JP4393399B2 - Photosensitive composition - Google Patents

Description

The present invention relates to a photosensitive composition.

A color filter used for a color liquid crystal display or the like has a color pixel layer (R, G, B) formed on a transparent substrate, and a gap between each color pixel of R, G, B (red, green, blue). In order to improve display contrast, a light shielding layer for a display device is formed. In particular, in an active matrix liquid crystal display element using a thin film transistor (TFT), a light shielding layer for a display device is required to have a high light shielding property in order to prevent deterioration in image quality due to current leakage due to light from the thin film transistor. The
As a method for forming a light shielding layer for a display device, for example, when a metal film such as chromium is used as a light shielding layer, a metal thin film is produced by vapor deposition or sputtering, and a photoresist is applied on the metal thin film. Then, a method of forming by exposing and developing the photoresist layer using a photomask having a light shielding layer pattern for a display device, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film. It is known (for example, refer nonpatent literature 1).

  Since this method uses a metal thin film, the obtained light-shielding layer for a display device can achieve a high light-shielding effect even when the film thickness is small, but at the time of manufacture, a vacuum film-forming process typified by vapor deposition or sputtering is used. There is a problem that an etching process using a liquid or a liquid is required, which increases costs and cannot be ignored. 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.

Further, as another method for forming a light shielding layer for a display device, a method using a photosensitive resin composition containing a light shielding pigment, for example, carbon black, is also known. Specifically, for example, R, After forming G and B pixels, a carbon black-containing photosensitive resin composition is applied onto the pixels, and the entire surface is exposed from the R, G, B pixel non-formation side of the transparent substrate. A method for forming a light shielding layer for an apparatus is known (for example, see Patent Document 1).
Although this method has a lower manufacturing cost than the method by etching the metal film, there is a problem that the film thickness is increased in order to obtain sufficient light shielding properties. There is concern that overlapping (steps) with R, G, and B pixels will occur, the flatness of the color filter will deteriorate, and cell gap unevenness will occur in the liquid crystal display element, leading to display defects such as color unevenness.
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 the above-described problems, and an object of the present invention is to provide a photosensitive composition capable of producing a light-shielding layer for a display device at a low cost with a thin film having high light-shielding performance. There is .

This object is achieved by providing a light shielding layer prepared photosensitive composition of the following display devices.
<1> A photosensitive composition comprising two or three silver deposition nuclei containing a sulfide, a photopolymerization initiator, a photopolymerizable monomer, and a binder.

According to the photosensitive composition of the present invention, a light-shielding layer for a display device can be produced at a low cost with a thin film having high light-shielding performance .

Hereinafter, the present invention will be described in detail.
[Photosensitive composition for producing light shielding layer for display device]
First, the photosensitive composition of this invention is demonstrated. The photosensitive composition of the present invention is characterized in that it contains two or three kinds of silver deposition nuclei containing sulfide , a photopolymerization initiator, a photopolymerizable monomer, and a binder. It can be suitably used as an image receiving layer for forming a nucleus-containing layer and a light shielding layer for a display device. These components will be described sequentially.

(Silver deposition nucleus)
The silver-deposited nuclei containing sulfide that can be used in the present invention can be obtained by carrying out according to a method for preparing a silver halide emulsion well known in the photographic industry. In principle, sulfide nuclei can be prepared by reacting a sulfide ion solution with a metal ion solution or a single solution of each, and the nuclei thus obtained can be applied to the present invention.
Silver deposition nuclei containing sulfides are compounds that help the developing agent reduce the transferable silver complex diffused from the silver halide emulsion layer to form silver fine particles. Specific examples of silver deposition nuclei containing sulfides include heavy metals such as iron, lead, zinc, nickel, tin, copper, chromium and cobalt, gold, silver (including colloidal silver), precious gold such as platinum and palladium. include sulfides genus, for example mercury, copper, zinc, silver, sulfides such as palladium. Further, selenides of the above heavy metals and noble metals can also be mentioned as preferred embodiments. For example , selenides such as lead, zinc and antimony are also preferable silver deposition nuclei. Among these, in particular, gold, platinum, sulphides of palladium are preferred.

As a compound that can be a sulfide ion for forming a silver deposition nucleus containing sulfide, for example, water-soluble sulfides such as sodium sulfide and potassium sulfide are preferable, but organic compounds such as acetone, diacetone alcohol, and methanol are preferable. It may be an ion-containing compound that is soluble in a solvent or a mixed solvent of these organic solvents and water and that can form sulfides with metal ions.
As the compound capable of becoming palladium ion, for example, a water-soluble palladium compound such as sodium salt or potassium salt of chloropalladic acid is preferable, but an organic solvent such as acetone, diacetone alcohol or methanol, or these organic solvent and water. It may be a palladium compound that is soluble in the mixed solvent. As the compound capable of becoming a gold ion, for example, chloroauric acid or a water-soluble salt thereof is preferable, but a gold compound which is soluble in an organic solvent such as acetone, diacetone alcohol or methanol or a mixed solvent of these organic solvent and water may be used. Good.

  In order to prepare a mixed nucleus containing a plurality of types of metals such as palladium sulfide and gold sulfide, for example, a binder solution and a sulfide ion solution described later are placed in a charging vessel in advance, and palladium and gold are stirred while stirring. , A method of adding a mixed solution of a plurality of metal ions used to form a mixed nucleus, a mixed solution of a binder solution and a plurality of metal ions are put in advance in a feed trough, and a sulfide ion solution is added while stirring A method or a method such as a method in which only a binder solution is added in advance to a charging bowl and a mixed solution of a plurality of metal ions and a sulfide ion solution are added simultaneously or with a time difference while stirring may be used.

The silver deposited nuclei containing sulfide thus obtained are preferably contained in the photosensitive composition of the present invention in an amount of 1 to 30% by mass, and more preferably in the range of 3 to 20% by mass. The quantification of the deposited nuclei can be carried out using a fluorescent X-ray measurement apparatus such as X-RAY SPECTROMETER 3370 manufactured by Rigaku.

(Photopolymerization initiator)
Since the photosensitive composition of the present invention is cured by exposure to form a pattern, a photopolymerization initiator capable of generating an initiation species by exposure, and a photopolymerizable monomer that cures by causing a polymerization reaction by the initiation species including the door.
Examples of the photopolymerization initiator that can be used in the present invention include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660 and acyloin ether compounds described in US Pat. No. 2,448,828. , Aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549,367 A combination of a triarylimidazole dimer and a p-aminoketone described in the specification, a benzothiazole compound and a trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, and described in US Pat. No. 4,239,850 Trihalomethyl-s-triazine compounds, US Pat. No. 42 Like trihalomethyl oxadiazole compounds described in 2976 Pat the like. Of these, trihalomethyl-s-triazine, trihalomethyloxadiazole, triarylimidazole dimer, Michler's ketone, and benzyldimethyl ketal are particularly preferable.
These photopolymerization initiators may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the photosensitive composition of the present invention is preferably 0.5 to 20% by mass, more preferably 2 to 15% by mass in terms of solid content, from the viewpoints of sensitivity and formed image strength. It is.

