/15/15), benzyl methacrylate / methyl methacrylate / methacrylic acid = (40/35/35), styrene / acrylic acid / methacrylic acid = (60/20/20), and the like. However, the numbers in parentheses indicate mass ratios.
The polymer binder is preferably in a volume ratio of 0.3: 1 to 100: 1 with respect to the metal fine particles, and more preferably in the range of 1.5: 1 to 30: 1. If this ratio is too large, the light shielding film becomes thick and disadvantageous. If it is too small, the required optical density may not be obtained.
The monomer preferably has a volume ratio of 0.3: 1 to 100: 1 with respect to the metal fine particles, and more preferably in the range of 1.5: 1 to 30: 1. If this ratio is too large, the light shielding film becomes thick and disadvantageous. If it is too small, the strength of the light shielding film may not be obtained.

In the case of producing a light-shielding film using a photosensitive metal fine particle-containing composition described later, a photopolymerizable monomer and / or oligomer is included in the composition, and these photopolymerization products are added. A polymer binder is preferred. In addition, these photopolymerizable monomers and / or oligomers preferably have thermal polymerizability. In this case, curing can be further advanced by further heat treatment after photopolymerization. Further, an alkali-soluble polymer as described above may be added to the composition.
As the monomer, ethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylol It is preferable to use polyfunctional acrylic monomers such as propanetri (meth) acrylate, 1,4-hexanediol (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These polyfunctional monomers can be polymerized (crosslinked) using light or heat as described above. Among them, bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazine-] is preferable. Those which are photopolymerized using a halomethyl-s-triazine compound such as 2-yl) phenyl] carbamoyl] phenyl] sebacate as a polymerization initiator are preferred.

(Compound having at least one sulfur atom and / or nitrogen atom)
By adding a compound having at least one of a thiol group, a thioether group, a thioxo group, an amino group, or an imino group as a compound having at least one sulfur atom and / or nitrogen atom, the dispersion of metal fine particles can be stabilized. Can be improved . Thiols, thioether, thioxo group, an amino group, an imino group may be a unsubstituted or may be in a form which is substituted.
Preferred examples of these compounds include the following.

Furthermore, terminal SH group-containing polyvinyl alcohol (for example, M205, M115 manufactured by Kuraray Co., Ltd.) is also preferable.
The amount of the compound added is preferably 0.1% by mass or more of the metal fine particles, more preferably 0.3 to 100% by mass, still more preferably 3 to 30% by mass, and particularly preferably 10 to 20% by mass. In addition to the above compounds, known dispersants, dispersion stabilizers, surfactants and the like may be used.

(Other additives)
In addition to the above fine particles, the following may be added to the light-shielding film of the present invention as required.
(1) Pigment A black pigment such as carbon black can be used as the pigment. The addition amount of the pigment is preferably 50% by mass or less, and particularly preferably 30% by mass or less of the fine particles of the present invention. When the added amount of the pigment exceeds 50% by mass, the thickness of the light-shielding film necessary for obtaining a necessary optical density increases, and the quality of red, blue, and green pixels formed thereon decreases.
In addition to black, the light-shielding film of the present invention may further contain blue or other pigments for color adjustment. The addition amount of these non-black pigments is 40% by mass or less, preferably 20% by mass or less of the fine particles of the present invention. When the added amount of the non-black pigment exceeds 40% by mass, the color of the light shielding film may be deteriorated.
(2) Surfactant A surfactant can be added to the light-shielding film of the present invention for the purpose of improving coating properties and improving dispersion stability of fine particles. As the surfactant, nonionic, anionic and cationic surfactants can be used without particular limitation. Among these, anionic surfactants are particularly preferable from the viewpoint of liquid stability. A fluorosurfactant is a preferred surfactant.
Preferred examples of the surfactant include C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) ₁₄ H, C ₈ F ₁₇ SO ₃ Li, C ₇ F ₁₅ COONH ₄ , and C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OPO (OH) ₂ . Furthermore, F110, F113, F120, F150, F176PF, F177, and F780 (all are the Dainippon Ink and Chemicals Co., Ltd. make, an oligomer type fluorine-type surfactant) etc. can be mentioned.
(3)
The light-shielding film of the present invention may further contain a polymer dispersion stabilizer for improving the dispersion stability of the fine particles of the present invention. Examples of these polymer dispersion stabilizers include polyvinyl alcohol, acrylamide / acrylic acid copolymer, styrene maleic anhydride copolymer, sodium polyacrylate, and sodium alginate.
The polymer dispersion stabilizer is described in, for example, “Pigment Dispersion Technology (Technical Information Association, Inc., issued in 1999)”.

