KR101157870B1 - Photosensitive composition, photosensitive transfer material, light shielding layer for display device, color filter, liquid crystal display device, substrate with light shielding layer for display device and method of manufacturing the same - Google Patents

Abstract

 A photosensitive composition and a photosensitive transfer material capable of manufacturing a light shielding layer for a display device at a thin film and having a high light shielding performance, and at a low cost, and a method for manufacturing a light shielding layer for a display device having a thin film, having a high light shielding performance and at a low cost. to provide.

At least 1 type of silver immersion nucleus is contained, The light-shielding layer for display apparatuses can be obtained using this.

Description

Photosensitive composition, photosensitive transfer material, substrate with light blocking layer for display device, color filter, liquid crystal display device and light shielding layer for display device and method for manufacturing thereof {PHOTOSENSITIVE COMPOSITION, PHOTOSENSITIVE TRANSFER MATERIAL, LIGHT SHIELDING LAYER FOR DISPLAY DEVICE, COLOR FILTER, LIQUID CRYSTAL DISPLAY DEVICE, SUBSTRATE WITH LIGHT SHIELDING LAYER FOR DISPLAY DEVICE AND METHOD OF MANUFACTURING THE SAME}

 The present invention provides a photosensitive composition, a photosensitive transfer material, a light shielding layer for a display device fabricated using the same, a substrate including a color filter including the light shielding layer for a display device, a liquid crystal display element and a light shielding layer for a display device, and the The manufacturing method of the board | substrate with which the light shielding layer for display devices was formed is provided.

In the color filter used for a color liquid crystal display, a colored pixel layer (R, G, B) is formed on a transparent substrate, and in the gap of each colored pixel of R, G, B (red, green, blue), For the purpose of improving display contrast, a light shielding layer for a display device is formed. In particular, in an active matrix drive type liquid crystal display device using a thin film transistor TFT, a high light shielding property is required for a light shielding layer for a display device in order to prevent deterioration in image quality caused by current leakage due to light of the thin film transistor.

As a method of forming a light shielding layer for a display device, for example, when a metal film such as chromium is used as the light shielding layer, a metal thin film is produced by a vapor deposition method or a sputtering method, and a photoresist is applied on the metal thin film, and then A method of exposing and developing a photoresist layer using a photomask having a light shielding layer pattern for a display device, then etching the exposed metal thin film, and finally removing the resist layer on the metal thin film is known (for example, See Non-Patent Document 1).

Since this method uses a metal thin film, the obtained light shielding layer for a display device can obtain a high light shielding effect even when the film thickness is small, whereas in manufacturing, a vacuum film forming process such as a vapor deposition method, a sputtering method, or an etching process using a liquid is used. There is a problem that this becomes necessary, the cost increases, and the load on the environment cannot be ignored. Moreover, since it is a metal film, there also exists a problem that a reflectance is high and display contrast is low under strong external light. There is a means of using a low-reflection chromium film (such as two layers of metal chromium and chromium oxide), but it can not be denied that the cost increases further.

As another method of forming the light shielding layer for a display device, a method of using a photosensitive resin composition containing a light-shielding pigment, for example, carbon black, is also known. Specifically, for example, R, G, B on a transparent substrate are used. After forming a pixel, a method of forming a light shielding layer for a display device of a self-aligning display device, which is formed by coating a carbon black-containing photosensitive resin composition on the pixel and exposing the entire surface from the R, G, and B pixel non-forming surface side of the transparent substrate, is known. (For example, refer patent document 1).

This method has a lower manufacturing cost than the method by etching the metal film, but has a problem that the film thickness becomes thick in order to obtain sufficient light shielding properties. As a result, the light shielding layer for display devices and R, G, B pixels There is a possibility that overlapping (step difference) occurs, flatness of the color filter worsens, cell gap deviation of the liquid crystal display element occurs, and lead to display defects such as color deviation.

Patent Document 1: Japanese Patent Publication No. 62-9301

(Non-Patent Document 1) 218-220 pages of Color TFT LCD Display issued by Kyoritsu Shoten Co., Ltd. (April 10, 1997)

 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a photosensitive composition and a photosensitive transfer material capable of producing a light shielding layer for a display device with a thin film, high light shielding performance, and low cost. Another object of the present invention is to provide a light shielding layer for a display device and a method for manufacturing the same, which are thin films, have high light shielding performance, and can be manufactured at low cost. Still another object of the present invention is to provide a color filter and a liquid crystal display device having a light shielding layer for a display device of the present invention, which is a thin film and high light shielding performance, and a light shielding layer substrate for a display device with a thin film and high light shielding performance and a method of manufacturing the same. It is to offer.

The problem is solved by providing a substrate having a photosensitive composition for manufacturing a light shielding layer and a photosensitive transfer material of a display device, a light shielding layer for a display device and a method of manufacturing the same, and a color filter, a liquid crystal display device, and a light shielding layer for a display device. do.

<1> Photosensitive composition containing at least 1 type of silver immersion nucleus.

<2> Photosensitive composition containing at least 1 type of silver deposition nucleus, a photoinitiator, a photopolymerizable monomer, and a binder.

<3> The photosensitive composition as described in <1> or <2>, in which the silver deposit nucleus contains at least a sulfide.

<4> A photosensitive transfer material having at least a photosensitive silver immersion core layer formed on a support, wherein the photosensitive silver immersion core layer contains at least one silver immersion nucleus, a photopolymerization initiator, a photopolymerizable monomer, and a binder. Photosensitive transfer material.

After exposing and developing the photosensitive silver immersion nucleus layer formed on a board | substrate using the photosensitive composition in any one of <5> said <1> to <3>, or the photosensitive transfer material as described in said <4>, A light shielding layer for a display device, wherein silver is deposited.

On the <6> light-transmissive substrate, each pixel which consists of a colored layer and has 2 or more pixel groups which show a different color, and comprises the said pixel group is isolate | separated from each other by the light shielding layer for display apparatuses. And said light shielding layer for display devices is a light shielding layer for display devices as described in said <5>.

<7> At least one liquid crystal display device comprising at least one color filter, a liquid crystal layer, and a liquid crystal driving means between a pair of light transmissive substrates, wherein the color filter is the color filter according to the above <6>. Liquid crystal display device.

&Lt; 8 > A liquid crystal display device comprising a color filter, a liquid crystal layer, and liquid crystal drive means between at least one pair of optically transmissive substrates, wherein the liquid crystal drive means has an active element and the < 5 between each active element. The light shielding layer for display apparatuses described in <> is formed, The liquid crystal display element characterized by the above-mentioned.

<9> A substrate having a light shielding layer for a display device having a light transmissive substrate and a light shielding layer formed on the substrate, wherein the light shielding layer is a light shielding layer for a display device according to <5>. A substrate on which a light shielding layer is formed.

Forming a photosensitive silver immersed nucleus layer containing at least one silver immersed nucleus, a photopolymerization initiator, a photopolymerizable monomer, and a binder on the light transmissive substrate; An exposure step of photopolymerizing the exposure part, a step of removing the unexposed part by the developing solution, and forming a silver immersion nucleus pattern, and applying a silver complex treatment solution composed of a silver halide emulsion and a silver solvent to the silver immersion nucleus pattern. The manufacturing method of the board | substrate with a light shielding layer for display apparatuses which has a process which deposits silver.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[Photosensitive composition for manufacturing light shielding layer for display device]

First, the photosensitive composition of this invention is demonstrated. The photosensitive composition of this invention contains at least 1 type of silver deposition nucleus, It is characterized by the above-mentioned. Moreover, in the 2nd aspect of this invention, further, it contains a photoinitiator, a photopolymerizable monomer, and a binder, All are as an aqueous phase layer for forming the photosensitive silver immersion nucleus layer and the light shielding layer for display devices. It can be used preferably. These components will be described sequentially.

(Silver immersion nucleus)

The silver immersion nucleus that can be used in the present invention is obtained by carrying out according to the preparation method of the silver halide emulsion which is well known in the photography industry. In principle, a nucleus made of sulfide can be prepared by reacting a sulfide ion solution with a metal ion solution or each single solution, and the nucleus thus obtained can be applied to the present invention.

The silver nucleus nucleus is a compound that helps to form a silver fine particle by reducing the developmental agent of the transfer silver complex salt which has diffused from the halogenated emulsion layer. Specific examples of silver deposition nuclei include heavy metals such as iron, lead, zinc, nickel, tin, copper, chromium and cobalt, and precious metals such as gold, silver (including colloidal silver), platinum, and palladium. In addition, sulfides and selenides of noble metals, for example, sulfides such as mercury, copper, zinc, silver, and palladium, and selenides such as lead, zinc, and antimony are also preferred silver deposit cores. Among these, gold, platinum, palladium and sulfides thereof are particularly preferable.