In the present invention, a polymer compound having photosensitivity can also be used as a photopolymerization initiator. Examples of such a photosensitive polymer compound include those containing a cinnamoyl group or a maleimide group, which are photosensitive groups, in the structure of the polymer compound.
Specific examples include photosensitive polymer compounds described in JP-A-2-157762, British Patent Nos. 1112277, 13131390, 1341004, and 1377747.
Such a photosensitive polymer compound can be used in place of or in addition to the photopolymerization initiator. The preferable addition amount of the photosensitive polymer compound in the photosensitive composition is in the range of 20 to 80% by mass in terms of solid content.

(Photopolymerizable monomer)
As the photopolymerizable monomer need use in the present invention has at least one addition-polymerizable ethylenically unsaturated group in the molecule and a boiling point compounds described above 100 ° C. at atmospheric pressure and the like.
Specifically, for example, monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate;
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (( (Meth) acryloyloxypropyl) ether, tri ((meth) acryloyloxyethyl) isocyanurate, tri ((meth) acrylic Yl oxy-ethyl) cyanurate, glycerin tri (meth) acrylate, after obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerol (meth) those who acrylated;

Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-37 Polyfunctional (meth) acrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and the like described in each publication of No. 52-30490.
Among these, from the viewpoint of polymerizability and film strength after polymerization, more preferred examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol pentane. Mention may be made of (meth) acrylates.
The content of the photopolymerizable monomer in the photosensitive composition of the present invention is preferably 20 to 80% by mass, more preferably 40 to 60% by mass in terms of solid content, from the viewpoint of the balance between film strength after polymerization and developability. %.

(binder)
The photosensitive composition of the present invention, from the viewpoint of film property improvement and improved removability of unexposed portions, it contains an alkali-soluble binder.
As the alkali-soluble binder that can be used in the present invention, specifically, compounds selected from the following broad types of polymer compounds can be used in combination. As compounds that can be combined, silver deposition nucleus dispersibility is good and compatibility with photopolymerizable monomers and photopolymerization initiators is good, alkali developer solubility, organic solvent solubility, strength, softening temperature. It is preferable to appropriately select those that are suitable for the correlation with other combined components.

As such an alkali-soluble binder, specifically, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester, a styrene / maleic anhydride copolymer, and the copolymer and alcohols A copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferably used.
The weight average molecular weight of the binder is preferably in the range of 5,000 to 200,000.
A plurality of binders may be used in combination, but the preferable content of the binder in the photosensitive composition is in the range of 20 to 80% by mass with respect to the total solid content as the total amount of the binder.

In addition to the above components, various components such as a thermal polymerization inhibitor, a solvent, and an adhesion promoter can be further added to the photosensitive composition of the present invention as necessary.
The thermal polymerization inhibitor is a composition that exhibits stable storage when a combination of an addition polymerizable unsaturated monomer (corresponding to the photopolymerizable monomer of the present invention) and a photopolymerization initiator as described above is used as the photosensitive component. Specific examples include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis ( 3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

[Photosensitive transfer material for image-receiving layer preparation for forming light-shielding layer for display device]
Next, a description will be given image-receiving layer (photosensitive silver deposition nuclei containing layer) fabrication photosensitive transfer material for forming a light shielding layer for Viewing device.
A photosensitive transfer material for preparing an image receiving layer can be obtained by forming an image receiving layer comprising the photosensitive composition of the present invention on a support.
The transcription material, on a support, may be those provided sequentially at least a layer containing silver halide, a silver deposition nuclei containing layer formed by the photosensitive composition, addition, inversion A photographic material, that is, a support provided with only an image receiving layer may be used, and a silver halide emulsion layer may be applied to the surface of the image receiving layer to form an image.
In any transfer material, when image formation is performed by transferring to a permanent support such as a glass substrate, that is, when a light shielding layer for a display device described later is formed, a silver halide emulsion layer is formed on the image receiving layer. It is preferable to provide the stacked layers.

The support in the transcription material, a temporary support, during image formation, or be removed after imaging is general. Examples of such a support, using a polyester, a known supports such as polystyrene be able to. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability. The thickness of the support is preferably about 15 to 200 μm, more preferably about 30 to 150 μm, from the viewpoints of shape stability, dimensional stability against heating during the lamination step, and cost.
The temporary support may be provided with a conductive layer as described in JP-A-11-149008 as required.
Viewing apparatus for shielding layer image receiving layer fabrication photosensitive transfer material of the photosensitive composition of the present invention as described above, dissolved in a suitable solvent, the support (may be a temporary support) above It is obtained by forming an image receiving layer for preparing a light shielding layer for a display device by coating and drying.

  Examples of solvents that can be used for coating the photosensitive composition include benzene, toluene, xylene, cyclohexane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate. , Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, methanol , Ethanol, 1-propanol, 2-propanol, butanol, se - butanol, t-butanol, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, .gamma.-butyrolactone, .epsilon.-caprolactam, dimethyl sulfoxide, hexamethylphosphoramide, water, and the like can be listed. These may be used alone or as a mixture of two or more depending on the purpose.

The coating method is not particularly limited, and known methods such as a spinner (spin method, slit and spin method), a winder, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder (FAS method, etc.), etc. It can form by apply | coating and drying using an applicator. In the case where a layer of an alkali-soluble thermoplastic resin described later is provided, the layer can be similarly formed.
The coating amount of the image receiving layer is appropriately selected according to the purpose, but in general, the coating amount after drying is preferably 0.2 to 2.0 μm.

Coated in the transcription material, on the image-receiving layer containing silver deposition nuclei, improving luster and smoothness of the surface, or in order to prevent damage of the silver deposition nuclei containing image-receiving layer, a release layer or a protective layer May be.

(Thermoplastic resin layer)
In transcription material, support and image-receiving layer, or between the intermediate layer described later and the support, it is preferable to provide a thermoplastic resin layer.
The thermoplastic resin layer plays a role as a cushioning material that can absorb irregularities on the surface of the support, or irregularities on the underlying surface such as irregularities caused by images already formed. It is preferable to be formed of a resin having a property that can be deformed according to the above.
Preferred resins for use in the thermoplastic resin layer, a phenol resin, a polyamide resin, fluorine resin, polyacetal resin, ABS resin, polyimide, polyethylene, polyvinyl chloride, polycarbonate resin, methacrylic resin, polypropylene, polystyrene, urea resin, epoxy resin, Examples include diallyl phthalate resin and PRO NORYL resin. Specifically, “Handbook of Polymer Materials” (published by Corona, edited by The Society of Polymer Science, published February 20, 1978), Table 1, Table 102. 1 and the resin described in Table 103 on page 103.
Among the above resins, the thermoplastic resin layer film and improving, it is preferable to use the alkali-soluble thermoplastic resin from the viewpoint of removability of improvement of the unexposed portion, the alkali-soluble thermoplastic made of such a resin It is preferable to provide a resin layer.