(substrate)
As the substrate used in the present invention, a glass substrate usually used in a display device is preferable. As the glass substrate, a glass substrate using known glass such as soda glass, low alkali glass, non-alkali glass or the like can be used. Examples of the glass substrate include those described in “Introduction to liquid crystal display engineering (Hanae Suzuki, published by Nikkan Kogyo Shimbun (1998))”. As other substrates, transparent plastics such as silicon wafers and polyolefins can also be used. Furthermore, a TFT substrate can also be used.
The thickness of the substrate is preferably from 0.5 to 3 mm, more preferably from 0.6 to 2 mm.

The light shielding film of the present invention has a structure in which the aforementioned fine particles are dispersed in a polymer binder. The thickness of the light shielding film is preferably 0.05 to 0.5 μm, more preferably 0.1 to 0.3 μm. If the thickness exceeds 0.5 μm, the unevenness of the substrate provided with the light shielding film (the difference between the portion provided with the light shielding film and the portion provided with no light shielding) becomes too large, and a BRG pixel is formed on this in a later step. Inconvenience occurs. Conversely, the necessary optical density of less than 0.1 μm cannot be obtained, causing problems such as a decrease in contrast of the display device.
The content of fine particles in the light-shielding film of the present invention is 5 to 70%, more preferably 10 to 50% in terms of volume fraction. The volume fraction referred to here is the ratio of the total volume of the fine particles of the present invention to the total volume of the light shielding film.
If the volume fraction is less than 5%, the film thickness exceeds 1 μm in order to obtain the necessary optics. Conversely, when the volume fraction exceeds 70%, there arises a problem that the dispersion stability of the fine particles is lowered.
The optical density of the light-shielding film of the present invention is preferably 2.0 or more, in the present invention is 3.5 or more. If the optical density is less than 2.0, the display quality of the display device such as a reduction in contrast is deteriorated.

[Metal fine particle-containing composition]
Fine metal particles-containing composition of the present invention (light-shielding film prepared coating solution), the fine metal particles selected from the group consisting of a polymeric binder, silver, gold, platinum, palladium, tungsten and titanium, and sulfur atoms and / or thiol groups a nitrogen atom as a compound having one or more, thioether group, a thioxo group, that compound SP value having at least one amino group or an imino group Yusuke contains a 9.0 or more solvents. Metallic fine particle-containing composition may be photosensitive be non-photosensitive.
<Non-photosensitive metal fine particle-containing composition>
The non-photosensitive metal fine particle-containing composition used in the present invention contains a polymer binder, metal fine particles and a compound having at least one sulfur atom and / or nitrogen atom as described above, and further contains a solvent or the like as necessary. To do.
A known organic solvent can be used as the solvent. Particularly preferred organic solvents include methyl alcohol, isopropyl alcohol, MEK, ethyl acetate, toluene and the like. Water is also preferred as the solvent. These solvents may be mixed and used as necessary.
Also, those having an SP value of 9.0 or more, which will be described later, can be used.