As a compound which can be a sulfide ion for forming a silver nucleation nucleus, for example, water-soluble sulfides such as sodium sulfide and potassium sulfide are preferable, but an organic solvent such as acetone, diacetone alcohol or methanol, or a mixed solvent of these organic solvents and water An ion-containing compound which is soluble in and which can form sulfides with metal ions may be used.

As a compound which can be a palladium ion, water-soluble palladium compounds, such as sodium salt or potassium salt of palladium chloride, for example, are preferable, but an organic solvent such as acetone, diacetone alcohol or methanol, or a mixed solvent of these organic solvents and water Palladium compound which melt | dissolves may be sufficient. As the compound capable of becoming a gold ion, for example, chlorinated acid chloride or a water-soluble salt thereof is preferable, but an organic solvent such as acetone, diacetone alcohol or methanol, or a gold compound dissolved in a mixed solvent of these organic solvents and water may be used.

In order to prepare a mixed nucleus containing plural kinds of metals such as palladium sulfide and gold sulfide, for example, a mixed nucleus such as palladium and gold is added while stirring and putting a binder solution and a sulfide ion solution described later in an input container. A method of adding a mixed solution of a plurality of metal ions used to form a solution, a method of adding a mixed solution of a binder solution and a plurality of metal ions to an input container in advance, and a method of adding a sulfide ion solution while stirring, or an input container What is necessary is just to introduce the method of adding a mixed solution of several metal ions, and a sulfide ion solution simultaneously or adding time difference, stirring only putting a binder solution previously.

It is preferable that 1-30 mass% is contained in the photosensitive composition of this invention, and, as for the silver deposition nucleus obtained in this way, it is more preferable that it is the range of 3-20 mass%. The deposition nuclei can be quantified using a fluorescence X-ray measuring apparatus, for example, manufactured by Rigga Co., Ltd., X-RAP SPECTOR OMRETR 3370, or the like.

(Photoinitiator)

Since the photosensitive composition of this invention hardens | cures by exposure and forms a pattern, it is preferable to contain the photoinitiator which can generate | occur | produce a starting species by exposure, and the photopolymerizable monomer hardened | cured by generating a polymerization reaction by the said starting species. Do.

As an example of the photoinitiator which can be used for this invention, the bisinal poly ketaldonyl compound disclosed by US patent 2367660, the acyl phosphorus compound described in US patent 2448828, US patent 2722512 Aromatic acyloin compounds substituted with α-hydrocarbons described in the specification, polynuclear quinone compounds described in each specification of US Pat. No. 3046127 and US Pat. No. 2951758, triarylimidazole dimers described in US Pat. Combination of amino ketones, benzothiazole compound and trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl-s-tree described in US Pat. No. 4,39,850. Azine compounds, trihalomethyloxadiazole compounds described in the specification of U.S. Patent No. 4212976, and the like. Among them, trihalomethyl-s-triazine, trihalomethyloxadiazole, triarylimidazole dimer, Michler's ketone and benzyl dimethyl ketal are particularly preferable.

You may use these photoinitiators individually or in mixture of 2 or more types.

As for content of the photoinitiator in the photosensitive composition of this invention, 0.5-20 mass% is preferable in conversion of solid content from a viewpoint of a sensitivity and the image intensity formed, More preferably, it is 2-15 mass%.

In this invention, the high molecular compound which has photosensitivity can also be used as a photoinitiator. As such a photosensitive high molecular compound, what contains the cinnamoyl group, maleimide group, etc. which are photosensitive groups in the structure of a high molecular compound is mentioned.

Specifically, the photosensitive polymer compound described in Unexamined-Japanese-Patent No. 2-157762, British Patent 1112277, 1313390, 131344, 1377747, etc. is mentioned.

Such a photosensitive high molecular compound can be used instead of or in addition to the said photoinitiator. The preferable addition amount in the photosensitive composition of a photosensitive high molecular compound is 20-80 mass% in conversion of solid content.

(Photopolymerizable monomer)

As a photopolymerizable monomer used preferably for this invention, the compound which has at least 1 addition-polymerizable ethylenically unsaturated group in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is mentioned.

Specific examples thereof include 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, trimetholethane tri (meth) acrylate, trimetholpropane tri (meth) acrylate, trimetholpropanedi (meth) acrylic Latene, 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, trimetholpropane tri ((meth) acryloyloxypropyl) ether, tri ((meth) acryloyloxyethyl) isocyanurate, tri ((meth) acryloyl After adding ethylene oxide or propylene oxide to polyfunctional alcohols such as oxyethyl) cyanurate, glycerin tri (meth) acrylate, trimetholpropane or glycerin (Meth) a acrylated;

The urethane acrylates described in Japanese Patent Publications No. 48-41708, Japanese Patent Publications No. 50-6034, and Japanese Patent Publication Nos. 51-37193, Japanese Patent Publication Nos. 48-64183, and Japanese Patent Publications Polyfunctional (meth) acrylates such as the polyester acrylates described in 49-43191 and Japanese Patent Laid-Open No. 52-30490, and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acids; And the like.

Especially, from a viewpoint of polymerizability and the film strength after superposition | polymerization, as a more preferable example, a trimethol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate is mentioned.

As for content of the photopolymerizable monomer in the photosensitive composition of this invention, 20-80 mass% is preferable in conversion of solid content from a viewpoint of the balance of the film strength after superposition | polymerization, and developability, More preferably, it is 40-60 mass%.

(bookbinder)

It is preferable that the photosensitive composition of this invention contains an alkali-soluble binder from a viewpoint of a film improvement and the removal property of an unexposed part.

As an alkali-soluble binder which can be used by this invention, specifically, the compound selected from the following broad types of high molecular compounds can be used in combination. As the compound which can be combined, the silver immersion nucleus dispersibility is good, and the compatibility with the synthetic monomer and the photopolymerization initiator is good, and the alkali developer solubility, the organic solvent solubility, the strength, the softening temperature, and the like are suitable. It is preferable to select suitably in correlation with.

Specific examples of such alkali-soluble binders include copolymers of (meth) acrylic acid and (meth) acrylic acid esters, styrene / maleic anhydride copolymers, and reactants of the copolymers and alcohols. The copolymer of (meth) acrylic acid and (meth) acrylic acid ester is used.

It is preferable that the mass mean molecular weight of a binder is the range of 5,000-200,000.

Although a binder may be used in combination of multiple types, preferable content of the binder in the photosensitive composition is 20-80 mass% with respect to all solid content as a total amount of a binder.

In addition to the said component, various components, such as a thermal polymerization inhibitor, a solvent, and an adhesion promoter, can be added to the photosensitive composition of this invention as needed.

The thermal polymerization inhibitor is added for the purpose of increasing the storage stability of the composition when using a combination of the above-mentioned addition polymerizable unsaturated monomer (corresponding to the photopolymerizable monomer of the present invention) and the photopolymerization initiator 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, etc. are mentioned.

[Photosensitive Transfer Material for Manufacturing Water Phase Layer for Forming Shading Layer for Display Device]

Next, the photosensitive transfer material for manufacturing the water phase layer (photosensitive silver nucleus containing layer) for forming the light shielding layer for display devices of this invention is demonstrated.

By forming the aqueous layer which consists of the photosensitive composition of this invention on a support body, the photosensitive transfer material for aqueous phase preparation can be obtained.

This transfer material in the present invention may be one in which a layer containing at least silver halide and a silver deposition nucleus layer formed of the photosensitive composition are sequentially formed on a support, and also on the transfer material of the present invention, that is, on a support. The formation of image formation may be performed by applying a silver halide emulsion layer to the surface of the aqueous phase layer, using only one formed therein.

In any of the transfer materials, when transferring to a permanent support such as a glass substrate to form an image, that is, a light shielding layer for a display device described later, it is preferable to form a silver halide emulsion layer on the aqueous phase layer.

The support in the transfer material of the present invention is generally removed at the time of image formation or after image formation, but a known support such as polyester or polystyrene can be used as the support. Especially, the polyethylene terephthalate biaxially stretched is preferable from a viewpoint of cost, heat resistance, and dimensional stability. As for the thickness of a support body, about 15-200 micrometers is preferable from a viewpoint of shape stability, dimensional stability, and cost with respect to the heating at the lamination process, and it is more preferable that it is about 30-150 micrometers.