  Examples of the resin contained in the alkali-soluble 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, vinyltoluene and (meta ) Saponified product with acrylic ester copolymer, poly (meth) acrylic ester, and saponified product such as (meth) acrylic ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. At least one kind is preferable, but the organic polymer described in “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968) Of these, those soluble in an alkaline aqueous solution can also be used. Of these thermoplastic resins, those having a softening point of 80 ° C. or less are preferable. In the present specification, both or one of acrylic acid and methacrylic acid may be referred to as “(meth) acrylic acid”, and the same applies to derivatives thereof.

As a component of the thermoplastic resin layer, it is preferable to select and use the above-described resin having physical properties of a weight average molecular weight of 50,000 to 500,000 (Tg = 0 to 140 ° C.), and a weight average molecular weight of 6 It is more preferable to select and use in the range of 10,000 to 200,000 (Tg = 30 to 110 ° C.).
Specific examples of resins that can be used include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-B-61-134756, JP-B-59-144615. 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 Nos. 448, 64-55551, 64-155550, 2-191955, 2-199403, 2-199404, 2-208602 Resins that are soluble in the alkaline aqueous solution described in the book. Particularly preferred is a methacrylic acid / 2 monoethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

Moreover, as a component of a thermoplastic resin layer, it is resin which has the physical property of the weight average molecular weight 50,000-500,000 mentioned above, and above-mentioned resin, Comprising: Weight average molecular weight 3,000-30,000 (Tg = 30-170 degreeC) ) Having physical properties are preferably selected and used in combination, and more preferably selected and used in a weight average molecular weight range of 4,000 to 20,000 (Tg = 60 to 140 ° C.).
These preferred specific examples can be selected from those described in the above patent specifications, and particularly preferably described in JP-B-55-38961 and JP-A-5-241340. Styrene / (meth) acrylic acid copolymer.

In addition, in the organic polymer composition constituting these thermoplastic resin layers, various plasticizers, various polymers and supercooling substances, adhesion improvers or surfactants are used in order to adjust the adhesive strength with the support. It is possible to add a release agent or the like.
Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono ( Addition reaction product with (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of rate, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate.
The amount of the plasticizer in the alkali-soluble thermoplastic resin layer is generally 200% by mass or less, preferably 20 to 100% by mass with respect to the thermoplastic resin.
The thickness of the alkali-soluble thermoplastic resin layer is preferably 6 μm or more. If the thickness of the thermoplastic resin is 6 μm or more, irregularities on the base surface can be completely absorbed. Further, the upper limit is generally about 100 μm or less, preferably about 50 μm or less, from the viewpoint of developability and production suitability.

  In the present invention, the solvent for the thermoplastic resin layer can be used without particular limitation as long as it can dissolve the resin constituting the layer, and examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, and isopropanol. It is done.

(Middle layer)
In sensitive optical transfer material, an intermediate layer may be provided between the support and the image receiving layer. This intermediate layer preferably functions as a protective layer of the image receiving layer, that is, an oxygen blocking layer after the transfer.
The resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble. Examples of the resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Further, a resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is not usually alkali-soluble, such as polyester, can also be used.

You may add additives, such as surfactant, to an intermediate | middle layer as needed.
The thickness of the intermediate layer is preferably from 0.1 to 5 μm, more preferably from 0.5 to 3 μm, from the viewpoint of a balance between oxygen barrier properties and removability of the intermediate layer during development.
The coating solvent for the intermediate layer is not particularly limited as long as the above resin dissolves, but water is preferable. A mixed solvent obtained by mixing the aforementioned water-miscible organic solvent with water is also preferable. Preferred examples 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 (Here, the mixing ratio represents the mass ratio.)

Sensitive light transfer material is on one side of the support was coated an image receiving layer containing silver deposition nuclei, on the other side of the support may be a back layer is coated. Further, a protective layer may be provided between the alkali neutralization layer and the neutralization timing layer on the image stabilizing layer and the image receiving layer containing silver deposition nuclei. When cellulose ester is used as the binder for silver deposition nuclei, the cellulose ester is hydrolyzed with an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, the alkaline water / alcohol mixed solution or the alkaline alcohol solution. It is preferable to make all or a part of the hydrophilic regenerated cellulose because an alkaline developer and a silver ion complex can easily penetrate and diffuse into the image receiving sheet.

  To improve the storage stability of the silver image formed in the present invention. A layer for capturing halide ions may be provided between the silver-deposited nucleus-containing image-receiving layer and the support. For example, an image preservability improving agent as described in JP-A-59-231537 may be used. You may make it contain in an image receiving layer.

(Processing method)
Transcription material obtained as described above is used by being cut to a desired size, processing method at that time, i.e., no particular restriction on the cutting method in processing, known methods can be used .

[Light-shielding layer for display device and method for producing the same]
The photosensitive silver deposited nucleus-containing layer or the photosensitive silver deposited nucleus-containing image receiving layer is imagewise exposed and developed to form a hardened silver deposited nucleus containing layer or image receiving layer on the pattern only in the exposed area.
By making the silver halide emulsion act on this silver deposition nucleus, silver is deposited on the silver deposition nucleus, the patterned silver deposition nucleus-containing layer or the image receiving layer is colored, an image is formed to form a silver deposition laminate, and light shielding Acts as a layer. This light shielding layer region can be used as a light shielding layer for a display device.
That is, the light shielding by using the tables shown apparatus for shielding layer image-receiving layer prepared photosensitive composition and, photosensitive compositions Viewing apparatus for shielding layer image receiving layer fabrication photosensitive transfer material used as the image-receiving layer it can be obtained Viewing apparatus for shielding layer by forming a layer.
Viewing apparatus for shielding layer can be obtained by the following manufacturing method.

  A first production method includes a silver deposition nucleus-containing layer, comprising at least one silver deposition nucleus, a photopolymerization initiator, a photopolymerizable monomer, and an alkali-soluble binder on a light-transmitting substrate. A step of forming an image, an exposure step of imagewise exposing this to cure the exposed portion, a development step of removing the image forming layer in the unexposed portion with a developing solution, and silver deposition by applying a silver complex processing solution Through the step of depositing silver on the core, an image portion, that is, a patterned light-shielding layer is formed to be a light-shielding layer for a display device.

