JP4663261B2 - Black matrix, transfer material, fine particle dispersion composition, color filter, display device, and method for producing black matrix - Google Patents

Description

  The present invention relates to a black matrix used for a color filter in a display device such as a liquid crystal display device, a manufacturing method thereof, a composition for forming the same, and fine particles.

  The black matrix referred to in the present invention means a black edge or a lattice shape between red, blue, and green pixels provided in the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, or a CRT display device. Or a stripe-like black edge, a dot-like or linear black pattern for shielding a TFT, and the like. The definition of the black matrix is described in Non-Patent Document 1, for example.

  The black matrix improves display contrast, and in the case of an active matrix liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to current leakage due to light, a high light shielding property (optical density OD). 3 or more) is required.

Conventionally, a black matrix using a sputtered film of a metal such as chromium is known. In this method, a sputtered metal film is formed on a substrate, and then a photosensitive resist layer is applied thereon, then the photosensitive resist layer is exposed and developed using a photomask having a black matrix pattern, and then the metal layer is formed. This is a method for forming a black matrix by etching and finally removing the photosensitive resist layer (see, for example, Non-Patent Document 2 for a black matrix using a chromium film).
According to this method, a black matrix having a high light-shielding property can be obtained with a thin layer of about 0.2 μm.

As a black matrix having a small environmental burden in production, a black matrix such as carbon black or titanium black dispersed in a polymer binder is known (see Patent Document 1). This is done by applying a coating liquid containing the black pigment, polymer, monomer, photopolymerization initiator, etc. on the substrate, and then exposing and developing the coating layer using a photomask having a black matrix pattern to form a black matrix. It is a method of forming.
In this method, unlike the method using a metal sputtered film, a black matrix can be obtained by a method with a small environmental load. However, since carbon black and titanium black have a smaller hiding power than the metal layer, a thickness of 1 μm or more is necessary to provide sufficient light shielding properties.

  In the case of a black matrix of 1 μm or more, there is a problem that the surface of red, blue and green pixels to be provided later is not smooth due to a step and color unevenness occurs. In order to prevent color unevenness, after red, blue, and color pixels are provided, the surface of the pixel is polished to ensure smoothness. However, both methods are very laborious and costly.

Furthermore, a method for forming a black matrix is disclosed in which a metal such as nickel is generated in a film using electroless plating (see Patent Document 2). Since this method also includes a plating step, the environmental burden of manufacturing is large as in the method using a metal sputtered film.
Also disclosed is a method of forming a black matrix in which a metal sulfide such as nickel is generated in a film using electroless plating (see Patent Document 3). Since this method also includes a plating step, the environmental burden of manufacturing is large as in the method using a metal sputtered film.

Therefore, a black matrix having a small environmental load, a thin layer and high light shielding properties, and a pigment capable of obtaining the black matrix have been desired.
"Liquid Crystal Display Equipment Dictionary" 2nd edition (Yasuhira Kanno, Nikkan Kogyo Shimbun, 1996) 64 pages "Next-generation LCD technology (issued by Tatsuo Uchida, Industrial Research Committee, 1994) 123 pages JP-A-62-9301 JP-A-5-241016 JP-A-7-218715

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a black matrix having a low environmental load, a thin layer and high light-shielding properties.

In view of such a situation, the present inventors have conducted intensive research, and as a result, a black matrix using core-shell fine particles having a shell made of a metal compound on the surface and having a core made of a metal inside solves the above problem, And it discovered that there was little light reflection of a metal and completed this invention.
That is, the present invention provides the following.

<1> A black matrix containing core-shell fine particles having a core made of metal inside and a shell made of a metal sulfide constituting the core on the surface .

<2> The black matrix according to <1>, wherein the number average particle diameter of the core-shell fine particles is in the range of 1 nm to 5000 nm.

<3> The black matrix according to <1> or <2> , wherein the ratio of the weight of the shell to the weight of the core-shell fine particles is 0.08 to 0.92 .

<4> The core-shell fine particles according to any one of <1> to < 3 >, wherein the metal is silver or palladium.
<5> On a temporary support, it has a core made of metal inside, has a shell made of a metal sulfide constituting the core on the surface, and contains core-shell fine particles whose metal is silver or palladium and a binder A transfer material having a transfer layer .
<6> The transfer material according to <5>, wherein the core-shell fine particles have a number average particle diameter in the range of 1 nm to 5000 nm.
<7> The transfer material according to <5> or <6>, wherein the ratio of the weight of the shell to the weight of the core-shell fine particles is 0.08 to 0.92.