Moreover, you may form the electroconductive layer described in Unexamined-Japanese-Patent No. 11-149008 as needed.

As described above, the photosensitive transfer material for producing an aqueous layer of the light shielding layer for a display device according to the present invention is dissolved in a suitable solvent and coated and dried on a support (which may be a support) as described above. It is obtained by forming the water phase layer for manufacturing a light shielding layer for.

Examples of the solvent 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, and 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, sec-butanol, t-butanol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, ε -Caprolactam, dimethyl sulfoxide, hexamethylphosphoramide, water, etc. are mentioned. These can be used individually or as a mixture of 2 or more types according to the objective.

There is no restriction | limiting in particular in the coating method, A well-known method, for example, a spinner (spin method, a slit and spin method), a powyer, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder (FAS method, etc.) It can form by apply | coating and drying using applicators, such as these. Even when forming the layer of alkali-soluble thermoplastic resin mentioned later, a layer can be formed by the same method.

Although the application amount of an aqueous phase layer is suitably selected according to the objective, it is generally preferable that it is 0.2-2.0 micrometers in the application amount after drying.

In the transfer material of the present invention, a peeling layer or a protective layer may be applied or formed on the aqueous layer containing the silver immersed nucleus for the purpose of improving the gloss and smoothness of the surface or preventing damage to the silver immersed nucleus-containing aqueous layer. good.

(Thermoplastic layer)

In the transfer material of the present invention, it is preferable to form a thermoplastic resin layer, particularly an alkali-soluble thermoplastic resin layer, between the support and the aqueous phase layer, or the support and the intermediate layer described later.

The alkali-soluble thermoplastic resin layer serves as a cushioning material capable of absorbing the unevenness of the underlying surface such as unevenness on the surface of the support or unevenness due to an already formed image or the like, and may be deformed according to the unevenness. It is preferable to form by resin which has a.

Examples of the resin contained in the alkali-soluble thermoplastic resin layer include saponified products of ethylene and acrylic acid ester copolymers, saponified products of styrene and (meth) acrylic acid ester copolymers, saponified products of vinyltoluene and (meth) acrylic acid ester copolymers, and poly Although it is preferable that it is at least 1 sort (s) chosen from (meth) acrylic acid ester, and saponified products, such as (meth) acrylic acid ester copolymers, such as butyl (meth) acrylic acid and vinyl acetate, it is also "Plastic performance manual" (Japan Plastic Industry Federation, Soluble in alkali aqueous solution among the organic polymers described in the Japan Plastic Molding Industry Association, published by the Japan Industrial Association, published October 25, 1968). Moreover, it is preferable that the softening point is 80 degrees C or less among these thermoplastic resins. In addition, in this specification, both or either of acrylic acid and methacrylic acid may be called "(meth) acrylic acid," and the same also in the case of the derivative | guide_body.

As a component of a thermoplastic resin layer, it is said resin, It is preferable to select and use what has physical property of the weight average molecular weight 50000-500000 (Tg = 0-140 degreeC), and the weight average molecular weight 60,000-200,000 (Tg = It is more preferable to select and use in the range of 30-110 degreeC).

As a specific example of resin which can be used, Japanese patent publication 54-34327, Japanese patent publication 55-38961, Japanese patent publication 58-12577, Japanese patent publication 54-25957, Japanese patent publication 61- 134756, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-92723, Japanese Patent Publication No. 54-99418, Japanese Patent Publication No. 54-137085, Japanese Patent Publication No. 57-20732, Japan Patent Japanese Patent Laid-Open No. 58-93046, Japanese Patent Laid-Open No. 59-97135, Japanese Patent Laid-Open No. 60-159743, OLS3504254, Japanese Patent Laid-Open No. 60-247638, Japanese Patent Laid-Open No. 60-208748, Japanese Patent Laid-Open 60-214354, Japanese Patent Publication No. 60-230135, Japanese Patent Publication No. 60-258539, Japanese Patent Publication No. 61-169829, Japanese Patent Publication No. 61-213213, Japanese Patent Publication No. 63-147159, Japanese Patent Publication No. 63-213837, Japanese Patent Publication No. 63-266448, Japanese Patent Publication No. 64-55551, Japanese Patent Publication No. 64-55550, Japan Examples of the resins soluble in the aqueous alkali solution described in each of the specifications of Japanese Patent Application Laid-Open No. 2-191955, Japanese Patent Laid-Open No. 2-199403, Japanese Patent Laid-Open No. 2-199404 and Japanese Patent Laid-Open No. 2-208602 are mentioned. Can be. Especially preferred is methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in the specification of Japanese Patent Application Laid-open No. 63-147159.

Moreover, as a component of a thermoplastic resin layer, it selects and uses together the resin which has the physical property of the weight average molecular weight 50000-500000, and the thing which has the physical property of weight average molecular weight 3000-30000 (Tg = 30-170 degreeC) as said resin. It is preferable to select and use together in the range of the weight average molecular weight 4000-20000 (Tg = 60-140 degreeC). Although these preferable specific examples can be selected from what is described in the said patent specification, Especially preferably, the styrene / described in each publication of Unexamined-Japanese-Patent No. 55-38961 and Unexamined-Japanese-Patent No. 5-241340 specification. (Meth) acrylic acid copolymer is mentioned.

Moreover, in order to adjust the adhesive force with a support body, in the organic polymer composition which comprises these thermoplastic resin layers, it is possible to add various plasticizers, various polymers, a supercooling substance, an adhesion improving agent, surfactant, a mold release agent, etc.

Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, diphenyl 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 Addition reaction product of polyethylene glycol mono (meth) acrylate, addition reaction product of organic diisocyanate with polypropylene glycol mono (meth) acrylate, condensation reaction product of bisphenol A and polyethylene glycol mono (meth) acrylate Can be mentioned.

As for the quantity of the plasticizer in an alkali-soluble thermoplastic resin layer, 200 mass% or less is common with respect to the said thermoplastic resin, Preferably it is 20-100 mass%.

As for the thickness of the alkali-soluble thermoplastic resin layer, 6 micrometers or more are preferable. If the thickness of the thermoplastic resin is 6 µm or more, the unevenness of the surface of the base can be completely absorbed. In addition, about an upper limit, about 100 micrometers or less are common from developability and aptitude for manufacture, Preferably it is about 50 micrometers or less.

In this invention, as a solvent of a thermoplastic resin layer, if melt | dissolving resin which comprises this layer, it can use without a restriction | limiting, for example, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, Isopropanol and the like.

(Middle floor)

In the photosensitive transfer material of the present invention, an intermediate layer may be formed between the support and the aqueous phase layer. After the transfer, the intermediate layer preferably functions as a protective layer of the aqueous phase layer, that is, an oxygen barrier layer.

There is no restriction | limiting in particular as resin which comprises an intermediate | middle layer as long as it is alkali-soluble. Examples of the resin include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. have. Moreover, the resin which copolymerized the monomer which has a carboxyl group and sulfonic acid group in resin which is not alkali-soluble normally like a polyester can also be used.

You may add additives, such as surfactant, to an intermediate layer as needed.

0.1-5 micrometers is preferable and, as for the thickness of an intermediate | middle layer from the viewpoint of the balance of oxygen barrier property and the removal property of the intermediate | middle layer at the time of image development, the range of 0.5-3 micrometers is more preferable.

As said coating solvent of an intermediate | middle layer, if said resin melt | dissolves, there will be no other restriction | limiting in particular, Although water is preferable. A mixed solvent in which water is mixed with the above-mentioned water miscible organic solvent is also preferable. Preferable specific 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 (wherein the mixing ratio indicates mass ratio)

In the photosensitive transfer material of the present invention, an aqueous phase layer containing a silver deposition nucleus may be coated on one side of the support, and a white layer may be coated on the other side of the support. In addition, a protective layer may be applied and formed between the alkali neutralizing layer and the neutralizing timing layer on the layer for image stabilization and the aqueous phase layer containing silver deposition nuclei. As a silver immersion nucleus binder, when cellulose ester is used, all or part of the hydrophilic acid is hydrolyzed by hydrolyzing the cellulose ester with an aqueous alkali solution such as sodium hydroxide or potassium hydroxide, the water / alcohol mixed solution of the alkali or the alcohol solution of the alkali. The use of regenerated cellulose is preferred because the alkali developer and the silver ion complex can be easily penetrated into the aqueous phase sheet and diffused.