The second manufacturing method is as follows.
Forming a photosensitive silver deposition nucleus-containing layer containing at least one rare silver deposition nucleus, a photopolymerization initiator, a photopolymerizable monomer, and a binder on a light-transmissive substrate; and a silver halide solvent. An image portion, that is, a patterned light-shielding layer is formed by applying a silver complex treatment solution to deposit silver on the silver deposition nucleus and a step of forming a silver deposition pattern by exposure / development. Thus, a light shielding layer for a display device is obtained.

[Silver halide emulsion]
The silver halide emulsion will be described. The silver halide emulsion is a photosensitive composition comprising a photosensitive layer containing one or more silver halide emulsions formed on a support in contact with the image receiving layer, or a silver halide emulsion containing a silver halide emulsion on the surface of the image receiving layer. What is necessary is just to apply by apply | coating an object coating liquid.
Any silver halide emulsion known in the field of silver salt photography can be used. As the silver halide, highly sensitive silver iodobromide (iodine content of 1 to 10 mol%) is particularly preferable. These can be used by being dispersed in an appropriate protective colloid material such as gelatin, casein, albumin, polyvinyl alcohol, polyacrylamide and the like.
Emulsions suitable for such applications are P. Glafkides, Chimie et Physique Photograph, Paul Montel, 1967, G.F. F. Duffin), Photographic Emulsion Chemistry (published by The Focal Press, 1966), V. L. Zelikman et al., Making and Coating. Photographic Emulsion (Making and Coating Photographic Emulsion, The Focal Press) It can be prepared by the method described in the company publication, 1964).

These silver halide emulsions can be subjected to chemical sensitization, spectral sensitization and supersensitization as required.
Antifoggants, hardeners, development accelerators, surfactants, antistatic agents, and the like can also be added.
The silver halide emulsion is preferably added in advance to the silver complex treatment solution or coated on the silver deposition nucleus-containing layer using a binder such as gelatin or PVA.

[Silver complex treatment solution]
The silver halide solvent used in the silver complex treatment solution of the present invention will be described. As the silver halide solvent, those used as “fixing agents” in the field of silver salt photography can be used.
Specific examples include thiosulfate and cyanate, and sodium thiosulfate, ammonium thiosulfate, sodium cyanate, and the like can be used. A combination of a cyclic imide and ammonia or an amine, such as a combination of uracil and an amine, is also a preferred silver halide solvent.
In addition to the silver halide solvent, the silver complex treatment solution of the present invention may contain a silver halide developing agent and an alkali agent as necessary.

  Suitable silver halide developing agents include benzene derivatives in which at least two hydroxyl and / or amino groups are substituted at the octo or para position of the benzene nucleus, such as hydroquinone, amidol, metol, glycine, p-aminophenol and pyrogallol and Hydroxylamines, especially primary and secondary aliphatic and aromatic N-substituted or β-hydroxylamines, which are soluble in aqueous alkali, such as hydroxylamine, N-methylhydroxylamine, N-ethyl Hydroxylamine and N-alkoxyalkyl substituted hydroxylamines such as those described in US Pat. No. 2,857,276 and those described in US Pat. No. 3,293,034 are included. Hydroxylamine derivatives having a tetrahydrofurfuryl group described in JP-A-49-88521 can also be used. In addition, amino reductones described in West German Patent (OLS) No. 2,009,054, No. 2,009,055 and No. 2,009,078, and U.S. Pat. No. 4,128,425. Heterocyclic amino reductones are also used. Further, tetraalkylredactic acid described in US Pat. No. 3,615,440 can also be used.

Further, the above developer can be used in combination with the auxiliary developer phenidone compound, p-aminophenol compound and ascorbic acid. Suitable silver halide solvents include conventional fixing agents such as sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate and those described in US Pat. No. 2,543,181, and combinations of cyclic imides and nitrogen bases. Examples include barbiturates, or combinations of uracil and ammonia or amines, and combinations as described in US Pat. No. 2,857,274.
Alternatively, silver halide can be added to the processing element to develop the patterned silver deposition nuclei.

In the present invention, the alkali agent used in the silver complex treatment liquid can be used without particular limitation as long as it is a substance that increases the pH of the silver complex treatment liquid, but sodium hydroxide and potassium hydroxide are preferred.
The silver complex treatment solution of the present invention is preferably treated at 0 ° C. to 50 ° C., more preferably 5 ° C. to 35 ° C. for 10 seconds to 30 minutes, more preferably 15 seconds to 10 minutes.
If the processing temperature is too low or the processing time is too short, the optical density of the light-shielding layer may be insufficient. Conversely, if the processing temperature is too high or the processing time is too long, the color tone of the light-shielding layer may deteriorate or reflectivity May increase.
In the silver complex treatment of the present invention, the silver complex treatment solution is preferably used in such an amount that silver is deposited in an amount of about 100 g to 100000 g, more preferably about 500 g to 5000 g per 1 g of the silver deposition nucleus. If the amount is too small, the optical density of the light shielding layer may be insufficient, and if the amount is too large, it is disadvantageous in terms of cost.

Sensitive light transfer material, since the provided photosensitive light shielding layer from the such image-receiving layer composition, from now on, making a thin film a and the display device for the light-shielding layer having a high optical density shielding layer Can do.

  The thickness of the light shielding layer constituting the light shielding layer for a display device of the present invention thus prepared is about 0.2 to 1.0 μm, preferably 0.6 μm or less. Since the light-shielding layer in the light-shielding layer for a display device according to the present invention is formed by depositing silver deposition nuclei having a high hiding power, even a thin film as described above has a sufficient optical density.

In order to form such a light-shielding layer in a pattern suitable for the light-shielding layer for a display device, this image-receiving material may be exposed through a photomask for the light-shielding layer for display device and then developed in a conventional manner. By this pattern exposure, only the exposed portion of the image receiving layer made of the photosensitive composition for producing a light-shielding layer image-receiving layer for a display device that contains silver deposition nuclei that are color forming elements is cured.
In order to color the formed image-receiving layer, the silver halide emulsion may be applied, but the method is arbitrary.

In order to apply the silver halide emulsion by the transfer method, a laminated material having a photosensitive layer containing a silver halide emulsion is prepared on a light-transmitting substrate, and an image receiving layer comprising the photosensitive composition of the present invention is prepared. After exposure / development through a photomask for a light-shielding layer for a display device, the photosensitive layer is arranged and laminated so that the photosensitive layer is in contact with the surface of the formed image-receiving layer pattern. A method of peeling and forming a light shielding layer for a display device may be employed.
Further, after exposing and developing a transfer material comprising the photosensitive composition of the present invention through a photomask for a light shielding layer for a display device, a composition coating solution containing a silver halide emulsion is applied to the surface of the image receiving layer pattern. Then, after applying for a predetermined time, by removing the coating liquid, the cured pattern can be colored to form a light shielding layer to obtain a light shielding layer for a display device. Further, after exposure through a photomask for a light-shielding layer for a display device, a developing solution containing a silver halide emulsion on the surface of the image-receiving layer pattern can be applied by a coating method to simultaneously perform development and color development. .
Furthermore, a light shielding layer having desired characteristics can be formed by combining both, that is, a transfer method and a coating method, to obtain a light shielding layer for a display device.
Method for producing Viewing apparatus for shielding layer does not need to carry out troublesome steps, and low cost.