< 8 > Core- shell fine particles having a core made of metal inside, a shell made of a metal sulfide constituting the core on the surface, and a metal made of silver or palladium, a dispersion medium, a polymer binder, a monomer, and light A fine particle dispersion composition containing a polymerization initiator.
<9> The fine particle dispersion composition according to <8>, wherein the number average particle diameter of the core-shell fine particles is in the range of 1 nm to 5000 nm.
<10> The fine particle dispersion composition according to <8> or <9>, wherein the ratio of the weight of the shell to the weight of the core-shell fine particles is 0.08 to 0.92.

< 11 > A color filter having the black matrix according to any one of <1> to <4> .

< 12 > A display device having the color filter according to < 11 >.

<13> A method for producing a black matrix, which is formed by a method including the following steps a and b.
a: Transferring the transfer layer of the transfer material according to any one of < 5 > to <7> to a substrate
b: Step of forming a black matrix by patterning

<14> A method for producing a black matrix, which is formed by a method including the following steps a and b.
a: The process of apply | coating and drying the composition in any one of < 8 >-<10> to a board | substrate.
b: Step of forming a black matrix by patterning

  According to the present invention, a black matrix having a high optical density, a small film thickness, and a small light reflection can be provided without using a plating technique with a complicated process and a large environmental burden and a vacuum technique with a large cost. That is, since the optical density can be increased at the core portion of the fine particles used in the present invention and the light reflection can be reduced at the shell portion, it is possible to provide a black matrix having a small film thickness and little light reflection.

[Core shell fine particles]
The core-shell fine particles of the present invention have a shell made of a metal compound on the surface and a core made of a metal inside.
Here, the term “metal” refers to that described in “Metal” on page 444 of the “Iwanami Physical and Chemical Dictionary (5th edition, published by Iwanami Shoten 1998)”. Among the metals forming the core inside the nanoparticle of the present invention, metals of Group 3 to Group 13 of the long periodic table are preferable. Of these, gold, silver, copper, palladium, platinum, tungsten, titanium, aluminum, nickel, and chromium are preferable, and silver is particularly preferable from the viewpoint of cost and stability.

The “metal compound” referred to in the present invention is a compound of the above metal and an element other than the metal.
Examples of compounds of metals and other elements include metal oxides, sulfides, sulfates, and carbonates. Of these, sulfides are particularly preferred because of their color tone and ease of fine particle formation. Examples of metal compounds include copper oxide (II), manganese oxide, iron sulfide, silver sulfide, copper sulfide (II), titanium black, etc., but silver sulfide is from the viewpoint of color tone, ease of fine particle formation and stability. Particularly preferred.
The metal constituting the metal compound forming the shell and the metal forming the core may be the same or different. However, the same kind is preferable from the viewpoint of easy particle formation.

Shape and size of core-shell fine particles The shape of the core-shell fine particles of the present invention is not particularly limited. It is not necessarily a true sphere, and may be a spheroid, an indefinite shape, or a polyhedron such as a regular hexahedron or a regular octahedron.
The average particle diameter of the core-shell fine particles of the present invention is preferably in the range of 1 to 5000 nm, more preferably in the range of 2 to 500 nm, and still more preferably in the range of 5 to 100 nm. Particles having an average particle size of less than 1 nm are difficult to produce, and if it exceeds 5000 nm, the stability of the dispersion in which the particles are dispersed is lowered.
The term “particle size” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area. The “average particle size” refers to the average value obtained by obtaining the above particle size for a large number of particles.
The ratio between the core radius and the shell weight of the core-shell fine particles of the present invention is not particularly limited.
The ratio of the weight of the shell to the weight of the particles is desirably 0.05 to 0.95, more preferably 0.08 to 0.92. If the weight ratio is too large, the light shielding property is deteriorated. On the other hand, if the weight ratio is too small, the light reflectance is increased, which is not preferable.

[Method for producing core-shell fine particles]
There is no restriction | limiting in particular in the formation method of the core-shell fine particle of this invention. Typical methods include the following.
(1) A method of forming a metal compound shell on the surface of a metal particle prepared by a known method by oxidation, sulfurization or the like. For example, there is a method in which metal fine particles are dispersed in a dispersion medium such as water and sulfides such as sodium sulfide and ammonium sulfide are added. There is also a method in which metal particles are brought into contact with a gas such as hydrogen sulfide or ozone to sulfidize or oxidize the surface. By these methods, the surface of the particles is sulfided or oxidized to form core-shell fine particles.
In this case, the metal to be used can be prepared by a known method such as a gas phase method or a liquid phase method. The method for forming metal particles is described in, for example, “Latest Trends in Technology and Application of Ultrafine Particles II (issued by Sumibe Techno Research Co., Ltd. 2002)”.
(2) A method of continuously forming a metal compound shell on the surface in the process of forming metal particles.
For example, there is a method in which a reducing agent is first added to a metal salt solution to form a metal core, and then a sulfide is added to form a metal sulfide shell.
In order to adjust the amount ratio of the surface metal compound to the metal inside the core-shell fine particles, in the case of a metal sulfide, a method of controlling the amount of sulfide to be added is preferable.

