WO2006112439A1 - Procédé de production d’un filtre de couleur, filtre de couleur, élément d’affichage à cristaux liquides, et dispositif d’affichage à cristaux liquides - Google Patents

Procédé de production d’un filtre de couleur, filtre de couleur, élément d’affichage à cristaux liquides, et dispositif d’affichage à cristaux liquides Download PDF

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Publication number
WO2006112439A1
WO2006112439A1 PCT/JP2006/308045 JP2006308045W WO2006112439A1 WO 2006112439 A1 WO2006112439 A1 WO 2006112439A1 JP 2006308045 W JP2006308045 W JP 2006308045W WO 2006112439 A1 WO2006112439 A1 WO 2006112439A1
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Prior art keywords
color filter
separation wall
substrate
layer
composition
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PCT/JP2006/308045
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English (en)
Japanese (ja)
Inventor
Hideaki Ito
Daisuke Kashiwagi
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Fujifilm Corporation
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Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Priority to JP2007528140A priority Critical patent/JP4990139B2/ja
Publication of WO2006112439A1 publication Critical patent/WO2006112439A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
    • G03F7/343—Lamination or delamination methods or apparatus for photolitographic photosensitive material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70008—Production of exposure light, i.e. light sources
    • G03F7/70033—Production of exposure light, i.e. light sources by plasma extreme ultraviolet [EUV] sources

Definitions

  • Color filter manufacturing method color filter, liquid crystal display element, liquid crystal display device
  • the present invention relates to a method for manufacturing a color filter, a color filter, a liquid crystal element, and a liquid crystal display device, and in particular, has two or more pixel groups that exhibit different colors on a substrate, and each pixel constituting the pixel group Are separated from each other by a dark separation wall, and a method for producing a color filter formed by applying droplets by an ink jet or the like in the separation wall, a color filter, and a liquid crystal display provided with this color filter
  • the present invention relates to an element and a liquid crystal display device including the liquid crystal display element.
  • a color filter for a display device red, green, and blue dot-like images are arranged in a matrix on a substrate such as glass, and the boundaries are divided by dark color separation walls such as a black matrix. Structure.
  • a substrate such as glass is used as a support, and 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, repeated exposure and development.
  • Colored photosensitive resin solution method (colored resist method), 4) A method of transferring images formed on a temporary support sequentially to the final or temporary support, 5) A pre-colored photosensitive resin solution A colored layer is formed by coating on a temporary support, and then the photosensitive colored layer is transferred directly onto the substrate, exposed, and developed for a number of colors.
  • An image forming method (transfer method) is known. Also known is a method of forming each pixel using an inkjet method.
  • the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive layer resin solution.
  • the method of forming each pixel by using the ink jet method has a problem that the positional accuracy of the pixel is poor although the loss of the resin liquid is small and the cost is advantageous.
  • a color filter manufacturing method has also been proposed in which a black matrix that overcomes these problems is formed by a colored resist method to form a separation wall and RGB pixels are manufactured by an inkjet method. ing.
  • a separation wall forming method the surface of the separation wall becomes rough and fine irregularities are generated. For this reason, there is a problem that the surface resistance of the transparent electrode (ITO) formed on the color filter increases.
  • Patent Document 1 JP 2001-343518 A
  • the present invention has been made in view of the above situation. That is, according to the present invention, the surface roughness of the separation wall can be stably adjusted with few steps, and as a result, the surface resistance of the transparent electrode (ITO) formed on the color filter can be reduced.
  • An object of the present invention is to provide a manufacturing method, a color filter, a liquid crystal display element provided with the color filter, and a liquid crystal display device provided with the liquid crystal display element.
  • the substrate has two or more pixel groups exhibiting different colors on the substrate, and each pixel constituting the pixel group is separated from each other by a dark separation wall.
  • the method includes a step of forming a separation wall, and a step of applying a droplet of a colored liquid composition between the separation walls to form each pixel between the separation walls.
  • the substrate has two or more pixel groups exhibiting different colors on the substrate, and each pixel constituting the pixel group is separated from each other by a dark color separation wall.
  • the method includes a step of forming a separation wall, and a step of applying a droplet of a colored liquid composition between the separation walls to form each pixel between the separation walls.
  • the present invention has two or more pixel groups exhibiting different colors on a substrate, and each pixel constituting the pixel group is separated from each other by a dark color separation wall.
  • the method includes a step of forming a separation wall, and a step of applying a droplet of a colored liquid composition between the separation walls to form each pixel between the separation walls.