(Developer)
The alkaline aqueous solution used in the development step is preferably a dilute aqueous solution of an alkaline substance, but further includes a solution in which a small amount of an organic solvent miscible with water is added. Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium bicarbonate, potassium bicarbonate), Alkali metal silicates (sodium silicate, potassium silicate) Alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg 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.
In addition, when the developer contains the silver halide emulsion, the addition amount is preferably in the range of 0.3 to 3 moles of silver halide with respect to 1 mole of the silver halide-dissolving substance.

[Color filter]
Color filters, on the light transmitting substrate made of a colored layer, has two or more groups of pixels exhibiting different colors, each pixel constituting the pixel group of the display unit for light blocking layer together Hanarega The light-shielding layer for a display device according to the present invention is produced using the image-receiving layer composition for producing a light-shielding layer for a display device or a photosensitive transfer material according to the present invention. It is.
The number of pixel groups may be two, three, or four or more. For example, in the case of three, three hues of red (R), green (G), and blue (B) are used. When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable, and any arrangement may be used when four or more types of pixel groups are arranged.

As the light transmissive substrate used for the color filter, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.
In order to manufacture a color filter, after forming two or more pixel groups on a light-transmitting substrate by a conventional method, a light-shielding layer for a display device is formed as described above, or first, a light-shielding for a display device is formed. A layer may be formed, and then two or more pixel groups may be formed.
Since the color filter of the present invention includes the light shielding layer for display device as described above, the display contrast is high and the flatness is excellent.

[Liquid crystal display element]
One of the liquid crystal display element, as at least one with at least a color filter between the substrate of the optical transmission of a pair, the liquid crystal layer and a liquid crystal drive means (including a simple matrix drive method and the active matrix driving method) As the color filter, a color filter having a plurality of pixel groups as described above and each pixel constituting the pixel group being separated from each other by the light shielding layer for a display device of the present invention is used. .
Since the color filter has high flatness, a liquid crystal display element including the color filter does not cause cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness do not occur.
As another aspect of such a liquid crystal display element, at least one includes at least a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light transmissive substrates, and the liquid crystal driving means is an active element. (For example, TFT) and a light-shielding layer for a display device produced using the image-receiving layer composition for producing a light-shielding layer for a display device or a photosensitive transfer material of the present invention is formed between the active elements. Things.

[Substrate with light shielding layer for display devices]
Viewing apparatus for shielding layer-coated substrate has a light shielding layer provided on the light transmissive substrate. In this light-shielding layer, the silver complex diffused in a silver deposition pattern is deposited as silver fine particles, so that the particle diameter, aspect ratio, volume fraction, and the like of the silver fine particles differ depending on the thickness direction of the image receiving layer. Therefore, a pure black close to an achromatic color is obtained as compared with a light shielding layer prepared with silver fine particles having a sharp particle size distribution. Furthermore, since the volume fraction of the silver fine particles is smaller as the depth is increased, the silver fine particles are not fused even when heated. Therefore, when observed from the back surface of the light shielding layer, the color of the light shielding layer is maintained as pure black, which is preferable as a light shielding layer for a display device.

The substrate with Viewing apparatus for shielding layer can be used for the production of color filters.
The thickness of the light shielding layer in the substrate with a light shielding layer for a display device is preferably 0.2 to 2.0 μm, particularly preferably 0.2 to 0.9 μm. Since the light shielding layer in the light shielding layer substrate for a display device of the present invention is a dispersion of silver fine particles, even a thin film as described above has a sufficient optical density.

Hereinafter, the present invention will be described in more detail with reference examples and examples, but the present invention is not limited only to these examples.
( Reference Example 1)
1. Preparation of image-receiving material (adjustment of image-receiving layer coating solution containing photosensitive silver deposited nuclei)
A solution of 24.3 g of benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, weight average molecular weight = 30,000) dissolved in 380 g of acetone and 308 g of methyl ethyl ketone was added to a solution of 0.003 with stirring at 550 rpm. 07M sodium sulfide / 9-hydrate solution A solution of 16 ml and 36 ml of acetone was added at a rate of 1 ml / second, followed by stirring for 2 minutes, and then 0.070M palladium tetrachloride / disodium / trihydrate. A solution mixture of 16 ml of an aqueous solution and 36 ml of methanol was added at a rate of 1 ml per second, and stirring was continued for 5 minutes. These operations were performed at 25 ° C.

  Next, 17.3 g of benzyl methacrylate / methacrylic acid copolymer (molar ratio = 78/22, weight average molecular weight = 40,000), 132 g of methoxypropylene glycol acetate, 39.5 g of dipentaerythritol hexaacrylate, 2-trichloromethyl-5 -(P-styrylstyryl) -1,3,4-oxadiazol 2.02 g, phenothiazine 0.2228 g, MegaFack F176PF (Dainippon Ink Chemical Co., Ltd., fluorine-based surfactant) 1.194 g was added. The mixture was stirred to obtain a photosensitive composition containing silver deposited nuclei, and a photosensitive silver deposited nuclei containing image-receiving layer coating solution was obtained.

(Formation of photosensitive silver-deposited image-receiving layer)
The photosensitive silver deposition nucleus-containing image-receiving layer coating solution is applied to a glass substrate using a spin coater so that the film thickness becomes 0.2 μm, and dried at 100 ° C. for 5 minutes. Formed. Next, the following protective layer coating solution 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 to obtain a photosensitive silver-deposited nucleus-containing image receiving material.

[Protective layer coating solution]
・ Polyvinyl alcohol (Pura205 manufactured by Kuraray Co., Ltd.) 3.0 parts by mass. Polyvinylpyrrolidone (PVP-K30 manufactured by GAF Corporation) 1.3 parts by mass. 50.7 parts by mass of distilled water. 45.0 parts by mass of methyl alcohol. Part

2. Production of light shielding layer for display device (exposure / development)
The image-receiving material obtained as described above was exposed at a surface energy of 70 mJ / cm ² from the coated surface side using an ultrahigh pressure mercury lamp through a photomask for a light shielding layer for a display device.
Next, the film was developed with a developing solution TCD (an alkali developer manufactured by Fuji Photo Film Co., Ltd.) at 33 ° C. for 20 seconds, washed with water, dried with an air knife and dried. Further, the film was heat-treated at 240 ° C. for 50 minutes to form an image-receiving layer pattern (silver deposition nucleus pattern) containing silver deposition nuclei.