[Dispersion composition]
Next, the particle dispersion composition in which the core-shell fine particles of the present invention used for black matrix preparation is dispersed will be described.
There is no restriction | limiting in particular as a dispersion medium of a dispersion composition, Various things, such as water, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, acetone, methyl alcohol, n-propyl alcohol, i-propyl alcohol, can be used.
The core-shell fine particle concentration of the particle dispersion composition of the present invention is desirably 0.01 to 70% by mass, more preferably 0.1 to 30% by mass. When the concentration is less than 0.01% by mass, the amount of the dispersion composition for obtaining the necessary particles increases, which is disadvantageous. On the other hand, when the concentration exceeds 70% by mass, the stability of the composition decreases.

In addition to the core-shell fine particles and the dispersion medium, a dispersant, a surfactant, and the like may be added to the particle dispersion composition of the present invention.
As the dispersant, known dispersants such as polyvinyl alcohol, acrylamide, sodium polyacrylate, sodium alginate, acrylamide / acrylic acid copolymer, styrene / maleic anhydride copolymer can be used. As the dispersant, for example, those described in “Pigment Dispersion Technology, Technical Information Association (issued in 1999)” can be used.
As the surfactant, known anionic, cationic, nonionic or betaine surfactants can be used, and among these, anionic surfactants are preferred from the viewpoint of stability.
Examples of preferable anionic surfactants include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dioctylsulfosuccinate, sodium oleate and the like. For example, “Surfactant Handbook (Tokiyuki Yoshida, Shinichi Shindo, Tadayoshi Ogaki, Kazuyoshi Yamanaka, Optical Book Co., Ltd., published in 1987)”
It is described in. Further, as a surfactant, C ₈ F ₁₅ SO ₂ N (C ₂ H ₅ ) (CH ₂ O) ₁₄ H, C ₈ F ₁₇ SO ₃ Li, C ₇ F ₁₅ COONH ₄ , C ₈ F ₁₇ SO ₂ (C Fluorine surfactants such as ₂ H ₅ ) C ₂ H ₄ OPO (OH) ₂ , F110, F113, F176PF, F117, and F780 (all oligomer type fluorine surfactants manufactured by Dainippon Ink & Chemicals, Inc.) Is also preferable.

[Black Matrix]
Next, the black matrix of the present invention will be described.
As described above, the black matrix of the present invention can be used for a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, etc. Among them, it is particularly preferable to use it for a liquid crystal display device.
The black matrix preferably has a thickness of 0.1 to 0.8 μm, more preferably 0.2 to 0.6 μm. When the thickness is less than 0.1 μm, the light-shielding property is lowered, and when the thickness exceeds 0.8 μm, the surface of red, blue, and green pixels to be provided thereafter is not smooth and color unevenness occurs.

The optical density of the black matrix is preferably 3.0 or more, more preferably 3.5 or more. When the optical density is less than 3, the contrast is lowered and the display quality is lowered.
Although there is no restriction | limiting in particular in the volume fraction of the core-shell fine particle in a black matrix, Usually, 5 to 70%, More preferably, the range of about 10 to 50% is desirable. If the volume fraction is less than 5%, the necessary light shielding properties cannot be obtained, and if it exceeds 70%, the black matrix becomes brittle.
In the case of the black matrix of the present invention, performances such as heat resistance, light resistance, chemical resistance, surface smoothness and hardness generally required for a color filter are required. For details on the required performance, see page 189 of “Color Filter Deposition Technology and Chemicals (Sequentially Supervised by Watanabe, CMC Co., Ltd., published in 1998)”, “Next Generation Liquid Crystal Display Technology (Tatsuo Uchida, Industrial Research Committee, 1994) Issued) ”on page 117. The necessary performance can be controlled by the pigment / binder ratio, binder type, exposure and heat treatment conditions, etc., as in the known black matrix.