<Photosensitive metal fine particle-containing composition>
In addition, the photosensitive metal fine particle-containing composition used in the present invention includes a photosensitive resin composition constituting a polymer binder after photopolymerization (in addition to the photopolymerizable monomer and / or oligomer as described above, photopolymerization start A fine particle, and a compound having one or more sulfur atoms and / or nitrogen atoms. As the photosensitive resin composition, those described in paragraphs 0016 to 0022 and 0029 of JP-A No. 10-160926 can be used in addition to the photosensitive resin composition containing the monomer and / or oligomer as described above. Furthermore, other photopolymerizable monomers may be used in combination.
When metal fine particles are used as an aqueous dispersion, such as the silver colloid, the photosensitive resin composition must be aqueous. Examples of such a photosensitive resin composition include those described in paragraphs 0015 to 0023 of JP-A-8-271727, and commercially available products such as “SPP-M20”, “Toyo Gosei Kogyo Co., Ltd.” SPP-H-13 "and the like.

<Preparation of metal fine particle-containing composition>
In order to prepare the metal fine particle-containing composition (photosensitive or non-photosensitive), components such as metal fine particles, the compound, and a polymer binder (including a photosensitive resin composition) are mixed and dispersed together in a solvent. However, it is preferable to prepare a dispersion of metal fine particles in advance using the compound and add a polymer binder or the like to the dispersion.
The solvent used for the preparation of the metal fine particle dispersion is not particularly limited, and among them, those having an SP value of 9.0 or more are preferable. The “SP value” is also called a solubility parameter, and is expressed by the square root of the cohesive energy density. In the present invention, the SP value means that described in page 838 of “Adhesion Handbook” (edited by the Japan Adhesive Society, published by Nikkan Kogyo Shimbun, first published in 1971).
For example, n-hexane / 7.3, toluene / 8.9, ethyl acetate / 9.1, methyl ethyl ketone / 9.3, acetone / 10.0, ethyl alcohol / 12.7, methyl alcohol / 14.5, water /23.4. Here, the unit of the SP value is “(cal / cm ³ ) ^1/2 ”.
When using a metal fine particle dispersion having an SP value of 9.0 or more, the dispersibility is particularly good, and a sufficient optical density can be achieved even with a thin film.

The metal fine particle dispersion can be prepared by subjecting a mixture containing the metal fine particles, the compound and the solvent to a dispersion treatment using a known disperser such as a paint shaker, a ball mill, or an Eiger mill.
The metal fine particle-containing composition can be prepared by adding and mixing a binder or a photosensitive composition to the metal fine particle dispersion prepared as described above.

[Production of light shielding film]
The light-shielding film for a display device of the present invention is a method for producing a light-shielding film by applying and drying a metal fine particle-containing composition having no photosensitivity or photosensitivity on a substrate, or on a temporary support. Using a photosensitive transfer material having a photosensitive light-shielding layer formed by applying and drying the photosensitive metal fine particle-containing composition, and producing the photosensitive light-shielding layer by a method of transferring to a substrate, etc. Can do.
When the light-shielding film of the present invention is patterned, the light-shielding film or photosensitive light-shielding film produced by the method as described above is further patterned. As a patterning method, a method by exposure and development, a method of removing unnecessary portions by laser heat (ablation method), a photosensitive resist film is applied on the light-shielding film of the present invention provided on a substrate, and this is exposed and developed. There is a method of removing the photosensitive resist film after patterning. In the present invention, any of these methods can be used, but the following method is preferable from the viewpoint of simplicity of the process and resolution of patterning.
(1) A layer formed by applying and drying a non-photosensitive metal fine particle-containing composition on a substrate (hereinafter sometimes referred to as a light-shielding layer) is formed, a photoresist is applied thereon, and then exposure is performed. Method of patterning a photoresist layer by development and then dissolving and removing the light shielding layer together with the photoresist layer (2) Layer formed by applying and drying a photosensitive metal fine particle-containing composition on a substrate (Sometimes referred to as a photosensitive light-shielding layer), and patterning the photosensitive light-shielding layer by exposure and development (removing non-exposed portions) (3) photosensitive metal fine particles on a temporary support The composition is coated and dried to form a photosensitive light-shielding layer, and then the photosensitive light-shielding layer is transferred to the substrate, and the photosensitive light-shielding layer on the substrate is exposed and developed (removes the non-exposed portion). Patterning method (photosensitive transfer material A method of using a)
All of these methods can form a light-shielding film by a simpler process than conventional methods using vapor deposition or sputtering. In particular, a method using a photosensitive transfer material is a very preferable method because there is no aggregation of fine particles that occurs when a composition containing metal fine particles is stored for a long period of time.