[Preparation of silver complex treatment solution]
A silver complex treatment solution having the following composition was prepared.
・ 323% of 40% potassium hydroxide aqueous solution
・ Zinc oxide 9.75g
・ 75 g of N, N-bis-methoxyethylhydroxyamine
-Triethanolamine aqueous solution (4.5 parts of triethanolamine with respect to 6.2 parts of water) 17.14 g
・ Tetrahydropyrimidinethione 0.4g
・ 2,4-Dimercaptopyrimidine 0.35g
・ Uracil 80g
・ Water 1193g

  To this solution, silver iodobromide having an average particle diameter of 1.1 μm (AgI content of 6.0 mol%, homogeneous structure), 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, An emulsion-containing silver complex treatment solution prepared by adding the following sensitizing dyes A, B, and C so as to have the following coating amounts is applied on a silver deposited nucleus-containing layer on which a pattern is formed. It applied by thickness.

Silver iodobromide, [silver equivalent 2.0],
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene [0.01],
The following sensitizing dye A [3.2 × 10 ⁻⁴ ],
The following sensitizing dye B [3.2 × 10 ⁻⁴ ],
The following sensitizing dye C [1.2 × 10 ⁻⁴ ],
In addition, the number in [] represents the solid content conversion application amount in g / m ² unit.
As described above, a sample was prepared in which a photosensitive silver-deposited laminate and a protective layer were provided on a glass substrate.

After coating, the film was kept at 25 ° C. for 40 seconds to deposit silver on the silver deposition nuclei. Then, the excess silver complex processing liquid was removed with 30 degreeC distilled water, water was turned off with the air knife, and it dried. By this treatment, removal of the uncured image-receiving layer and formation of a patterned light-shielding layer by coloring the cured image-receiving layer pattern in black are performed in one step, and Reference Example 1 having a patterned light-shielding layer The light shielding layer for display devices was obtained.

[Evaluation of light shielding layer for display device]
1. Film thickness measurement The film thickness was measured by the following method. The sample coated with the image receiving layer was exposed from the coated surface side using an ultrahigh pressure mercury lamp under the condition of an exposure energy of 70 mJ / cm ² to cure the image receiving layer. In the formed light-shielding layer for a display device, the film thicknesses of the image receiving layer forming region and the non-forming region (region of the support only) were measured using a stylus type surface roughness meter P-1 (manufactured by TENKOP). The thickness of the image receiving layer was measured by measuring and taking the difference between the two.
2. Measurement of optical density The optical density of the film was measured by the following method. The silver deposit laminated on the glass substrate is exposed to 500 mJ / cm ² from the coated surface side using an ultrahigh pressure mercury lamp, and then this optical density is measured using a Macbeth densitometer (Macbeth TD-904). Measure (OD). Separately, the optical density (OD ₀ ) of the glass substrate is measured by the same method, and the difference between the two, that is, the value obtained by subtracting OD ₀ from OD is taken as the optical density of the film.

3. Formation of Blue, Red, and Green Pixels and Evaluation of Pixel Bubbles Samples R1, G1, and B1 described in Example-1 of Japanese Patent Application Publication No. 2002-341127 on a glass substrate on which a light-shielding layer for a display device is formed. A pixel of each color was formed using The method described in this patent was also used for the pixel formation method.
Since the pixels of each color are formed on the unevenness of the light shielding layer for the display device, air bubbles may enter between the glass substrate and each color pixel. The degree of bubble generation was measured by the following method.
The number of bubbles was counted visually using an optical microscope for a total of 300 pixels, each of 100 pixels of the three colors on the glass substrate. The smaller the number, the better.

4). Change in hue of light-shielding layer for display device by heating The change in hue of light-shielding layer for display device before and after the glass substrate on which the light-shielding layer for display device was formed was heat-treated at 220 ° C. for 2 hours was visually evaluated. In the following evaluation, what is practically acceptable is an AC level.
No change at all A
Slightly metallic luster B
Slight metallic luster, but practically acceptable C
Metal luster that is an obstacle to practical use D
Full metallic luster E
The above evaluation results are shown in Table 1.

(Examples 8 to 11)
Instead of the 0.070M palladium tetrachloride / disodium / trihydrate aqueous solution used in the formation of silver deposited nuclei in Reference Example 1, the same concentration of palladium tetrachloride / disodium / trihydrate aqueous solution, chloroauric acid aqueous solution, and except that the chloroplatinic acid solution were combined in the proportions shown in Table 1 to form a light shielding layer for a display device in the same manner as in reference example 1, was evaluated in the same manner. The results are also shown in Table 1.

(Examples 20 to 23 )
Reference Example 1, without forming a protective layer on the image-receiving layer surface, further, except for changing the amount of exposure from 70 mJ / cm ² to 500 mJ / cm ² to form a light shielding layer for a display device in the same manner as in Reference Example 1 The same evaluation was performed. The results are also shown in Table 1.

  As is clear from the results in Table 1, it was found that the light shielding layer for a display device of the present invention has a high optical density and excellent light shielding properties despite the thin thickness of the light shielding layer. Moreover, the generation | occurrence | production of the bubble which can be confirmed visually at the time of pixel formation was not recognized, but it was suitable also for formation of a color filter. Furthermore, since almost no change in hue after heating was observed and the thermal stability was high, it was clear that high durability could be exhibited even when used in liquid crystal display elements.

(Examples 32-35 )
1. Preparation of Transfer Material A biaxially stretched 75 μm thick polyethylene terephthalate support was coated with a thermoplastic resin layer coating solution having the following composition so as to have a thickness of 15 μm using a slide coater and dried at 100 ° C. for 5 minutes. Next, the protective layer coating solution used in Reference Example 1 was applied thereon as an intermediate layer so that the dry film thickness was 1.5 μm and dried at 100 ° C. for 5 minutes.
[Thermoplastic resin layer coating solution]
・ Methyl methacrylate / 2-ethylhexyl acrylate /
Copolymer of benzyl methacrylate / methacrylic acid = 54/12/5/29 (number average molecular weight 80000) 58 parts ・ Copolymer of styrene / acrylic acid = 70/30 (number average molecular weight 7000) 136 parts ・ Polyfunctional acrylate (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) 90 parts ・ Fluorosurfactant (F176PF, manufactured by Dainippon Ink & Chemicals, Inc.) 1 part ・ Methyl ethyl ketone 541 parts ・ 1-methoxy-2-propanol 63 Part: Methyl alcohol 111 parts Further, on the intermediate layer, the same photosensitive silver deposited nucleus-containing layer coating solution as used in Reference Example 1 and Examples 8 to 11 was applied and dried to prepare a transfer material.