  • a color filter manufactured by the method for manufacturing a color filter according to the first aspect wherein the separation wall has a surface roughness Ra value of 6 nm or less. provide.
  • the separation wall has a surface roughness Ra value of 5 nm or less.
  • a liquid crystal display device provided with the color filter of any one of the above embodiments is provided. Furthermore, as another aspect of the present invention, a liquid crystal display device provided with the above liquid crystal display element is provided.
  • a photosensitive transfer material is laminated on a substrate that does not require a dry etching step, and a temporary support of the photosensitive transfer material is left.
  • the layer made of the photosensitive composition on the substrate is exposed in a simple process of having an oxygen-blocking film layer thereon. Therefore, it is possible to stably improve fine irregularities on the surface of the separation wall.
  • the method for producing a color filter of the third aspect of the present invention it is possible to stably perform the separation by a simple process of exposing the layer made of the photopolymerizable composition on the substrate in an oxygen-poor atmosphere. Fine irregularities on the surface of the wall can be improved.
  • the method for producing a color filter of the present invention has two or more pixel groups exhibiting different colors on a substrate, and the pixels constituting the pixel group are separated from each other by a dark color separation wall.
  • a method for producing a color filter comprising: a step of forming a separation wall; and a droplet of a colored liquid composition is applied between the separation walls to form each pixel between the separation walls. And a process.
  • the step of forming the separation wall includes a step of laminating the photosensitive transfer material on the substrate, and exposing the photosensitive transfer material while leaving the temporary support of the photosensitive transfer material. (Hereinafter, also referred to as “first embodiment”).
  • the step of forming the separation wall includes a step of forming a layer made of a photosensitive composition on a substrate, and a photosensitive composition in a state having an oxygen blocking film layer thereon. And a step of exposing a layer comprising (hereinafter also referred to as “second embodiment”).
  • the step of forming the separation wall includes a step of forming a layer made of the dark color photopolymerizable composition on the substrate, and a layer made of the dark color photopolymerizable composition in an oxygen-poor atmosphere. (Hereinafter also referred to as “third embodiment”).
  • the separation wall on the substrate is a photosensitive composition containing a colorant (“dark color separation wall”) in the method for producing the color filter of the first embodiment. It is formed from a photosensitive transfer material produced using a “color photosensitive composition” or a “dark color composition”. Further, in the method for producing a color filter of the second embodiment, it is formed from a photosensitive composition containing a colorant (both “dark color photosensitive composition” and “dark color composition”). The In the method for producing the color filter of the third embodiment, the photopolymerizable composition containing the colorant (also referred to as “dark color photopolymerizable composition” or “dark color composition”) is used. It is formed.
  • the dark color composition is a composition having a high optical density, and the value thereof is 2.5 or more force S, preferably 2.5 to 100.0 force S, 2.5 to 6 0 force S is more preferable, and 3.0 to 5.0 is particularly preferable.
  • the dark color composition is preferably a photopolymerizable composition in the first embodiment and the second embodiment because it is preferably cured by a photoinitiating system as described later.
  • it is a photopolymerizable composition.
  • the optical density of the dark color composition with respect to the exposure wavelength is preferably 2.0 to 10.0, more preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. It is. If it is less than 0, the shape of the separation wall may not be as desired, and if it exceeds 10.0, polymerization may not be started and it may be difficult to produce the separation wall itself.
  • colorant used in the present invention include those given the color index (C.I.) numbers described in the following dyes and pigments.
  • Organic pigments, inorganic pigments, dyes and the like can be suitably used for the dark color composition of the present invention.
  • the dark color composition layer is required to have light shielding properties, carbon black, titanium oxide, 4
  • light-shielding agents such as metal oxide powders such as iron oxide, metal sulfide powders, and metal powders
  • a mixture of pigments such as red, blue, and green can be used.
  • Known colorants dye and pigments
  • the pigment is uniformly dispersed in the dark color composition.
  • the ratio of the colorant in the solid content of the dark color composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass from the viewpoint of shortening the development time. More preferably, it is 50-55 mass%.
  • a black colorant is preferable.
  • Further examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, graphite, and the like. Among these, carbon black is preferable.
  • the pigment is desirably used as a dispersion.
  • This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later.
  • the vehicle is a part of a medium that disperses a pigment when the paint is in a liquid state! /, A part of a liquid that binds to the pigment and hardens the coating film (binder). And a component to be dissolved and diluted (organic solvent).