In order to improve the preservation of the silver image formed in the present invention, a layer for trapping halide ions may be formed between the silver-immersed nucleus-containing aqueous layer and the support, and is described in, for example, Japanese Patent Laid-Open No. 59-231537. An image preservation improver may be contained in the aqueous phase layer.

(Processing method)

Although the transfer material of this invention obtained as mentioned above is cut | disconnected to a predetermined | prescribed size and used, there is no restriction | limiting in particular in the processing method at that time, ie, the cutting method at the time of processing, A well-known method is applicable.

[Shading Layer for Display Device and Manufacturing Method Thereof]

The photosensitive silver immersed nucleus layer or the photosensitive silver immersed nucleus-containing aqueous phase layer is exposed in image form and developed to form a cured silver immersion core layer or aqueous phase layer on the pattern only in the exposed region.

By acting a silver halide emulsion on the silver immersion nucleus, silver is deposited on the silver immersion nucleus to develop a patterned silver immersion nucleus layer or an aqueous phase layer, which is imaged to form a silver immersion layer to function as a light shielding layer. This light shielding layer region can be used as the light shielding layer for display device.

That is, by forming the light shielding layer using the above-mentioned photosensitive composition for manufacturing the light shielding layer aqueous layer for display device of the present invention, or the photosensitive transfer material for manufacturing the light shielding layer aqueous layer for display device using the photosensitive composition as an aqueous layer, The light shielding layer for display devices of this invention can be obtained.

The light shielding layer for display devices of this invention can be obtained with the following manufacturing methods.

The first manufacturing method comprises the step of forming a silver immersed core layer comprising an at least one silver immersed nucleus, a photopolymerization initiator, a photopolymerizable monomer, and an alkali-soluble binder on a light transmissive substrate, and exposing it in an image form. The image portion, i.e., the exposure portion for curing the exposed portion, the developing step for removing the image forming layer of the unexposed portion with the developing solution, and the step for depositing silver on the silver deposition nucleus by applying the silver deposit treatment liquid. A patterned light shielding layer is formed to form a light shielding layer for a display device.

The second manufacturing method is as follows.

Forming a photosensitive silver immersed core layer containing at least one silver immersion nucleus, a photopolymerization initiator, a photopolymerizable monomer and a binder on a transparent substrate, and applying a silver complex treatment solution containing a silver halide solvent to apply silver immersion from a silver halide emulsion. Through the process of depositing silver on the red nucleus and the process of forming a silver deposition pattern by the exposure phenomenon, an image portion, that is, a patterned light shielding layer, is formed to be a light shielding layer for a display device.

[Halogenated silver emulsion]

Silver halide emulsions are described. The silver halide emulsion may be applied by contacting the photosensitive layer containing one or more silver halide emulsions formed on the support with the aqueous phase layer, or by applying a photosensitive composition coating liquid containing silver halide emulsion on the surface of the aqueous phase layer.

The silver halide emulsion used here can apply any thing known in the field of silver dye photography. As silver halide, highly sensitive silver iodide (iodine content 1-10 mol%) is especially preferable. These may be dispersed and used in suitable protective colloidal materials such as gelatin, casein, albumin, polyvinyl alcohol, polyacrylamide and the like.

Suitable emulsions for this use are: Graffkide (Ｐ．Ｇｌａｆｋｉｄｅｓ) by Simi et Physics Photographics F. The Finn, Photographic Emulsion Chemistry (Published in 1966), V. Published by Ｔｈｅ ＦｏｃａｌＰｒｅｓｓ, 이. L. Making and coating photographic emulsion of J. Lichman et al. (Ｖ．Ｌ．Ｚｅｌｉｋｍａｎ ｅｔ ａｌ.).

These silver halide emulsions can be subjected to chemical sensitization, spectroscopic sensitization, and darkening sensitization as necessary.

In addition, an antifogging agent, a film hardening agent, a developing accelerator, a surfactant, an antistatic agent and the like may be added.

It is preferable to add a silver halide emulsion to a silver complex process liquid previously, or to apply it to a silver deposit core layer using binders, such as gelatin and PVA.

[Sliver Treatment Liquid]

The silver halide solvent used for the silver complex process liquid of this invention is described. As a silver halide solvent, what is used as a "fixing agent" in the field of silver salt photograph can be used. Specific examples include thiosulfate and cyanate, and sodium thiosulfate, ammonium thiosulfate, sodium cyanate and the like can be used. Moreover, the combination of cyclic imide, ammonia, or an amine, for example, the combination of uracil and an amine, is also a preferable silver halide solvent.

In the silver complex treatment solution of the present invention, a silver halide developing agent and an alkali agent may be added, in addition to the silver halide solvent.

Suitable silver halide development agents include benzene derivatives in which at least two hydroxyl and / or amino groups are substituted with octo or para positions of the benzene nucleus, for example hydroquinone, amidol, methol, glycine, p-aminophenol and pyrogallol and Hydroxylamines, in particular primary and secondary aliphatic and aromatic N-substituted or β-hydroxylamines, which are soluble in aqueous alkalis, for example hydroxylamine, N-methylhydroxylamine, N-ethyl Hydroxylamines and those described in US Pat. No. 2,857,276 and N-alkoxyalkyl substituted hydroxylamines described in US Pat. No. 3,293,034. The hydroxylamine derivative which has a tetrahydrofurfuryl group described in Unexamined-Japanese-Patent No. 49-88521 is also used. In addition, aminoreductones described in West German Patent Nos. 2,009,054, 2,009,055 and 2,009,078, and heterocyclic aminoreductons described in US Pat. No. 4,128,425 are also used. In addition, tetraalkyl reductic acid described in US Pat. No. 3,615,440 can also be used.

In addition, the phenidone compound, p-aminophenol compound and ascorbic acid of the auxiliary developer can be used in combination with the developer. Suitable silver halide solvents include conventional fixatives 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, for example Barbi. Tours, or combinations of uracil with ammonia or amines, and combinations described in US Pat. No. 2,857,274.

It is also possible to add silver halides to the treatment element and develop patterned silver deposition nuclei. The alkali agent of the present invention can be used without particular limitation as long as it is a substance that increases the pH of the silver complex treatment solution, but sodium hydroxide and potassium hydroxide are preferred.

It is preferable to process the silver complex process liquid of this invention for 10 to 30 minutes, More preferably, for 15 to 10 minutes in 0-50 degreeC, More preferably, it is the range of 5-35 degreeC. If the treatment temperature is too low or the treatment time is too short, the optical concentration of the light shielding layer may be insufficient. On the contrary, if the treatment temperature is too high or the treatment time is too long, the shade of the light shielding layer may be deteriorated or the reflectance may be increased. .

In the silver complex treatment of the present invention, the silver complex treatment liquid preferably uses an amount of about 100 g to 10,000 g, and more preferably about 500 g to 5000 g of silver per 1 g of silver deposition core. If the amount is too small, the optical concentration of the light shielding layer may be insufficient, and if the amount is too large, the cost is disadvantageous.

Since the photosensitive transfer material of this invention forms the photosensitive light shielding layer from the above-mentioned aqueous layer composition, it can manufacture the light shielding layer for display devices provided with the light-shielding layer which is a thin film and high optical density from this. .

Thus, the film thickness of the light shielding layer which comprises the light shielding layer for display apparatuses of this invention produced is about 0.2-1.0 micrometer, Preferably it is 0.6 micrometer or less. Since the light shielding layer in the light shielding layer for display devices of this invention deposits the silver deposition nucleus with high hiding power, even such a thin film has sufficient optical density.

In order to form such a light shielding layer in a light shielding layer for display devices, this water phase material may be exposed through a photomask for light shielding layer for display by a conventional method and then developed. By this pattern exposure, only the exposure part of the aqueous layer which consists of the photosensitive composition for light-shielding layer aqueous layer manufacture for display apparatuses containing the silver deposition nucleus which is a coloring element hardens.

In order to develop the formed patterned aqueous 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 transmissive substrate, and an aqueous layer made of the photosensitive composition of the present invention is used as a light shielding layer photomask for a display device. After exposure and development through the photosensitive layer, the photosensitive layer may be disposed on the surface of the formed aqueous layer pattern so as to be in contact with each other, and after applying for a predetermined time, the photosensitive layer may be peeled off to form a light shielding layer for a display device.

Furthermore, after exposing and developing the transfer material which consists of the photosensitive composition of this invention through the light-shielding layer photomask for display apparatuses, after apply | coating the composition coating liquid which contained the silver halide emulsion to the surface layer pattern surface, and apply | coating for predetermined time, a coating liquid It is also possible to form a light-shielding layer by developing a hardened pattern by removing the light-shielding layer to obtain a light-shielding layer for a display device. After exposure through a light shielding layer photomask for a display device, development and color development can be carried out simultaneously by applying a developer containing silver halide emulsion on the surface of the aqueous phase pattern.