[Transfer material and black matrix forming method using the same]
<Transfer material>
First, the transfer material of the present invention will be described. The transfer material of the present invention is a material having at least one transfer layer on a temporary support. The transfer material of the present invention may further be provided with a thermoplastic resin layer, an intermediate layer, a protective layer, a release layer, etc., if necessary. In particular, the thermoplastic resin layer and the intermediate layer are effective for improving the transferability and sensitivity of the transfer layer.

Temporary support As the temporary support used in the transfer material of the present invention, a known support such as polyester or polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of strength, dimensional stability, chemical resistance, and cost. The thickness of the temporary support is desirably 15 to 200 μm, more preferably 30 to 150 μm. If the thickness is too large, it is disadvantageous in terms of cost. If the thickness is too small, there is a disadvantage that the temporary support is deformed by the heat of the drying process or lamination process after coating.

Transfer layer The transfer layer of the transfer material of the present invention comprises a coating liquid obtained by adding a polymer, a monomer, a polymerization initiator, a polymerization inhibitor, a surfactant, a pigment and the like to the fine particle dispersion composition as necessary. It is obtained by coating and drying on a temporary support.
The transfer layer of the present invention preferably has a photosensitivity. The following can be used about the monomer added in order to provide photosensitivity, a polymerization initiator, and a polymerization inhibitor.
The transfer layer can be developed with an aqueous alkali solution, and can be developed with an organic solvent. In view of safety and the cost of the developer, a transfer layer that can be developed with an aqueous alkaline solution is preferable. The photopolymerizable composition that can be developed in an alkaline aqueous solution contains a carboxylic acid group-containing binder, a polyfunctional acrylic monomer, and a photopolymerization initiator as main components.

  Here, as the polyfunctional acrylic monomer, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-hexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) (Meth) acrylates such as acrylate are preferred.

As the carboxylic acid group-containing binder, a copolymer of an unsaturated organic acid compound such as acrylic acid or methacrylic acid and an unsaturated organic acid ester compound such as methyl acrylate, ethyl acrylate or benzyl methacrylate is preferable. For example, there are the following.
MAA / BzMA = 40/60 (35000), MAA / MMA / BzMA = 20/20/60 (14000), AA / MMA / BzMA = 20/60/20 (8000), AA / MMA / EA = 20/75 / 5 (60000) and MAA / St = 40/60 (42000).
However, MAA, AA, BzMA, MMA, EA, and St represent methacrylic acid, acrylic acid, benzyl methacrylate, methyl methacrylate, ethyl acrylate, and styrene, respectively. The ratio represents the mass ratio of the monomers, and the number in () represents the number average molecular weight of the polymer.
Examples of the photopolymerization initiator include a composition containing a halomethyloxadiazole compound, a vicinal polyketadonyl compound, an acyloin ether compound, a benzothiazole compound, an oxadiazole compound, or a halomethyl-s-triazine compound. be able to. Preferred examples of the photopolymerization initiator include bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate, US Pat. No. 4,239,850. And the trihalomethyl-s-triazine compounds described in US Pat. No. 4,221,976, and the like.

  Further, the preferred content of each component is expressed as mass% in the total solid content, the core-shell fine particles are 10% to 50%, the polyfunctional acrylate monomer is 10% to 50%, and the carboxylic acid group-containing binder is 20%. 60%, photopolymerization initiator is 1% to 20%. However, the photopolymerizable composition that can be used in the present invention is not limited to these, and can be appropriately selected from known ones.

In addition to this, a known polymerization inhibitor, a pigment other than black or black, a dye other than black or black, a surfactant, or the like may be added to the transfer layer as necessary.
The thickness of the transfer layer is preferably from 0.1 to 0.8 μm, more preferably from 0.2 to 0.6 μm. When the thickness is less than 0.1 μm, the light-shielding property of the formed black matrix decreases, and when the thickness exceeds 0.8 μm, the surface of the red, blue, and green pixels provided after forming the black matrix does not become smooth and color unevenness occurs. .

Thermoplastic resin layer Examples of the resin constituting the thermoplastic resin layer of the transfer material include acrylic resin, polystyrene resin, polyester, polyurethane, rubber resin, vinyl acetate resin, polyolefin resin, and copolymers thereof. it can. Although it is not essential that the resin constituting the thermoplastic resin layer of the present invention is alkali-soluble, it is desirable that the resin be alkali-soluble.
Specific examples of the resin constituting the thermoplastic resin layer include a saponified product of ethylene and an acrylic ester copolymer, a saponified product of styrene and a (meth) acrylic ester copolymer, styrene / (meth) acrylic acid / ( (Meth) acrylic acid terpolymers, saponified products of vinyltoluene and (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, (meth) acrylic such as (meth) acrylic acid butyl and vinyl acetate Saponification products such as acid ester copolymers, soluble in alkaline aqueous solutions of organic polymers by “Plastic Performance Handbook (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Federation (1968))” And so on.