  • disperser used for dispersing the pigment examples include, for example, a kneader described in Asakura Kunizo, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, page 438, Well-known dispersers such as Ronole Reminore, Atrider, Super Mill, Disorno, Homomixer, Sand Mill and the like can be mentioned. Further, the material may be finely pulverized by frictional force by mechanical grinding described on page 310.
  • the colorant (pigment) used in the present invention preferably has a number average particle size of 0.001 to 0.1 m, more preferably 0.01 to 0.08 m, from the viewpoint of dispersion stability. ⁇ Preferred! / On the other hand, when the average particle diameter of the pigment exceeds 0.1 ⁇ m, the polarization is canceled by the pigment, and the contrast is lowered.
  • particle size refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle size” refers to the above-mentioned particle size for many particles. This means the average value of 100 pieces.
  • the dark color composition in the present invention preferably comprises at least a binder “fat” polymer, a polymerization initiator, and a monomer in addition to the colorant.
  • a binder “fat” polymer e.g., polyethylene glycol dimethacrylate copolymer
  • a polymerization initiator e.g. polyethylene glycol dimethacrylate copolymer
  • a monomer e.g., polyst copol dimethacrylate, polyst copolymer, polymerization inhibitors, surfactants, solvents, adhesion promoters and the like.
  • the dark color composition be thermoplastic, which preferably becomes soft or tacky at a temperature of at least 150 ° C. From such a viewpoint, it can be modified by adding a compatible plasticizer.
  • the binder used in the dark color composition is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain.
  • a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain.
  • Examples include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-B-59-53836.
  • Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid as described in Japanese Utility Model Publication No. 59-71048 A copolymer etc. can be mentioned.
  • the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned.
  • a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used.
  • Particularly preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid and others. And a multi-component copolymer with the above monomer.
  • These binder polymers having a polar group may be used alone or in the form of a composition used in combination with an ordinary film-forming polymer.
  • a thermal initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are generally used.
  • a photoinitiation system it is preferable to use a photoinitiation system.
  • the photopolymerization initiator used here generates an active species that initiates polymerization of the polyfunctional monomer described later by irradiation with visible rays (ultraviolet rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc.). It can be selected appropriately from known photopolymerization initiators or photopolymerization initiator systems.
  • a trihalomethyloxazole derivative or s -triazine derivative substituted with a trino or romethyl group described in JP-A-2001-117230, a trihalomethyl-S described in US Pat. No. 4239850, and the like a triazine compound, a trihalomethyl group-containing compound such as the trihalomethyl oxadiazole compound described in U.S. Pat. No. 421297 6;
  • At least one selected from trino, romethyl group-containing compounds, atalidine compounds, acetophenone compounds, bisimidazole compounds, and triazine compounds is particularly preferred. It is preferable to contain at least one selected from a containing compound and an atalidine compound. Torino, romethyl group-containing compounds, and atalidine compounds are also useful in that they are versatile and inexpensive.
  • the compound containing trihalomethyl group is 2-trichloromethyl mono 1 (p styrylstyryl) 1, 3, 4 oxadiazole, and the atalidine compound is 9-phenolacridine, and 6- [p- (N, Nbis (ethoxycarbolmethyl) amino) phenol -L] —2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) 5 trichloromethyl-1,3-, 4-oxadiazole and other compounds containing trihalomethyl groups, and Michler's ketone, 2,2 ' Bis (2,4 dichlorophenol) 4,4 ', 5,5' tetraphenol 1
  • hexaryl bisimidazole compound is preferably used in an amount of 0.5 to 25% by mass, more preferably 1 to 15% by mass, based on the total amount of the binder polymer and the photopolymerizable monomer.
  • the photopolymerization initiator may be used alone or in combination of two or more! /.
  • the total amount of the photopolymerization initiator in the dark composition is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition.
  • the total amount is less than 0.1% by mass, the photocuring efficiency of the dark color composition is low, and it may take a long time for exposure.
  • the total amount exceeds 20% by mass, it is formed during development. The resulting image pattern may be lost or the surface of the pattern may become rough.
  • the photopolymerization initiator may be configured using a hydrogen donor in combination.
  • the hydrogen donor is preferably a mercabtan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved.
  • the term “hydrogen donor” as used herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.
  • the mercabtan compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups bonded directly to the mother nucleus.
  • mercabbutane-based hydrogen donor a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “a”).
  • Mining hydrogen donor may have a mercapto group and an amino group at the same time.
  • mercaptan-based hydrogen donor examples include 2 mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4 thiadiazole, 2-mercapto-2,5 dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferred, and 2-mercaptobenzothiazole is particularly preferred.