In addition, by combining both the transfer method and the coating method, a light shielding layer having desired characteristics can be formed to obtain a light shielding layer for a display device.

The manufacturing method of the light shielding layer for display devices of this invention does not need to perform a complicated process, and is low cost.

(developer)

The aqueous alkali solution used in the developing step is preferably a lean aqueous solution of an alkaline substance, but also includes a small amount of an organic solvent miscible with water. Suitable alkaline materials include alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium bicarbonate, potassium hydrogen carbonate), alkali metal silicates (Sodium silicate, potassium silicate) alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (e.g., 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.

When the developer contains the silver halide emulsion, the amount of addition is preferably in the range of 0.3 to 3 mol of silver halide per 1 mol of the silver halide dissolving material.

[Color Filter]

The color filter of the present invention comprises a color layer on a light-transmissive substrate and has two or more pixel groups representing different colors, and each pixel constituting the pixel group is isolated from each other by a light shielding layer for a display device. The said light shielding layer for display apparatuses is a light shielding layer for display apparatuses of this invention produced using the water phase layer composition for light shielding layer preparation for display apparatuses, or the photosensitive transfer material of this invention.

The pixel group may be two, three, or four or more. For example, in three cases, three colors of red (R), green (G), and blue (B) are used. When arranging three types of pixel groups of red, green, and blue, an arrangement such as mosaic type or triangle type is preferable, and any arrangement may be used when arranging four or more types of pixel groups.

As a light transmissive substrate used for a color filter, well-known glass plates or plastic films, such as a soda glass plate, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, etc. which have a silicon oxide film on the surface are used.

In order to produce a color filter, after forming two or more pixel groups by a conventional method on a light transmissive board | substrate, even if it forms a light shielding layer for display apparatuses as mentioned above, or a light shielding layer for display apparatuses is formed initially, Thereafter, two or more pixel groups may be formed.

Since the color filter of this invention is equipped with the above light shielding layer for display apparatuses, display contrast is high and it is excellent in flatness.

[LCD]

At least one of the liquid crystal display elements of the present invention is provided with at least one of a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of light transmissive substrates. As the color filter, a color filter having a plurality of pixel groups as described above and in which each pixel constituting the pixel group is 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, in the liquid crystal display device including the color filter, no cell gap deviation occurs between the color filter and the substrate, and display defects such as color deviation do not occur.

In another embodiment of the liquid crystal display device, at least one of the liquid crystal display device includes at least one color filter, a liquid crystal layer, and liquid crystal drive means on a pair of light transmissive substrates, and the liquid crystal drive means is an active element (for example, a TFT). And the light shielding layer for display devices produced using the water-receiving layer composition for manufacturing the light shielding layer for display device of the present invention or the photosensitive transfer material is formed between the respective active elements.

[Substrate with Shading Layer for Display Device]

The board | substrate with which the light shielding layer for display devices of this invention was formed has a light shielding layer formed on the light transmissive substrate. In the light shielding layer, since the silver particles diffused on the silver deposition pattern are deposited as silver fine particles, the particle size, aspect ratio and volume fraction of the silver fine particles vary depending on the thickness direction of the aqueous layer. Therefore, compared with the light shielding layer prepared with the silver fine particle whose particle size distribution was sharp, pure black near to achromatic color is obtained. In addition, since the volume fraction of the silver fine particles becomes smaller in the thickness direction, the silver fine particles are not fused even when heated. Therefore, when it observes from the back surface of a light shielding layer, the color taste of a light shielding layer is maintained in pure black, and it is preferable as a light shielding layer for display devices.

Moreover, the board | substrate with which the light shielding layer for display devices of this invention was formed can be used for manufacture of a color filter.

0.2-2.0 micrometers is preferable and, as for the film thickness of the light shielding layer in the board | substrate with this light shielding layer for display apparatuses, 0.2-0.9 micrometer is especially preferable. Since the light shielding layer in the light shielding layer board | substrate for display apparatuses of this invention disperse | distributed silver fine particles, even such thin films have sufficient optical density.

(Example)

Although an Example is given to the following and this invention is demonstrated to it in more detail, this invention is not limited only to these Examples.

Example 1

1. Fabrication of waterborne materials

(Adjustment of the photosensitive silver immersion nucleus-containing aqueous layer coating liquid)

0.07 M sulfide while stirring at 550 rpm in a vessel containing 24.3 g of a benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, mass average molecular weight = 30,000) dissolved in 380 g of acetone and 308 g of methyl ethyl ketone. After adding 16 ml of an aqueous solution of sodium 9 hydrochloride and 36 ml of acetone at a rate of 1 ml per second, stirring was continued for 2 minutes, followed by 16 ml of an aqueous 0.070 M solution of palladium tetrasodium tetrasodium trihydrate. And 36 ml of a methanol mixture were added at a rate of 1 ml per second, and stirring was continued for 5 minutes. These operations were performed at 25 degreeC.

Next, 17.3 g of benzyl methacrylate / methacrylic acid copolymer (molar ratio = 78/22, mass average molecular weight = 40,000), 132 g of methoxy propylene glycol acetate, 39.5 g of dipentaerythritol hexaacrylate, and 2-trichloromethyl- 2.02 g of 5- (P-styrylstyryl) -1,3,4-oxadiazole, 0.2228 g of phenothiazine, and 1.194 g of Megapack F176PF (Dinipon Ink, Fluorinated Surfactant) were added and stirred, The photosensitive composition which consists of silver immersion nucleus was obtained, and it was set as the photosensitive silver immersion nucleus containing aqueous layer coating liquid.

(Formation of photosensitive silver-immersed nuclear-containing aqueous layer)

The photosensitive silver immersed core-containing aqueous layer coating solution was applied to a glass substrate using a spin coater so as to have a film thickness of 0.2 µm, and dried at 100 ° C. for 5 minutes to form a photosensitive silver immersed core-containing aqueous layer. Then, using the spin coater, the following protective layer coating liquid was apply | coated so that a dry film thickness might be set to 1.5 micrometers, and it dried at 100 degreeC for 5 minutes, and obtained the photosensitive silver immersion core containing aqueous phase material.

[Protective Layer Coating Liquid]

Polyvinyl alcohol (PLA205 made by CRARE Co., Ltd.) 3.0 parts by mass

Polyvinylpyrrolidone (PHP-K30, manufactured by BAF Corporation)... 1.3 parts by mass

?Distilled water… 50.7 parts by mass

? Methyl Alcohol? 45.0 parts by mass

2. Fabrication of light shielding layer for display device

(Exposure or phenomenon)

The water phase material obtained as described above was exposed at a surface energy of 70 mJ / cm 2 from the application surface side using an ultrahigh pressure mercury lamp through a light shielding layer photomask for display device. Subsequently, it developed and washed with 33 degreeC for 20 second with the developing solution TCD (alkali developing solution manufactured by Fujishashin Film Co., Ltd.), and water was removed by air knife, and it dried. Furthermore, it heat-processed at 240 degreeC for 50 minutes, and formed the pattern (silver immersion nucleus pattern) of the aqueous layer containing silver immersion nucleus.

[Preparation of Silver Complex Treatment Liquid]

The silver complex treatment liquid prepared the thing of the following composition.

40% aqueous potassium hydroxide solution… 323 ml

Zinc oxide… 9.75 g

N, N-bis-methoxyethylhydroxyamine... 75 g

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? 0.35 g

? Urasil… 80g

?water… 1193 g

Silver iodide (AgI content 6.0 mol% homogeneous structure), 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, following sensitizing dyes A, B, A silver complex treatment solution containing an oil agent prepared by adding C to each of the following coating amounts was applied on a patterned silver immersion core layer with a thickness of 40 microns in dry film thickness.

Silver iodide, [silver conversion 2.0],

4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene [0.01],

The following sensitizing dyes A [3.2 × 10 ⁻⁴ ],

The following sensitizing dyes B [3.2 × 10 ⁻⁴ ],

The following sensitizing dyes C [1.2 × 10 ⁻⁴ ],

In addition, the number in [] shows the amount of solid content conversion in g / m <2> unit.

As described above, a sample in which a photosensitive silver deposit layer and a protective layer were formed on a glass substrate was prepared.