These resins are preferably used by mixing two types (resin A and resin B) as follows.
The resin A has a weight average molecular weight of 50,000 to 500,000 and a glass transition temperature (Tg) in the range of 0 to 140 ° C., more preferably a weight average molecular weight of 60,000 to 200,000 and a glass transition temperature (Tg ) Is preferably in the range of 30 to 110 ° C. Specific examples of these resins include methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymers described in JP-A-63-147159.
The resin B has a weight average molecular weight of 3,000 to 30,000 and a glass transition temperature (Tg) in the range of 30 to 170 ° C., more preferably a weight average molecular weight of 4,000 to 20,000 and a glass transition temperature (Tg). ) Is preferably in the range of 60 to 140 ° C. Preferable specific examples include styrene / (meth) acrylic acid copolymers described in JP-A-5-241340.

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

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

It is preferable to use a mixture of two or more resins constituting the intermediate layer, and it is particularly preferable to use a mixture of polyvinyl alcohol and polyvinyl pyrrolidone. The mass ratio of the two is preferably polyvinylpyrrolidone / polyvinyl alcohol = 1/99 to 75/25, more preferably in the range of 10/90 to 50/50. If the mass ratio is less than 1/99, problems such as deterioration of the surface state of the intermediate layer and poor adhesion with the photosensitive resin layer coated on the intermediate layer may occur. Moreover, when the said mass ratio exceeds 75/25, the oxygen barrier property of an intermediate | middle layer falls and a sensitivity may fall.
The thickness of the intermediate layer is preferably from 0.1 to 5 μm, more preferably from 0.5 to 3 μm. If the thickness is less than 0.1 μm, the oxygen barrier property may decrease, and if the thickness exceeds 5 μm, the intermediate layer removal time during development may increase.

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

[Method for forming black matrix using transfer material]
Transfer A method for transferring the transfer material of the present invention to a substrate will be described. The transfer is preferably performed by laminating the transfer layer and the substrate in close contact. A known method can be used for laminating. For example, a laminator, a vacuum laminator or the like can be used at a temperature of about 60 to 150 ° C., a pressure of about 0.2 to 20 kg / cm ^{2, and} a line speed of about 0.05 to 10 m / min.
In the present invention, it is preferable to peel off the temporary support after lamination.

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

Developer As the developer, a dilute aqueous solution of an alkaline substance is used, but a developer added with a small amount of an organic solvent miscible with water may also be used. Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Mention may be made of morpholine, tetraalkylammonium hydroxides (for example tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01% by mass to 30% by mass, and the pH is preferably 8-14. Further, according to the properties such as oxidation of the transfer layer, for example, the pH of the developer can be changed to adjust the transfer layer so that the development by the film-like detachment can be performed.

  Suitable organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam and N-methylpyrrolidone. The concentration of the organic solvent miscible with water is generally 0.1 to 30% by mass.

A known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01 to 10% by mass.
The developer can be used as a bath solution or a spray solution. In order to remove the uncured portion of the transfer layer in a solid form (preferably in the form of a film), use a method such as rubbing with a rotating brush or a wet sponge in the developer, or spray pressure when the developer is sprayed. Is preferred. The temperature of the developer is usually preferably in the range of about room temperature to 40 ° C. It is also possible to put a water washing step after the development processing.

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

Post-exposure Further, after the development step, before the heat treatment, exposure may be performed to accelerate curing. This exposure can also be performed by the same method as the first exposure described above.

[Coating liquid and black matrix forming method using the same]
Coating Solution The black matrix of the present invention can be prepared by applying the following coating solution to a substrate.
It is preferable that the coating liquid used in the present invention also has photosensitivity as in the transfer layer of the transfer material. The photosensitive coating liquid can be obtained by adding a polymer, a monomer, a polymerization initiator, a polymerization inhibitor, a surfactant, a pigment and the like to the above-mentioned particle dispersion composition as necessary. As the monomer, polymerization initiator and other additives added for imparting photosensitivity, those described in the above-mentioned transfer layer section of the transfer material can be used.