  • amine-based hydrogen donor examples include 4, 4 'bis (dimethylamino) benzophenone, 4, 4'-bis (jetylamino) benzophenone, 4-jetylaminoacetophenone, 4 dimethylaminopropiophenone. , Ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzo-tolyl and the like. Of these, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (jetylamino) benzophenone are preferred, especially 4,4'-bis (jetylamino) benzophenone.
  • the hydrogen donor can be used alone or in admixture of two or more.
  • the formed image is difficult to drop off from the permanent support during development, and the strength and sensitivity can be improved. Therefore, it is preferable to use a combination of one or more mercabtan hydrogen donors and one or more amine hydrogen donors.
  • the combination of the mercabtan hydrogen donor and the amine hydrogen donor include 2 mercaptobenzozoazole Z 4, 4′-bis (dimethylamino) benzophenone, 2 mercaptobenzothioazole Z 4, 4′— Bis (jetylamino) benzophenone, 2 mercaptobenzoxazole Z 4, 4 ′ —bis (dimethylamino) benzophenone, 2 mercaptobenzoxazole Z 4, 4 ′ —bis (jetylamino) benzophenone, and the like.
  • More preferred combinations are 2-mercaptobenzothiazole / 4,4 ′ bis (jetylamino) benzophenone, 2-mercaptobenzoxazole Z 4, 4′—bis (jetylamino) benzophenone, and particularly preferred combinations are 2-mercapto Benzothiazole Z 4, 4 ′ Bis (jetylamino) benzoph It is Jenon.
  • the mass ratio (M: A) of the mercabtan hydrogen donor (M) and the amine hydrogen donor (A) in the case of combining the mercabtan hydrogen donor and the amine hydrogen donor is Usually, 1: 1 to 1: 4 is preferred, and 1: 1 to 1: 3 is more preferred.
  • the total amount of the hydrogen donor in the dark color composition is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition.
  • the hydrogen donor is preferably 0.5 to 25% by mass, more preferably 1 to 15% by mass, based on the total amount of the binder polymer and the photopolymerizable monomer. Used by.
  • the following compounds can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Atalylate, 2-Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, di Pentaerythritol penta (meth) acrylate, polyoxyethyl trimethylol propane tri (meth) acrylate, tris (2- (meth) attayllooxychetyl) isocyanurate,
  • compounds having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and hexamethylene diisocyanate
  • a reaction product with a diisocyanate such as toluene diisocyanate or xylene diisocyanate can also be used.
  • pentaerythritol tetraatalylate dipentaether.
  • the content of the polyfunctional monomer in the dark color composition is preferably from 5 to 80% by weight, particularly preferably from 10 to 70% by weight, based on the total solid content (mass) of the dark color composition. .
  • the content is less than 5% by mass, the resistance to the alkaline developer at the exposed portion of the dark color composition may be inferior.
  • the content exceeds 80% by mass, The tackiness may increase and handling may be inferior.
  • an organic solvent may be used in addition to the above components.
  • organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol methanol monomethyl ether ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, strength prolatatum, etc. I can list them.
  • a dark color composition can be applied to a substrate or a temporary support by using a slit-like nozzle described later.
  • the film thickness can be controlled to be uniform and uneven coating can be effectively prevented.
  • surfactant examples include those disclosed in JP-A-2003-337424 and JP-A-11-133600.
  • the content of the surfactant relative to the total solids in the dark composition 0.1 a 001 to 1% guar general, from 0.01 to 0.5 0/0 Power Preferably, from 0.03 to 0 . 3 0/0 force particularly preferred! /,.
  • the dark color composition of the present invention may contain an ultraviolet absorber as necessary.
  • the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724.
  • phenol salicylate 4 t-butyl phenol salicylate, 2, 4 t-Butylphenol 3 ', 5'-di-t- 4'-hydroxybenzoate, 4 t-butyl phenol salicylate, 2,4-dihydroxybenzophenone, 2 hydroxy-4-methoxy benzophenone, 2 hydroxy 1 4-n —Otoxybenzophenone, 2 -— (2′-hydroxy 5′-methylphenyl) benzotriazole, 2 -— (2′-hydroxy 3′—t-butyl—-5′-methylphenol) -5-clobenzobenzoazole, Ethyl 2 Cyan 3, 3— Di-phenolatarylate, 2, 2′-Hydroxy 1-methoxybenzophenone, Nickel dibutyl dithiocarbamate, Bis (2, 2, 6, 6-Tetramethyl-4-pyridine) Sebake , 4 t-butylphenol salicylate, salicylic acid phenol, 4-hydroxy 2, 2, 6, 6-tetramethyl-4-
  • the content of the ultraviolet absorber with respect to the total solid content of the dark color composition is generally 0.5 to 15%, preferably 1 to 12%, and particularly preferably 1.2 to 10%.