2. Production of light-shielding layer for display device Each transfer material and glass substrate obtained as described above were superposed so that the image-receiving layer and the glass surface were in close contact with each other, and both were bonded together using a laminator. The lamination conditions are a pressure of 0.8 kg / cm ² and a temperature of 130 ° C.
Thereafter, the polyethylene terephthalate support was peeled off to obtain a laminate in which the image receiving layer and the intermediate layer were transferred onto the glass substrate. This laminate is exposed through a mask for a light shielding layer for a display device using an ultrahigh pressure mercury lamp under the condition that the energy on the surface is 70 mJ / cm ² from the image receiving layer and intermediate layer formation side, and thereafter Then, development was performed sequentially using the following developers.

(1) Development processing was performed at 30 ° C. for 40 seconds using a development processing solution TPD (an alkali developing solution manufactured by Fuji Photo Film Co., Ltd.).
(2) Development processing was performed at 33 ° C. for 20 seconds using a developing solution TCD (an alkali developer manufactured by Fuji Photo Film Co., Ltd.).
(3) Using a developing solution TSD (an alkaline developer manufactured by Fuji Photo Film Co., Ltd.), development processing was performed at 33 ° C. for 20 seconds.
After the development processing, it was washed with water and water was cut off with an air knife. Furthermore, it heat-processed at 240 degreeC for 50 minutes, and formed the silver deposition nucleus containing layer pattern containing a silver deposition nucleus.
Thereafter, in Reference Example 1 a similar manner, the formation of the silver halide emulsion layer was subjected to silver complex treatment liquid immersion, with the light-shielding layer-provided substrate of Example 32 to 35 were evaluated in the same manner as in Reference Example 1. The results are shown in Table 2 below.

(Comparative Example 1)
1. Preparation of silver fine particles (Preparation of solution A)
To 50 g of demineralized gelatin, 1950 g of distilled water was added, and the resulting mixture was heated to about 40 ° C. to dissolve the gelatin. This was adjusted to pH 9.2 with 5% NaOH aqueous solution and kept at 40 ° C.
(Preparation of liquid B)
To 150 g of demineralized gelatin, 1350 g of distilled water was added and the resulting mixture was heated to about 40 ° C. to dissolve the gelatin. Similarly, the pH was adjusted to 9.2 with 5% NaOH aqueous solution. 160 g of silver nitrate dissolved in 16.0 g of calcium acetate and 320 ml of distilled water was dissolved by stirring, distilled water was added to adjust the final volume to 2000 ml, and the temperature was kept at 40 ° C.
(Preparation of liquid C)
Dissolve 110 g of sodium sulfite (anhydrous) in 700 ml of distilled water, mix 80 g of hydroquinone in 70 ml of methanol and 80 ml of water, add distilled water to adjust the final volume to 2000 ml, Kept warm.

Liquid B and liquid C were added simultaneously over 10 seconds while liquid A was rapidly stirred. Ten minutes later, a solution prepared by dissolving 1600 g of anhydrous sodium sulfate in 70 ml of concentrated hydrochloric acid and 8000 ml of distilled water was added, and the mixture was stirred for 80 minutes, then allowed to settle and cooled. After removing the supernatant, it was immediately rinsed with distilled water until no precipitate was formed even when the Br salt solution was added. After draining, it was redissolved at 40 ° C. The product (re-dissolved solution) was then cooled to near the gelling temperature and passed through a small hole into the cooled water, thereby forming a very fine noodle.
It was washed with 20 g of sodium sulfite (anhydrous) and 0.6 g of NaOH dissolved in 2000 ml of distilled water, and further washed with 20 g of glacial acetic acid dissolved in 2000 ml of distilled water. The resulting black slurry particles 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 to wash away all salts.
When the washed black silver dispersed in the gel slurry was melted, the water content of the product was adjusted so as to obtain a black silver dispersion having a silver concentration of 1.5% by mass.

(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 5% by weight papain 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 discarding the supernatant, it was washed with distilled water and the gelatin degradation product decomposed with the enzyme was removed. 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 30 nm using a bead disperser (zirconia beads 0.3 mm).

2. Preparation of Photosensitive Layer Coating Solution The following additives were added to the silver fine particle dispersion A-1 obtained as described above to prepare a photosensitive layer coating solution.
[Coating liquid for photosensitive layer]
Silver fine particle dispersion A-1 40.0 g
・ Propylene glycol monomethyl ether acetate 40.0g
・ Methyl ethyl ketone 37.6g
・ Fluorine surfactant 0.2g
(Dainippon Ink & Chemicals, F176PF (20%))
・ Hydroquinone monomethyl ether 0.001g
・ Dipentaerythritol hexaacrylate
(Added so that the volume fraction of silver fine particles in the photosensitive layer is 0.126)
Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl]
Phenyl] sebacate 0.1 g

3. Preparation of Protective Layer Coating Solution A protective layer coating solution similar to that used in Reference Example 1 was prepared.
4). Production of Photosensitive Material The photosensitive layer coating solution was applied to a glass substrate using a spin coater so that the optical density was 4.0 and dried at 100 ° C. for 5 minutes. Next, the protective layer coating solution was applied onto the coating layer using a spin coater so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 5 minutes.
5). Production of light-shielding layer for display device Using a mask for light-shielding layer for display device, exposure was performed using an ultra-high pressure mercury lamp under the condition that the energy on the surface was 70 mJ / cm ² from the coated surface side. Next, development processing was sequentially performed under the following conditions to obtain a light shielding layer for a display device.
(1) Development processing was carried out at 33 ° C. for 20 seconds using a developing solution TCD (an alkaline developer manufactured by Fuji Photo Film Co., Ltd.).
(2) Development processing was performed at 33 ° C. for 20 seconds using a developing solution TSD (an alkali developer manufactured by Fuji Photo Film Co., Ltd.).

[Evaluation of light shielding layer for display device]
The light shielding layer for display device was evaluated in the same manner as in Reference Example 1. The results are also shown in Table 2. In particular, the result of the change in the hue of the light shielding layer for the display device before and after the heat treatment was E rank indicating a complete metallic luster according to the above evaluation criteria, which was not practical.
The film thickness measurement result was 0.11 μm.

(Comparative Example 2)
1. Preparation of Photosensitive Transfer Material A biaxially stretched 75 μm thick polyethylene terephthalate support was coated with the same thermoplastic resin layer coating solution as used in Example 23 so that the thickness was 15 μm using a slide coater. Dry at 100 ° C. for 5 minutes. Next, an intermediate layer coating solution similar to that of Example 32 was applied thereon so as to have a dry film thickness of 1.5 μm, and dried at 100 ° C. for 5 minutes. Further, the same photosensitive layer coating solution as used in Comparative Example 1 was applied and dried to prepare a photosensitive transfer material.