(Application method to the substrate)
There is no restriction | limiting in particular as a coating method to the board | substrate or temporary support body of the said metal fine particle containing composition. 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.

(Exposure and development)
The exposure and development are preferably performed as follows.
The light source used for exposure is selected according to the photosensitivity of the photoresist layer or the photosensitive light-shielding layer. For example, a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or an argon laser can be used. 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.

  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% by mass to 30% by mass, and the pH is preferably 8-14. Depending on the properties such as oxidation of the photosensitive light-shielding layer of the present invention, for example, the pH of the developer can be changed so that development by film-like detachment of the present invention 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-. Examples include 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 organic solvent miscible with water is generally 0.1 to 30% by mass.

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

The developer can be used as a bath solution or a jetting solution. In order to remove the uncured portion such as the light-shielding light-shielding layer in a solid form (preferably in a film form), a method such as rubbing with a rotating brush or a wet sponge in the developer, or when the developer is sprayed A method using an injection pressure 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.

After the development step, heat treatment may be performed as necessary. By this treatment, the photosensitive light-shielding layer cured by exposure can be heated and cured to improve the solvent resistance and alkali resistance. As a heating method, a method of heating a developer substrate in an electric furnace, a dryer or the like, a method of heating with an infrared lamp, or the like can be used.
The heating temperature and heating time depend on the composition and thickness of the photosensitive light-shielding layer, 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.
In addition, after the development process, 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.

(Protective layer)
In the present invention, after the formation of the photosensitive light-shielding layer, a step of providing a protective layer on the photosensitive light-shielding layer may be added before exposure. The protective layer is provided to block oxygen during exposure and increase the sensitivity of the photosensitive light-shielding layer. For this reason, a layer mainly composed of an oxygen barrier resin such as polyvinyl alcohol is preferable. This layer is unnecessary after the formation of the light-shielding film, and is removed by development.

[Photosensitive transfer material]
The photosensitive transfer material used in the method (3) is provided with a photosensitive light-shielding layer obtained by applying and drying the photosensitive metal fine particle-containing composition on a temporary support. In the photosensitive transfer material, a thermoplastic resin layer is preferably provided between the temporary support and the photosensitive light-shielding layer, and an alkali-soluble intermediate is further provided between the thermoplastic resin layer and the photosensitive light-shielding layer. It is preferable to provide a layer.
The temporary support is preferably chemically and thermally stable and made of a flexible material. Specifically, a thin sheet of Teflon (registered trademark), polyethylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. Moreover, when providing a thermoplastic resin layer, it is preferable that peelability with this is favorable. The thickness of the support is suitably from 5 to 300 μm, particularly preferably from 20 to 500 μm.
<Thermoplastic resin layer>
Examples of the resin constituting the thermoplastic resin layer of the present invention include acrylic resins, polystyrene resins, polyesters, polyurethanes, rubber resins, vinyl acetate resins, polyolefin resins, and copolymers thereof. Although it is not essential that the resin constituting the thermoplastic resin layer of the present invention is alkali-soluble, it is desirable that the resin be alkali-soluble.

  Specific examples of the resin constituting the thermoplastic resin layer include a saponified product of ethylene and an acrylic ester copolymer, a saponified product of styrene and a (meth) acrylic ester copolymer, styrene / (meth) acrylic acid / ( (Meth) acrylic acid terpolymers, saponified products of vinyltoluene and (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, (meth) acrylic such as (meth) acrylic acid butyl and vinyl acetate Alkaline aqueous solutions of organic polymers based on saponified products such as acid ester copolymers, “Plastic Performance Handbook” (published by Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by Industrial Research Council, published October 25, 1968) At least one of those soluble in water.