After application, it was kept at 25 ° C. for 40 seconds and silver was deposited on the silver immersion nucleus. Thereafter, excess silver complex treatment solution was removed with distilled water at 30 ° C, and water was removed with an air knife to dry. By this treatment, the removal of the uncured aqueous layer and the formation of the patterned light shielding layer due to the color of the cured aqueous layer pattern developing in black are performed in one step, and thus the patterned light shielding layer of Example 1 is provided. The light shielding layer for display devices was obtained.

[Evaluation of Shading Layer for Display Device]

1. Film thickness measurement

The film thickness was measured by the following method. The sample to which the aqueous layer was applied was exposed to light at a coating surface of 70 mJ / cm 2 using an ultrahigh pressure mercury lamp to cure the aqueous layer. In the formed light shielding layer for display devices, the film thicknesses of the aqueous phase layer forming region and the unformed region (the region of the support body only) were measured by using a stylus type surface roughness meter P-1 (manufactured by TEENPOP Co., Ltd.). The thickness of the aqueous layer was measured by taking.

2. Measurement of optical concentration

The optical density of the film was measured by the following method. 500 mJ / cm <2> is exposed to the silver deposition layer apply | coated and formed on the glass substrate using the ultrahigh pressure mercury lamp on the application surface side, and this optical density is measured using a Macbeth densitometer (TD-904 made from Macbeth) (OD). The optical concentration (OD ₀ ) of the separate glass substrate is measured in the same manner, and the difference between them, that is, the value obtained by subtracting the _{O 0} from the _O D, is taken as the optical density of the film.

3. Formation of blue, red, green pixels and evaluation of bubble of pixel

The pixels of each color were formed on the glass substrate in which the light shielding layer for display devices was formed using the sample R1, G1, B1 of Example-1 of Unexamined-Japanese-Patent No. 2002-341127. The method of this patent description was used also for the method of pixel formation.

Since pixels of each color are formed on the unevenness of the light shielding layer for display devices, bubbles may enter between the glass substrate and the pixels of each color. The degree of bubble generation was measured by the following method.

A total of 300 pixels of each of the three pixels of the glass substrate were visually counted in the number of bubbles by using an optical microscope. The smaller the number, the better.

4.Color change of light shielding layer for display device by heating

The change of the color of the light shielding layer for display devices before and after heat-treating the glass substrate which formed the light shielding layer for display apparatuses at 220 degreeC for 2 hours was visually evaluated. Moreover, what is practically acceptable in the following evaluation is a thing of A-C level.

No change seen at all: A

Very little metallic luster: B

Slightly metallic, but practically acceptable: C

Metallic luster enough to be impaired in practical use: D

Complete metallic gloss: E

Table 1 shows the results of the above evaluation.

(Examples 2-7)

Aqueous concentration of aqueous gold chloride solution (Example 2), aqueous iridium chloride solution (Example 3), instead of the 0.070 M aqueous solution of palladium tetrachloride-2 sodium-3 hydrochloride used in the formation of the silver immersion nucleus in Example 1, Except for using the cupric chloride aqueous solution (Example 4), the chloroplatinic acid aqueous solution (Example 5), the aqueous osmium dichloride solution (Example 6) and the silver nitrate aqueous solution (Example 7), respectively, the same method as in Example 1 The light shielding layer for devices was formed and the same evaluation was performed. The results are written together in Table 1.

(Examples 8-11)

Instead of the 0.070 M aqueous solution of palladium tetrachloride-2 sodium-3 hydrochloride used in the formation of the silver immersion nucleus in Example 1, an aqueous solution of palladium tetrachloride-2 sodium-3 hydrochloride of the same concentration, aqueous solution of chloric acid, aqueous solution of chloroplatinic acid, And the light-shielding layer for display apparatuses formed in the same manner as Example 1 except having used the silver nitrate aqueous solution in the ratio shown in Table 1, and performed the same evaluation. The results are written together in Table 1.

Example 12

In Example 1, after forming the photosensitive silver-deposited nucleus-containing aqueous layer, silver iodide (AgI content 6.0 mol% homogeneous structure) with a mean particle size of 1.1 mu m, 4-hydroxy-6-methyl-1,3,3a, 7- The tetrahalide and the following sensitizing dyes A, B, and C were added to the following coating amounts, respectively, to prepare a prepared silver halide emulsion.

Silver iodide, [silver conversion 2.0]

4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene [0.01],

The sensitizing dye A [3.2 × 10 ⁻⁴ ],

The sensitizing dye B [3.2 × 10 ⁻⁴ ],

The sensitizing dye C [1.2 × 10 ⁻⁴ ],

Gelatin [2.0],

In addition, the number in [] shows the amount of solid content conversion in unit of g / m <2>.

Furthermore, the protective layer coating liquid of Example 1 was apply | coated so that a dry film thickness might be set to 1.5 micrometers, and the photosensitive silver immersion core containing aqueous phase material was formed. The photosensitive silver-deposited nucleus-containing water phase material obtained as described above was exposed to the surface energy of 70 mJ / cm 2 from the application surface side using an ultrahigh pressure mercury lamp through a photomask for light shielding layers for display devices.

Next, the solution of the following composition of the temperature of 10 degreeC was apply | coated to the thickness of 40 micron, it hold | maintained at 10 degreeC for 50 second, and silver was deposited on silver immersion nucleus.

40% aqueous potassium hydroxide solution… 323 ml

Zinc oxide… 9.75 g

N, N-bis-methoxyethylhydroxyamine... 75 g

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? 0.35 g

? Urasil… 80g

?water… 1193 g

After that, the excess silver complex treatment solution and the silver halide emulsion layer were removed with distilled water at 10 ° C., and water was dried with air knife. Furthermore, it heat-processed at 240 degreeC for 50 minutes, and formed the light shielding layer for patterned display devices. Evaluation of this light shielding layer for display devices was performed similarly to Example 1.

(Examples 13 to 24)

In Examples 1 to 12, a light shielding layer for a display device was formed in the same manner as in Example 1 except that a protective layer was not formed on the surface of the aqueous phase layer and the exposure dose was changed from 70 mJ / cm 2 to 500 mJ / cm 2. , Did the same evaluation. The results are written together in Table 1.

(Table 1)

As can be seen 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 small thickness of the light shielding layer. Moreover, generation | occurrence | production of the bubble which can be seen visually at the time of pixel formation was not confirmed, and it was also suitable for formation of a color filter. In addition, since the change in color after heating was hardly confirmed and the thermal stability was also high, it was clear that high durability could be expressed even when used in a liquid crystal display device.

(Examples 25 to 35)

1. Production of transfer materials

A 75 μm-thick polyethylene terephthalate support was applied to a thermoplastic resin layer coating liquid 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. Then, the protective layer coating liquid used in Example 1 as an intermediate | middle layer was apply | coated so that dry film thickness might be 1.5 micrometer on this, and it dried at 100 degreeC for 5 minutes.

[Thermoplastic resin layer coating liquid]

Copolymer of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid = 54/12/5/29 (number average molecular weight 80000). Part 58

Styrene / acrylic acid = 70/30 copolymer (number average molecular weight 7000). Part 136

? Polyfunctional acrylate (JP-500, product made by Shin-Nakamura Kagaku Co., Ltd.)… 90 parts

Fluorine-based surfactants (F176FP, manufactured by Dainippon Ink & Chemicals, Inc.); chapter 1

? Methyl ethyl ketone? Part 541

? 1-methoxy-2-propanol? Part 63

? Methyl Alcohol? 111 copies

Furthermore, on the said intermediate | middle layer, the photosensitive silver immersion nucleus layer coating liquid similar to what was used in Examples 1-11 was apply-dried, and the transfer material was produced.

2. Fabrication of light shielding layer for display device

Each of the transfer materials and the glass substrate obtained as described above were overlapped so that the aqueous layer and the glass surface were in close contact with each other, and both were bonded using a laminator. Lamination conditions are pressure 0.8kg / cm <2>, temperature 130 degreeC.

Thereafter, the polyethylene terephthalate support was peeled off to obtain a laminate obtained by transferring an aqueous layer and a protective layer onto a glass substrate. The laminated body is exposed through a mask for light shielding layers for display devices using ultra-high pressure mercury lamps under conditions such that the energy on the surface becomes 70 mJ / cm 2 from the side of the surface of the aqueous layer and the intermediate layer. Using the above, development was carried out.

(1) Developing solution The developing process was carried out at 30 ° C. for 40 seconds using a TDP (alkali developer manufactured by Fujishashin Film Co., Ltd.).

(2) Development process The solution was developed at 33 ° C. for 20 seconds using a TCD (alkali developer made by Fujishashin Film Co., Ltd.).