Application | coating and drying In this invention, a coating liquid is apply | coated to a board | substrate. There is no restriction | limiting in particular as a coating method to a board | substrate. For example, a spin coating method described in JP-A-5-240111, a die coating method described in JP-A-9-323472, and the like can be used. The coating method is described in, for example, “Coating Engineering (written by Yuji Harasaki, Asakura Shoten, published in 1972)”.
The film thickness after drying is preferably 0.1 to 0.8 μm, more preferably 0.2 to 0.6 μm. When the thickness is less than 0.1 μm, the light-shielding property of the formed black matrix decreases, and when the thickness exceeds 0.8 μm, the surface of the red, blue, and green pixels provided after forming the black matrix does not become smooth and color unevenness occurs. .

Patterning The patterning of the present invention is preferably performed by exposure and development. For these, the method described in the method of forming a black matrix using a transfer material can be used.

Substrate As the substrate used in the present invention, a glass substrate usually used in a display device is preferable. As the glass substrate, a glass substrate using known glass such as soda glass, low alkali glass, non-alkali glass or the like can be used. As other substrates, transparent plastics such as silicon wafers and polyolefins can also be used. The thickness of the substrate is preferably from 0.5 to 3 mm, more preferably from 0.6 to 2 mm. The glass substrate and the plastic substrate are described, for example, on page 157 of “Reflective color LCD integrated technology (Tatsuo Uchida, CMC Co., Ltd., issued in 1999)”.

[Color filter]
The color filter of the present invention is a substrate provided with a black matrix of the present invention and further provided with pixel groups exhibiting two or more colors, for example, red, blue and green pixel groups.
There is no particular limitation on the method of forming the pixel group. Known methods such as a photolithography method, an etching method, and a printing method can be used. These methods are described in, for example, “Color Filter Film Formation Technology and Chemicals” (supervised sequentially by Watanabe, CMC Co., Ltd., issued in 1998).

Of these methods, the photolithography method is preferable. Specific methods include the following.
The first is a method using a resist solution containing a pigment or a dye. In this method, first, a resist is applied to a substrate, dried, exposed through a photomask, and then developed to create a color filter.
The second is a method using a transfer material having a transfer layer containing a pigment or dye. In this method, first, a transfer material is laminated on a substrate, exposed through a photomask, and then developed to form a color filter.

The arrangement method (BRG pixel pattern) of the pixel group of the color filter of the present invention is not particularly limited. An arrangement method such as a stripe type, a block type, or a checkered type can be used. A TFT type in which the pixel has an uneven shape can also be used. These arrangement methods are described, for example, on page 14 of “Color Filter Film Formation Technology and Chemicals” (supervised sequentially by Watanabe, CMC Co., Ltd., issued in 1998).
The chromaticity range of the color filter of the present invention is the same as that of the conventional color filter. The chromaticity range and related backlights are also described, for example, on page 15 of the aforementioned “Color filter deposition technology and chemicals (supervised sequentially by Watanabe, CMC Co., Ltd., issued in 1998)”.

  In the case of the color filter of the present invention, the heat resistance, light resistance, chemical resistance, surface smoothness, hardness and the like described for the black matrix are required.

[Display device]
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, see “Electronic Display Device (Akio Sasaki, Industrial Research Co., Ltd., 1990)
) ”,“ Display devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989) ”and the like.
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. For example, “Next generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”
It is described in. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. A color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center).

In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The black matrix of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shimadzu Co., Ltd., issued by 1994)”, “2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute published in 2003)
It is described in.

[Target use]
The black matrix of the present invention can be applied to applications such as portable terminals such as televisions, personal computers, liquid crystal projectors, game machines, and mobile phones, digital cameras, and car navigation systems without particular limitation.

[Example 1] (Preparation of silver particles / acetone system)
0.95 g of polymer P-1 was added to 200 g of an acetone dispersion of silver particles (average particle size 30 nm, concentration 2.5% by mass) and stirred for 30 minutes.
P-1: vinyl chloride / vinyl acetate = 60/40 (mass ratio) copolymer, weight average molecular weight 5000
Next, with stirring, an aqueous solution of sodium sulfide having a concentration of 7.2% by mass was added so that the sulfidation rate of the metal became the value shown in Table 1.

The “sulfidation rate” mentioned here is the proportion of metal particles that are sulfided. 0% of the sulfide is not sulfided at all, 100% is the state that the entire particle is completely sulfided. To express. The liquid temperature when the aqueous sodium sulfide solution was added was 23 ° C.
After addition of the aqueous sodium sulfide solution, stirring was continued for 30 minutes.
Silver core-shell fine particles having a silver sulfide shell were prepared by the above process.
These core shell fine particles were evaluated by the following method. The results are shown in Table 1.