These resins are preferably used as a mixture of the following two types.
That is, among these resins, the weight average molecular weight is in the range of 50,000 to 500,000 and the glass transition temperature (Tg) is in the range of 0 to 140 ° C. [hereinafter also referred to as resin (A)], more preferably weight. An average molecular weight of 60,000 to 200,000 and a glass transition temperature (Tg) of 30 to 110 ° C. can be selected and used. Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-1444615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP-A-60-159743, OLS3254254, JP-A-60-247638, JP-A-60-208748, JP-A-60-214354, JP-A-60-230135, JP-A-60-258539 JP-A 61-169829, JP-A 61-213213, JP-A 63-147159, JP-A 63-213837, JP-A 63-26 No. 448, JP-A-64-55551, JP-A-64-155550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, Japanese Patent Application No. Resins that are soluble in an alkaline aqueous solution described in each specification of Japanese Patent No. 4139653. Particularly preferred is a methacrylic acid / 2 monoethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

  Further, among the various resins described above, the weight average molecular weight is 3,000 to 30,000, and the glass transition temperature (Tg) is in the range of 30 to 170 ° C. [hereinafter also referred to as the resin (B)], and more preferably. A weight average molecular weight of 4,000 to 20,000 and a glass transition temperature (Tg) of 60 to 140 ° C. can be selected and used. Preferable specific examples can be selected from those described in the above-mentioned patent specifications, and particularly preferable are styrene / (metabolites described in JP-B-55-38961 and JP-A-5-241340. ) Acrylic acid copolymer.

  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., reticulation occurs and the thermoplastic resin protrudes to the periphery during transfer. And contaminate the permanent support. When the weight average molecular weight of the resin (A) exceeds 500,000 or the glass transition temperature (Tg) exceeds 140 ° C., bubbles are generated between pixels during transfer or the alkali aqueous solution removability of the thermoplastic resin is deteriorated.

  The thickness of the thermoplastic resin is preferably 6 μm or more. This is because if the thickness of the thermoplastic resin is 5 μm or less, it is impossible to completely absorb the unevenness of the base of 1 μm or more. The upper limit is about 100 μm or less, preferably about 50 μm or less, from the viewpoint of the ability to remove alkaline aqueous solution and the suitability for production.

  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. For example, methyl ethyl ketone, n-propanol, i-propanol and the like can be used.

Moreover, it is preferable to provide an alkali-soluble intermediate layer between the thermoplastic resin and the photosensitive light-shielding layer to prevent layer mixing of both layers during coating.
(Alkali-soluble intermediate layer)
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 photosensitive resin 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.

  In the photosensitive transfer material, since the photosensitive light-shielding layer is produced from the coating liquid containing the fine particles of the present invention as described above, it is possible to produce a light-shielding film having a thin film and high optical density. .

A method for transferring the photosensitive transfer material of the present invention to a substrate will be described. The transfer is preferably performed by laminating the photosensitive light-shielding layer and the substrate in close contact. As a laminating method, a conventionally known laminator, vacuum laminator or the like can be used. An auto-cut laminator can also be used to increase the friction. The heating temperature at the time of lamination is preferably about 60 to 150 ° C., and the pressing pressure is preferably about 0.2 to 20 kg / cm ² . In the present invention, the lamination is preferably performed at a substrate line speed of about 0.05 to 10 m / min.
After lamination, the temporary support is peeled off.

  The photosensitive transfer material of the present invention is exposed and developed after lamination to the substrate. The methods described above can be used for exposure and development.

[Display substrate]
The display device substrate of the present invention is such that the light shielding film as described above is formed on the substrate. Examples of the substrate are the same as those described above.