(3) Development treatment solution The development process was performed at 33 degreeC for 20 second using TSD (alkali developing solution manufactured by Fujishashin Film Co., Ltd.).

After the development treatment, water washing was performed and water was removed with an air knife. Furthermore, it heat-processed at 240 degreeC 50 minutes, and formed the silver deposition core layer pattern containing a silver deposition nucleus.

Thereafter, the silver halide emulsion layer was formed and the silver body treatment solution was immersed in the same manner as in Examples 1 to 11 to obtain a substrate having a light shielding layer. The evaluation similar to Example 1 was performed about these samples.

Table 2

(Comparative Example 1)

1.Production of silver fine particles

(Preparation of A Amount)

1950 g of distilled water was added to 50 g of demineralized gelatin, and the obtained mixture was heated to about 40 ° C to dissolve gelatin. It was prepared at pH 9.2 by 5% NAOH aqueous solution, and it kept warm at 40 degreeC.

(Preparation of amount of B)

1350 g of distilled water was added to 150 g of demineralized gelatin, and the obtained mixture was heated to about 40 ° C to dissolve gelatin. Similarly, it prepared in 9.H 9.2 with 5% NAOH solution. 160 g of nitric acid dissolved in 16.0 g of calcium acetate and 320 ml of distilled water was stirred and dissolved, distilled water was added, the final volume was adjusted to 2000 ml, and the temperature was kept at 40 ° C.

(Preparation of the amount of C)

110 g of sodium sulfite (anhydrous) was dissolved in 700 ml of distilled water, and 80 g of hydroquinone was dissolved in 70 ml of methanol and 80 ml of water. Then, distilled water was added to adjust the final volume to 2000 ml. Insulated by.

While liquid A was rapidly stirred, liquid B and liquid C were added simultaneously over 10 seconds. After 10 minutes, a solution in which 1600 g of anhydrous sodium sulfate was dissolved in 70 ml of concentrated hydrochloric acid and 8000 ml of distilled water was added, stirred for 80 minutes, and then precipitated and cooled. After the supernatant was removed, it was immediately rinsed with distilled water until the precipitate could not be precipitated even if the ferric salt solution was added. After removing water, the solution was redissolved at 40 ° C. Subsequently, the product (re-dissolved solution) was cooled to near the gelling temperature, and passed through a small hole into the cooled water, thereby forming a very fine noodle.

20 g of sodium sulfite (anhydrous) and 0.6 g of NAOH were dissolved in 2000 ml of distilled water, and 20 g of glacial acetic acid was washed in 2000 ml of distilled water. The obtained black slurry particle | grain was wash | cleaned by passing tap water through the slurry in the nylon mesh bag, washing water passed through the bag for about 30 minutes, and all the salts were wash | cleaned.

The water | moisture content of the product was adjusted so that the wash | cleaned black silver which disperse | distributed to the gel slurry may obtain the black silver dispersion which has the silver of the density | concentration of 1.5 mass%.

(Production of silver fine particles)

To 5000 g of the silver dispersion slurry obtained as described above, 25 g of a dispersant (Rapizol B-90, manufactured by Nihon Yushi Co., Ltd.) and 1000 g of 5% by mass aqueous solution of papain were added and stored at 37 ° C. for 24 hours. The solution was centrifuged at 2000 rpm for 5 minutes and the silver fine particles were allowed to settle. After discarding the supernatant, it was washed with distilled water to remove the enzyme decomposed gelatin decomposition products. Subsequently, the silver fine particles 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 16.4 g of methyl ethyl ketone 1.05 g of Solsper's 20000 (Avisia Co., Ltd. dispersant) were mixed. The silver fine particle dispersion A-1 of 30 nm of average particle diameters was obtained using this bead disperser (zirconia beads 0.3mm).

2. Adjustment of coating liquid for photosensitive layer

The following additive was added to the silver fine particle dispersion A-1 obtained as mentioned above, and it was set as the coating liquid for photosensitive layers.

[Coating liquid for photosensitive layer]

Silver particulate dispersion A-1... 40.0 g

Propylene Glycol Monomethyl Ether Acetate 40.0 g

? Methyl ethyl ketone? 37.6 g

? Fluorinated Surfactant…? 0.2 g

(Made by Dainippon Ink, F176FP (20%))

Hydroquinone monomethyl ether 0.001g

Dipentaerythritol hexaacrylate (added so that the volume fraction in the photosensitive layer of silver fine particles becomes 0.126) 0.001g

Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate. 0.1g

3.Preparation of protective layer coating liquid

The same protective layer coating liquid as used in Example 1 was adjusted.

4. Fabrication of photosensitive material

The coating liquid for photosensitive layers was apply | coated to the glass substrate using the spin coater so that optical density might be 4.0, and it dried at 100 degreeC for 5 minutes. Then, the said protective layer coating liquid was apply | coated so that dry film thickness might be set to 1.5 micrometers using the spin coater, and it dried at 100 degreeC for 5 minutes.

5. Fabrication of light shielding layer for display device

Exposure was performed on the application surface side using the ultrahigh pressure mercury lamp on the surface where the surface energy becomes 70 mJ / cm <2> through the mask for light-shielding layers for display devices. Subsequently, development was performed sequentially under the following conditions to obtain a light shielding layer for a display device.

(1) Development Treatment The solution was developed at 33 ° C. for 20 seconds using a TCD (alkali developer manufactured by Fujishashin Film Co., Ltd.).

(2) Developing solution The developing process was carried out at 33 ° C. for 20 seconds using TSD (Alkali developer manufactured by Fujishashin Film Co., Ltd.).

[Evaluation of Shading Layer for Display Device]

In the same manner as in Example 1, the light shielding layer for display device was evaluated. The results are written together in Table 2. In particular, the result of the color change of the light shielding layer for display devices before and after the heat treatment was an E rank indicating complete metallic gloss according to the above evaluation criteria, which was not practical.

In addition, the result of the film thickness measurement was 0.11 micrometer.

(Comparative Example 2)

1. Preparation of photosensitive transfer material

The same thermoplastic resin layer coating liquid as used in Example 23 was applied to a biaxially stretched polyethylene terephthalate support having a thickness of 15 μm using a slide coater and dried at 100 ° C. for 5 minutes. Subsequently, the intermediate layer coating liquid of Example 25 was apply | coated so that a dry film thickness might be 1.5 micrometer on this, and it dried for 100 minutes at 100 degreeC. Furthermore, the coating liquid for photosensitive layers similar to what was used by the comparative example 1 was apply | coated and dried, and the photosensitive transfer material was produced.

2. Fabrication 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 the same laminator as in Example 23 above. Lamination conditions are pressure 0.8 kg / cm <2>, temperature 130 degreeC.

Thereafter, the polyethylene terephthalate support was peeled off. Exposure was performed through the mask for light-shielding layers for display apparatuses on the application surface side using the ultrahigh pressure mercury lamp on condition that energy on surface will be 70 mJ / cm <2>. Subsequently, after developing in order under the following conditions, it washed with water, water was removed with the air knife, and the light shielding layer for display devices was obtained.

(1) Development treatment solution The development process was performed at 30 degreeC for 40 second using TDP (alkali developing solution manufactured by Fujishashin Film Co., Ltd.).

(2) Development treatment solution The development process was performed at 33 degreeC for 20 second using TCD (alkali developing solution manufactured by Fujishashin Film Co., Ltd.).

(3) Development Treatment The solution was developed at 33 ° C. for 20 seconds using a TDS (Alkali developer manufactured by Fujishashin Film Co., Ltd.).

[Evaluation of Shading Layer for Display Device]

In the same manner as in Example 1, the light shielding layer for display device was evaluated. The results are written together in Table 2. In particular, the result of the color change of the light shielding layer for display devices before and after the heat treatment was an E rank indicating complete metallic gloss according to the above evaluation criteria, which was not practical.

In addition, the result of the film thickness measurement was 0.11 micrometer.

(Comparative Example 3)

1. Preparation of resist coating liquid

The following black resist coating liquid was applied onto a glass substrate so as to have an optical density (OD) of 4.0, and dried at 100 ° C. for 5 minutes. The intermediate layer coating liquid was apply | coated so that dry film thickness might be set to 1.5 micrometers, and it dried at 100 degreeC for 5 minutes. In addition, an intermediate | middle layer coating liquid is common with Examples 25-35.