[Average particle size measurement]
100 fine particles were photographed with FE-SEM (F-900 manufactured by Hitachi, Ltd.). The magnification is 30000 times. For each photographed image, the diameter of a circle equal to this was determined, and this was taken as the diameter of the particle. The diameters obtained for 100 particles were averaged to obtain the average diameter of the particles.

[Shell weight ratio]
The weight ratio of the shell in the particles was calculated from the number of moles of silver and sulfur in the particles. The number of moles of both was determined by fluorescent X-ray analysis using a fluorescent X-ray analyzer Type 3370E (manufactured by Rigaku Corporation) on a sample obtained by spin-coating a particle dispersion on a polyethylene terephthalate support. Sulfur and silver moles each m _s, When m _A, the number of moles of Ag2S shell m _s, the number of moles of the core of Ag becomes m _A -2m _s.
Therefore, the weight ratio of the shell to the core is (m _s /247.8):(m _A -2 m _s /107.9)
become.

Example 2 (Preparation of silver particles / aqueous system)
9.5 g of a lime-processed gelatin aqueous solution (concentration: 10 mass%) was added to 200 g of an aqueous dispersion of silver particles (average particle diameter: 75 nm, concentration: 5 mass%) and stirred for 30 minutes.
Next, with stirring, an aqueous solution of sodium sulfide having a concentration of 7.2% by mass was added so that the sulfidation rate of the metal became the value shown in Table 1.
Stirring was continued for 30 minutes. The liquid temperature at the time of adding the sodium sulfide aqueous solution was 40 ° C.
Silver core-shell fine particles having a silver sulfide shell were prepared by the above process.
Evaluation similar to Example 1 was implemented about the obtained sample. The results are shown in Table 1.

Example 3 (Preparation of Pd particles / acetone system)
Example 3 was carried out in the same manner as in Example 1 except that palladium particles (average particle size 15 nm, concentration 10% by mass) were used instead of silver particles. The results are shown in Table 1.

Example 4 (silver particles / transfer material)
[Preparation of photosensitive transfer layer coating solution]
The following additives were added to the fine particle dispersion prepared in Examples 1 and 3 to prepare a photosensitive transfer layer coating solution.
Fine particle dispersion of any of Samples 1-1 to 1-6 of Example 1 and 3-1 to 3-6 of Example 3
159.6g
Polymer P-2 0.19g
F780F (Dainippon Ink & Chemicals, Inc. Fluorosurfactant 20%) 0.03g
Hydroquinone monomethyl ether 0.0001g
Dipentaerythritol hexaacrylate 0.19g
Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.001 g
(Polymer P-2: benzyl methacrylate / methacrylic acid = 60/40 (wt / wt), number average molecular weight 35000)

[Preparation of intermediate layer coating solution]
The following components were mixed to obtain an intermediate layer coating solution.
Polyvinyl alcohol (Kuraray Co., Ltd. PVA205) 3.0g
Polyvinylpyrrolidone (GAP Corporation PVP-K30) 1.5g
Distilled water 50.5g
Methyl alcohol 45.0g

[Thermoplastic resin layer coating solution formulation]
Copolymer of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid = 54/12/5/29 (number average molecular weight 80000)
58g
Copolymer of styrene / acrylic acid = 70/30 (number average molecular weight 7000) 136g
BPE-500 (Shin-Nakamura Chemical Co., Ltd. polyfunctional acrylate) 90g
F780F (Dainippon Ink Chemical Co., Ltd. Fluorosurfactant 20%) 1g
Methyl ethyl ketone 541g
63 g of 1-methoxy-2-propanol
Methyl alcohol 111g

[Create transfer material]
Using a slit coater, a thermoplastic resin layer coating solution was applied to a biaxially stretched 75 μm thick polyethylene terephthalate support using a slit coater and dried at 100 ° C. for 3 minutes.
Next, an intermediate layer coating solution was applied thereon so as to have a dry thickness of 1.5 μm, and dried at 100 ° C. for 3 minutes. Further, a photosensitive transfer layer coating solution was coated thereon so as to have an optical density of 3.8 and dried at 100 ° C. for 3 minutes. Transfer materials 4-1 to 4-12 were prepared by the above procedure.