2. Preparation of light-shielding layer for display device The photosensitive transfer material and the glass substrate were superposed so that the photosensitive layer and the glass surface were in close contact with each other, and both were bonded together using a laminator similar to that used in Example 32 above. . The lamination conditions are a pressure of 0.8 kg / cm ² and a temperature of 130 ° C.
Thereafter, the polyethylene terephthalate support was peeled off. Through the mask for the light shielding layer for the display device, exposure was performed using an ultrahigh pressure mercury lamp under the condition that the energy on the surface was 70 mJ / cm ² from the coated surface side. Next, development processing was sequentially performed under the following conditions, followed by washing with water, and water was removed with an air knife to obtain a light-shielding layer for a display device.
(1) Development processing was performed at 30 ° C. for 40 seconds using a developing solution TPD (an alkaline developer manufactured by Fuji Photo Film Co., Ltd.).
(2) Development processing was performed at 33 ° C. for 20 seconds using a developing solution TCD (an alkali developer manufactured by Fuji Photo Film Co., Ltd.).
(3) Development processing was performed at 33 ° C. for 20 seconds using a developing solution TSD (an alkaline developer manufactured by Fuji Photo Film Co., Ltd.).

[Evaluation of light shielding layer for display device]
The light shielding layer for display device was evaluated in the same manner as in Reference Example 1. The results are also shown in Table 2. In particular, the result of the change in the hue of the light shielding layer for the display device before and after the heat treatment was E rank indicating a complete metallic luster according to the above evaluation criteria, which was not practical.
The film thickness measurement result was 0.11 μm.

(Comparative Example 3)
1. Preparation of resist coating solution The following black resist coating solution was coated on a glass substrate so that the optical density (OD) was 4.0, and dried at 100 ° C for 5 minutes. On this, the intermediate layer coating solution was applied so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 5 minutes. The protective layer coating solution is the same as in Reference Example 1.
Black resist coating solution:
-CFP-FF-775B (C.I.PB15: 6 dispersion manufactured by Fuji Film Orin Co., Ltd.) 4.50 parts -CFP-FF-293Y (C.I.PY139 dispersion liquid manufactured by Fuji Film Orin Co., Ltd.) 3.37 parts-CFP-FF-802V (CI. PV23 dispersion manufactured by Fuji Film Orin Co., Ltd.) 4.16 parts-CFP-FF-949K (carbon black dispersion manufactured by Fuji Film Orin 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) pheny Le)
Carbamoyl] phenyl] sebacate 0.238 parts ・ The following copolymer (methyl isobutyl ketone 30 mass% solution) 0.065 parts

2. Preparation of light-shielding layer for display device The photosensitive material coated with the black resist coating solution is applied with an ultrahigh pressure mercury lamp through a mask for light-shielding layer for display device, and the energy on the surface is 70 mJ / cm ² The exposure was performed under the following conditions. Subsequently, after performing development processing sequentially under the following conditions, it was washed with water, and water was removed with an air knife to obtain a light shielding layer for a display device.
(1) Development processing was carried out at 33 ° C. for 20 seconds using a developing solution TCD (an alkaline developer manufactured by Fuji Photo Film Co., Ltd.).
(2) Development processing was performed at 33 ° C. for 20 seconds using a developing solution TSD (an alkali developer manufactured by Fuji Photo Film Co., Ltd.).

[Evaluation of light shielding layer for display device]
The light shielding layer for display device was evaluated in the same manner as in Reference Example 1. The results are also shown in Table 2. The film thickness measurement result was 2.35 μm. Since it was such a thick light-shielding layer, in “the formation of blue, red, and green pixels and the evaluation of the bubbles in the pixels”, the number of bubbles that can be visually confirmed was counted to be 50 or more. It was not practical.

(Comparative Example 4)
1. Preparation of Photosensitive Transfer Material A biaxially stretched 75 μm thick polyethylene terephthalate support was coated with the same thermoplastic resin layer coating solution as used in Example 23 so that the thickness was 15 μm using a slide coater. Dry at 100 ° C. for 5 minutes. Next, an intermediate layer coating solution similar to that of Example 32 was applied thereon so as to have a dry film thickness of 1.5 μm, and dried at 100 ° C. for 5 minutes. Further, the same black resist coating solution as used in Comparative Example 3 was applied and dried to prepare a photosensitive transfer material.

2. Preparation of light-shielding layer for display device The photosensitive transfer material and the glass substrate were superposed so that the photosensitive layer and the glass surface were in close contact with each other, and both were bonded together using a laminator similar to that used in Example 32 above. . The lamination conditions are a pressure of 0.8 kg / cm ² and a temperature of 130 ° C.
Thereafter, the polyethylene terephthalate support was peeled off. Through the mask for the light shielding layer for the display device, exposure was performed using an ultrahigh pressure mercury lamp under the condition that the energy on the surface was 70 mJ / cm ² from the coated surface side. Subsequently, after performing development processing sequentially under the following conditions, it was washed with water, and water was removed with an air knife to obtain a light shielding layer for a display device.

(1) Development processing was performed at 30 ° C. for 40 seconds using a developing solution TPD (an alkaline developer manufactured by Fuji Photo Film Co., Ltd.).
(2) Development processing was performed at 33 ° C. for 20 seconds using a developing solution TCD (an alkali developer manufactured by Fuji Photo Film Co., Ltd.).
(3) Development processing was performed at 33 ° C. for 20 seconds using a developing solution TSD (an alkaline developer manufactured by Fuji Photo Film Co., Ltd.).

[Evaluation of light shielding layer for display device]
The light shielding layer for display device was evaluated in the same manner as in Reference Example 1. The results are also shown in Table 2. The film thickness measurement result was 2.35 μm. Since it was such a thick light-shielding layer, in “the formation of blue, red, and green pixels and evaluation of the bubbles in the pixels”, the number of bubbles that can be visually confirmed was counted, and it was 50 or more. It was not practical.

From the evaluation results of Examples 8 to 11, Examples 20 to 23, Examples 32 to 35, and Comparative Examples 1 to 4, the light shielding layer for a display device produced using the photosensitive composition of the present invention was formed by a coating method. In addition, both the thin film and the film formed by the transfer method show high optical density even in a thin layer, and there is no hue change after heating, and even when forming a color filter by forming pixels, the generation of bubbles is suppressed. It was found that it can be suitably used for optical elements and color filters.
On the other hand, the light-shielding layers for display devices of Comparative Examples 1 and 2 having a light-shielding layer in which silver fine particles are dispersed are excellent in light-shielding properties, but as the light-shielding layer for display devices because of a significant change in gloss after heat treatment, It turns out that it is not suitable for practical use. In addition, the light shielding layers for display devices of Comparative Examples 3 and 4 produced using the black resist coating solution have a large thickness of the light shielding layer, and the generation of bubbles during the formation of pixels is remarkable. It turned out that it is not suitable for the light shielding layer for apparatuses.

Claims (1)

A photosensitive composition comprising two or three kinds of silver deposition nuclei containing a sulfide, a photopolymerization initiator, a photopolymerizable monomer, and a binder .