[Color filters for display devices]
One aspect of the color filter for a display device of the present invention is the above-described light-shielding film (black matrix) on a color filter substrate and two or more pixel groups (hereinafter simply referred to as “pixel groups”) exhibiting different colors. There is a case.) The aforementioned substrate is used as the color filter substrate. A color filter having a light-shielding film as described above is excellent in light utilization efficiency, contrast, and wiring shielding properties.
According to another aspect of the color filter for a display device of the present invention, a TFT element substrate is used as a color filter substrate, and a light shielding film and a plurality of pixel groups are provided thereon. Furthermore, another mode in the case of using a TFT element substrate as a color filter substrate is such that only a black matrix is formed on the TFT element substrate and a pixel group is provided on another light transmissive substrate. Opening ratio is good.
The pixel group can be produced by a conventional method using a plurality of types of colored photosensitive resin composition for pixel formation or a photosensitive transfer material for pixel formation. Heat treatment is preferably performed after the pixel group is formed.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Examples 1-5
(Preparation of metal fine particle dispersion)
7.5 g of silver fine particles with an average particle size of 30 nm, 50 ml of the dispersion medium (water) listed in Table 1, and the above-mentioned compound of the type and amount listed in Table 1 are placed in a glass bottle with a capacity of 100 ml together with 35 g of 3 mm diameter glass beads. Then, dispersion treatment was performed for 2 hours using a paint shaker.

(Coating solution for black matrix preparation)
2 g of SPP-H-13 (photosensitive resin manufactured by Toyo Gosei Co., Ltd.) was added to 10 g of each of the metal fine particle dispersions to prepare a coating liquid for preparing a black matrix having photosensitivity.
(Production of black matrix)
Each black matrix preparation coating solution prepared as described above was applied to a glass substrate having a thickness of 1.1 mm, and then dried at 100 ° C. for 5 minutes. The coating thickness was such that the optical density of the dried film was 3.6.
Pattern exposure at 500 mJ / cm ² was performed from the coated surface side of the substrate through a black matrix production photomask using an ultrahigh pressure mercury lamp. Next, development processing (33 ° C., 20 seconds) was performed using an alkali developing solution TCD (manufactured by Fuji Photo Film Co., Ltd.) to obtain a black matrix.

Example 6 and Comparative Examples 4-6
A silver fine particle dispersion used in Example 6 and Comparative Examples 4 to 6 was prepared in the same manner as in Example 1 except that the compound and the dispersion medium were changed as shown in Table 1. The following photosensitive composition was added to 40 g of this silver fine particle dispersion to prepare a coating solution for preparing a black matrix.
(Photosensitive composition)
Surfactant (Dai Nippon Ink Chemical Co., Ltd. F176PF, 20% solution) 0.2g
0.001 g of hydroquinone monomethyl ether
Dipentaerythritol hexaacrylate 0.28g
Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.05 g

Moreover, the protective layer coating liquid of the following composition was prepared.
(Preparation of protective layer coating solution)
Polyvinyl alcohol (Kuraray Co., Ltd., PVA205) 3.0g
Polyvinylpyrrolidone (GAP Corporation, PVP-K30) 1.3g
Distilled water 50.7g
Methyl alcohol 45.0g

(Production of black matrix)
The black matrix preparation coating solution prepared as described above was applied to a glass substrate having a thickness of 1.1 mm, and then dried at 100 ° C. for 5 minutes. The coating thickness was such that the optical density of the dried film was 3.6. Next, a protective layer coating solution was applied onto this with a spin coater so that the dry film thickness was 1.5 μm, and then dried at 100 ° C. for 5 minutes.
From the coated surface side of the substrate, pattern exposure at 100 mJ / cm ² was performed using an ultrahigh pressure mercury lamp. Next, development processing (33 ° C., 20 seconds) was performed using an alkali developing solution TCD (manufactured by Fuji Photo Film Co., Ltd.) to obtain a black matrix.

Comparative Examples 1-3
A black matrix was prepared in the same manner as in Example 1 except that the compound and the dispersion medium were changed as shown in Table 1.