[Create Black Matrix]
The transfer material and the glass substrate are overlapped so that the photosensitive light-shielding layer is in contact with the glass substrate (thickness 1.1 mm), and the pressure is 0.8 kg / cm ² and the temperature is 130 using a laminator (VP-II manufactured by Osaka Laminator Co., Ltd.). Bonding was performed at 0 ° C. The polyethylene terephthalate support was then peeled off.
Subsequently, exposure was performed at 70 mJ / cm ² from the coated surface side using a super high pressure mercury lamp through a photomask, and then the following development was performed.
Development: Development processing solution TCD (Fuji Photo Film Co., Ltd. alkaline development solution) Development processing (33 ° C * 20 seconds)
Washing with water: (33 ° C * 20 seconds)
The obtained sample was heat-treated at 220 ° C. for 40 minutes.

[Evaluation of black matrix]
The following evaluation was performed about the obtained sample. The results are shown in Table 2.

[Optical density measurement]
The optical density of the film was measured by the following method.
The optical density of the fine particle-containing layer coated on the glass substrate was measured with a Macbeth densitometer (TD-904 manufactured by Macbeth) (OD). Separately, the optical density of the glass substrate was measured by the same method (OD ₀ ). The value obtained by subtracting OD ₀ from OD was defined as the optical density of the film.

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

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

[Reflectance measurement]
Using a spectrophotometer V-560 manufactured by JASCO Corporation and an absolute reflectance measuring device ARV-474 manufactured by JASCO Corporation on the glass substrate side (opposite the surface on which the coating film is formed) Absolute reflectance was measured. The measurement angle is 5 degrees and the wavelength is 500 nm.

Example 5 (silver particle / liquid cash register)
[Preparation of photosensitive coating solution]
Same as the photosensitive transfer layer coating solution of Example 4.
[Preparation of intermediate layer coating solution]
Same as the intermediate layer coating solution of Example 4.

[Create Black Matrix]
A photosensitive coating solution is applied to a glass substrate having a thickness of 1.1 mm using a spin coater so that the optical density is 3.8 and dried at 100 ° C. for 3 minutes, and then the intermediate layer coating solution is dried to a thickness. Was applied to 1.5 μm and dried at 100 ° C. for 3 minutes.
This sample was exposed, developed, and heat-treated in the same manner as in Example 4 to prepare Samples 5-1 to 5-12.
Evaluation similar to Example 4 was implemented about this sample. The results are shown in Table 3.

  As can be seen from Tables 2 and 3, the core-shell fine particles of the present invention have high optical density and low reflectance.

  Since the black matrix containing the core-shell fine particles of the present invention has high optical density and low reflectance, it is useful for display devices such as liquid crystal display devices, plasma display display devices, EL display devices, and CRT display devices.

Claims (14)

  A black matrix containing core-shell fine particles having a core made of metal inside and having a shell made of a metal sulfide constituting the core on the surface.   2. The black matrix according to claim 1, wherein the number average particle diameter of the core-shell fine particles is in the range of 1 nm to 5000 nm.   The black matrix according to claim 1 or 2, wherein the ratio of the weight of the shell to the weight of the core-shell fine particles is 0.08 to 0.92. The black matrix according to any one of claims 1 to 3 , wherein the metal is silver or palladium. A transfer layer having a core made of a metal on the temporary support, a shell made of a sulfide of the metal constituting the core on the surface, and a core-shell fine particle whose metal is silver or palladium and a binder A transfer material. 6. The transfer material according to claim 5, wherein the number average particle diameter of the core-shell fine particles is in the range of 1 nm to 5000 nm . The transfer material according to claim 5 or 6, wherein the ratio of the weight of the shell to the weight of the core-shell fine particles is 0.08 to 0.92 . Core- shell fine particles, dispersion medium, polymer binder, monomer, and photopolymerization initiator having a core made of metal inside, a shell made of a metal sulfide constituting the core on the surface, and the metal being silver or palladium A fine particle dispersion composition comprising: 9. The fine particle dispersion composition according to claim 8, wherein the number average particle size of the core-shell fine particles is in the range of 1 nm to 5000 nm. The fine particle dispersion composition according to claim 8 or 9, wherein the ratio of the weight of the shell to the weight of the core-shell fine particles is 0.08 to 0.92.   The color filter which has a black matrix of any one of Claims 1-4.   A display device comprising the color filter according to claim 11. A method for producing a black matrix, which is formed by a method comprising the following steps a and b.
a: transferring the transfer layer of the transfer material according to any one of claims 5 to 7 to a substrate
b: Step of forming a black matrix by patterning A method for producing a black matrix, which is formed by a method comprising the following steps a and b.
a: The process of apply | coating and drying the composition of any one of Claims 8-10 on a board | substrate.
b: Step of forming a black matrix by patterning