Black resist coating liquid:

CFP-FF-775B (C.PU15: 6 dispersion Fujifilm Orlean Co., Ltd.). 4.50part

CFP-FF-293Y (C.PI. 139 dispersion FUJIFILM ORIN CO., LTD.) Part 3.37

CFP-FF-802V (C.PI.23 dispersions manufactured by Fujifilm Orlean Co., Ltd.) Part 4.16

CFP-FF-949K (Carbon Black Dispersion FUJIFILM ORIN CORPORATION) Part 11.9

? MPM-AC (propylene glycol monomethyl ether acetate)... Part 18.9

? Methyl ethyl ketone? Part 52.0

Hydroquinone monomethyl ether 0.0022part

? Defentaerythritol hexaacrylate… Part 4.85

Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate. 0.238part

? Copolymer (30% by mass solution of methyl isobutyl ketone) 0.065part

2. Fabrication of light shielding layer for display device

The photosensitive material which apply | coated the said black resist coating liquid was exposed on the application surface side using the ultrahigh pressure mercury lamp on the coating surface side on the conditions which become 70 mJ / cm <2> using the mask for display devices. Subsequently, after developing in order under the following conditions, it washed with water, water was removed with the air knife, and the light shielding layer for display devices was obtained.

(1) Development Treatment The solution was developed at 33 ° C. for 20 seconds using a TCD (alkali developer manufactured by Fujishashin Film Co., Ltd.).

(2) Developing process The developing process was carried out at 33 degreeC for 20 second using TDS (alkali developing solution manufactured by Fujishashin Film Co., Ltd.).

[Evaluation of Shading Layer for Display Device]

The light shielding layer for display devices was evaluated in the same manner as in Example 1. The results are written together in Table 2. The result of the film thickness measurement was 2.35 μm. Since it was such a thick light-shielding layer, in "the formation of blue, red, green pixels, and the evaluation of the bubble of a pixel," the number of bubbles which can be visually recognized was counted as 50 or more, and it was impractical as a color filter.

(Comparative Example 4)

1. Preparation of photosensitive transfer material

The same thermoplastic resin layer coating liquid as used in Example 25 was apply | coated to the biaxially-stretched 75-micrometer-thick polyethylene terephthalate support body so that thickness might be set to 15 micrometers using the slide coater, and it dried at 100 degreeC for 5 minutes. Subsequently, the intermediate layer coating liquid of Example 25 was apply | coated so that a dry film thickness might be 1.5 micrometer on this, and it dried at 100 degreeC for 5 minutes. Furthermore, the coating liquid for black resists similar to what was used for the comparative example 3 was apply-dried, and the photosensitive transfer material was produced.

2. Fabrication 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 using the same laminator as used in Example 25 above. Lamination conditions are pressure 0.8 kg / cm <2>, temperature 130 degreeC.

Thereafter, the polyethylene terephthalate support was peeled off. Exposure was performed on the application surface side using the ultrahigh pressure mercury lamp on the conditions which become surface energy 70mJ / cm <2> through the mask for light-shielding layers for display devices. Subsequently, after developing in order under the following conditions, it washed with water, water was removed with the air knife, and the light shielding layer for display devices was obtained.

(1) Development Treatment The solution was developed at 30 ° C. for 40 seconds using a TDP (alkali developer manufactured by Fujishashin Film Co., Ltd.).

(2) Development Treatment The solution was developed at 33 ° C. for 20 seconds using a TCD (alkali developer manufactured by Fujishashin Film Co., Ltd.).

(3) Developing process The developing process was performed at 33 degreeC for 20 second using TDS (alkali developing solution manufactured by Fujishashin Film Co., Ltd.).

[Evaluation of Shading Layer for Display Device]

The light shielding layer for display devices was evaluated in the same manner as in Example 1. The results are written together in Table 2. The result of the film thickness measurement 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 bubble of a pixel," the number of bubbles which can be visually recognized was counted as 50 or more, and it was impractical as a color filter.

From the evaluation results of the above Examples 1 to 33 and Comparative Examples 1 to 4, the light shielding layer for a display device produced by the photosensitive composition of the present invention may be formed by a coating method or a thin layer, whether formed by a transfer method. It was also found that even when the pixel was formed and there was no color change after heating, and the pixel was formed to form a color filter, generation of bubbles was suppressed and it could be preferably used for an optical element or a color filter.

On the other hand, the light shielding layers for display devices of Comparative Examples 1 and 2 having light shielding layers in which conventional silver fine particles are dispersed have excellent light shielding properties, but are practically used as light shielding layers for display devices in that the change in gloss is remarkable after heat treatment. It was found that it is not suitable for. In addition, the light shielding layers for display devices of Comparative Examples 3 and 4 produced by using the coating liquid for black resist have a thick film thickness of the light shielding layer, and the generation of bubbles at the time of forming pixels is remarkable. It turned out that it is not suitable for the light shielding layer for devices.

According to the photosensitive composition of the present invention, a light shielding layer for a display device can be produced with a thin film and high light blocking performance and low cost. Moreover, the photosensitive transfer material using this photosensitive composition can be provided.

The light shielding layer for a display device of the present invention obtained by the photosensitive composition of the present invention is a thin film and has an effect of having high light shielding performance, and according to the method for manufacturing a substrate on which the light shielding layer for display device of the present invention is formed, such a display device The board | substrate which has a light shielding layer for can be manufactured easily at low cost.

Further, by forming the light shielding layer for a display device having the thin film and high light shielding performance of the present invention, it is possible to provide a substrate having a color filter and a liquid crystal display device having excellent characteristics and a light shielding layer for the display device having a thin film and high light shielding performance. have.

Claims (14)

2 or 3 types of silver immersion nuclei, a photoinitiator, a photopolymerizable monomer, and a binder, The photosensitive composition characterized by the above-mentioned. The photosensitive composition as claimed in claim 1, wherein the silver deposit nucleus contains at least a sulfide. The photosensitive composition according to claim 1, wherein the binder contains an alkali-soluble binder in the range of 20 to 80% by mass with respect to the solid content of the photosensitive composition. A photosensitive transfer material having at least a photosensitive silver immersion nucleus-containing layer formed on a support, wherein the photosensitive silver immersion nucleus-containing layer contains two or three silver immersion nuclei, a photopolymerization initiator, a photopolymerizable monomer, and a binder. material. 5. The photosensitive transfer material as claimed in claim 4, wherein said silver deposit nucleus contains at least a sulfide. The photosensitive transfer material according to claim 4, wherein the binder contains an alkali-soluble binder in the range of 20 to 80 mass% with respect to the solid content of the photosensitive silver immersion nucleus-containing layer. The photosensitive silver immersion nucleus-containing layer formed on the board | substrate using the photosensitive composition as described in any one of Claims 1-3, or the photosensitive transfer material as described in any one of Claims 4-6, is exposed and developed. After that, silver is deposited. On the light transmissive substrate, each pixel constituting the pixel group, which is composed of a colored layer and exhibits different colors, is separated from each other by a light shielding layer for display device. The light shielding layer for devices is a light shielding layer for display devices of Claim 7, The color filter characterized by the above-mentioned. A liquid crystal display device comprising at least one color filter, a liquid crystal layer, and a liquid crystal driving means between a pair of substrates having at least one light transmissive, wherein the color filter is the color filter according to claim 8. device. A liquid crystal display device comprising a color filter, a liquid crystal layer, and liquid crystal drive means between a pair of substrates, at least one of which is light transmissive, wherein the liquid crystal drive means has an active element, and between each active element is a liquid crystal display element. A liquid crystal display device comprising a light shielding layer for a display device. A substrate on which a light shielding layer for a display device having a light transmissive substrate and a light shielding layer formed on the substrate is provided, wherein the light shielding layer is a light shielding layer for a display device according to claim 7. Board. Forming a photosensitive silver immersion nucleus-containing layer containing two or three types of silver immersion nuclei, a photopolymerization initiator, a photopolymerizable monomer, and a binder on the light-transmitting substrate; Deposition of silver on the silver immersion nucleus by applying an exposure step of photopolymerizing the part, removing the unexposed portion by the developing solution, forming a silver immersion nucleus pattern, and applying a silver complex treatment solution containing a silver halide solvent to the silver immersion nucleus pattern. And forming a light shielding layer, wherein the light shielding layer for display device is formed. The method of manufacturing a substrate with a light shielding layer for a display device according to claim 12, wherein the silver deposition nucleus contains at least sulfide. The method for manufacturing a substrate with a light shielding layer for a display device according to claim 12, wherein the binder contains an alkali-soluble binder in the range of 20 to 80 mass% with respect to the solid content of the photosensitive silver immersion nucleus-containing layer.