[Evaluation of dispersibility and optical density of silver fine particles in black matrix]
Table 1 shows the dispersibility of the silver fine particles, the thickness of the black matrix, and the color tone in Examples 1 to 9 and Comparative Examples 1 to 3.
Evaluation of the dispersibility of the silver fine particles was performed by applying a silver fine particle dispersion on a glass substrate using a spin coater immediately after preparation, and observing with a light microscope what was dried at 100 ° C. for 2 minutes. By evaluating the dispersibility of the silver fine particles, the dispersibility of the silver fine particles in the silver fine particle dispersion and in the black matrix can be evaluated.
The evaluation of dispersibility was classified into 5 ranks from A to E. The photographs shown in FIGS. 1A to 1E show dispersion states corresponding to ranks A to E, respectively. The ranks A and B are practically acceptable.
The film thickness indicates the film thickness necessary to achieve an optical density of 3.6. For the measurement of the film thickness, a sample coated with a black matrix preparation coating solution was exposed to 100 mJ / cm ² from the coated surface side using an ultra-high pressure mercury lamp, and the thickness of the sample after exposure was touched. Measurement was performed using a needle type surface roughness meter P-1 (manufactured by TENKOP).
The color tone was evaluated by visual observation of the black matrix.

As Table 1 and FIG. 1 show, since the coating liquid of the present invention contains a specific compound, the dispersibility of the silver fine particles is good, and the dispersibility of the metal fine particles in the obtained black matrix is good. As a result, the black matrix can obtain a necessary optical density with a thin film thickness. Furthermore, the color tone of the black matrix is also black and good.
On the other hand, in Comparative Examples 1 to 3 in which the black matrix was produced without using the compound of the present invention, not only the dispersibility of the silver fine particles in the black matrix was poor, but also the film thickness of the black matrix was thick and the color tone was also high. A black color is not obtained, which is bad.
In addition, when the silver fine particle dispersions (Examples 1 to 6) were prepared using a dispersion medium having an SP value of 9.0 or more, the dispersibility of the silver fine particles in the black matrix is particularly good. The required optical density can be achieved with a thin film thickness.

FIG. 1A is a photograph showing a dispersion state of silver fine particles, and FIGS. 1A to 1E show dispersion states of ranks A to E, respectively.

Claims (9)

A metal fine particle-containing composition for producing light-blocking film for a display device, and the fine metal particles selected from the group consisting of a polymeric binder, silver, gold, platinum, palladium, tungsten and titanium, thiol group, thioether group , thioxo group, an amino group, or a compound having at least one imino group and a metal fine particle-containing composition S P value contains 9.0 or more solvents. The metal fine particle-containing composition according to claim 1 , wherein the metal fine particle-containing composition further contains a polymerizable monomer and a photopolymerization initiator and has photosensitivity.   A light-shielding film for a display device, which is provided on a substrate using the metal fine particle-containing composition according to claim 1 or 2, comprising a polymer binder, silver, gold dispersed in the polymer binder A fine metal particle selected from the group consisting of platinum, palladium, tungsten and titanium, and a compound having at least one of a thiol group, a thioether group, a thioxo group, an amino group, or an imino group, and having a thickness of 0.05 to A light-shielding film for a display device having an optical density of 3.5 μm or more at 0.5 μm.   4. The display device according to claim 3, wherein the compound having at least one of the thiol group, thioether group, thioxo group, amino group, or imino group is contained in an amount of 1% by mass or more of the metal fine particles. Light shielding film.   The method for producing a light-shielding film for a display device according to claim 3 or 4, further comprising a step of coating the substrate containing the metal fine particle-containing composition according to claim 1 or 2.   6. The method for producing a light-shielding film for a display device according to claim 5, wherein the metal fine particle-containing composition has photosensitivity, and the metal fine particle-containing composition coated on the substrate is patterned.   A light-shielding film for a display device produced by the production method according to claim 5.   A display device substrate comprising the light shielding film for a display device according to claim 3, 4, or 7.   A color filter for a display device, comprising the light-shielding film for a display device according to claim 3, 4, or 7.