  • the dark color composition of this invention contains a thermal-polymerization inhibitor.
  • the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butinole, p-creso-monole, pyrogalronole, t-butinore force teconore, benzoquinone, 4, 4'-thiobis (3 -Methyl-6t-butylphenol), 2,2'-methylenbis (4-methyl-6t-butylphenol), 2 mercaptobenzimidazole, phenothiazine and the like.
  • the content of the thermal polymerization inhibitor to the total solids in the dark composition 0.1 was 01 to 1% guar general, from 0.02 to 0.7 0/0 Power Preferably, 0. 05 ⁇ 0.5 0/0 force particularly preferred! /,.
  • the dark color composition of the present invention may contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like in addition to the above additives.
  • the substrate (permanent support) constituting the color filter a metallic support, a metal bonded support, glass, ceramic, synthetic resin film, or the like can be used.
  • a glass or a synthetic resin film having transparency and good dimensional stability is used.
  • a photosensitive transfer material described later is laminated on the substrate to dark color photosensitive property. After the dark color photosensitive resin layer made of the composition is transferred, the photosensitive transfer material is exposed with the temporary support of the photosensitive transfer material remaining.
  • the step of forming the separating wall includes a step of transferring a photosensitive transfer material, which will be described later, having at least a layer made of a photosensitive composition on the temporary support onto the substrate.
  • the optical density of the separation wall at 555 nm is not particularly limited, but is preferably 2.5 or more and 10 or less from the viewpoint of improving the contrast of the display device. More preferably, it is 3.0 or more and 10 or less, and particularly preferably 4.0 or more and 10 or less.
  • the range of 2.5 to 10 is preferable because good contrast can be obtained.
  • the dark photosensitive resin layer made of the dark color composition is exposed through the temporary support, the dark color separation wall that is hardly affected by oxygen is exposed. Surface roughness can be reduced.
  • the surface roughness Ra of the dark color separation wall in the present invention is preferably small, but is not particularly limited.
  • the surface roughness Ra value of the dark color separation wall is preferably 6 nm or less, more preferably 5. Onm or less, more preferably 4. Onm or less, particularly preferably 3.6 nm or less. It is.
  • the surface roughness Ra value of the dark color separation wall By setting the surface roughness Ra value of the dark color separation wall to 6 nm or less, it is possible to easily prevent the movement of the colored liquid composition that moves along the surface of the dark color separation wall to the adjacent pixel, As a result, it is preferable in terms of preventing color mixing due to movement of the coloring liquid composition between adjacent pixels.
  • the surface roughness of the dark color separation wall is a value measured with Rai IS B0601.
  • the height h of the dark color separation wall (the point H having the highest height of the dark color separation wall is H and a vertical line drawn on the substrate such as H).
  • color mixing can be prevented more effectively. If the height is less than 1. Color mixing occurs, and if it exceeds 10 m immediately, it tends to be difficult to form a dark color separation wall.
  • a method of providing an oxygen barrier film layer on a layer made of a photosensitive composition on a substrate in order to form a separation wall is as follows. ,
  • the method (1) is also simply referred to as a transfer method
  • the method (2) is also referred to as a coating method.
  • the oxygen barrier layer is a layer having an oxygen permeability of 50 Ocm V (m 2 ⁇ day ⁇ atm) or less, and the oxygen permeability is 100 cm 3 / it is preferable that (m 2 ⁇ day ⁇ atm) is less than or equal to, 50cm 3 / (m 2 ⁇ day ⁇ atm) or less der Rukoto more preferably! /,.
  • the oxygen permeability of the oxygen blocking layer is more than 500 cm 3 / (m 2 ′ day atm)
  • oxygen cannot be blocked efficiently, so that the separation wall is formed in the desired shape. It becomes difficult to make.
  • the oxygen barrier layer in the second embodiment is preferably a layer mainly composed of polyethylene, polyvinyl chloride-polyene, polybutyl alcohol, etc., among which a layer mainly composed of polyvinyl alcohol. I like it.
  • polybulal alcohol those having an acidity of 80% or more are preferable.
  • the content of the polybulal alcohol in the oxygen barrier layer of the present invention is preferably 25% by mass to 99% by mass, more preferably 50% by mass to 90% by mass, and particularly preferably 50% by mass to 80% by mass.
  • polymers such as polyvinyl pyrrolidone and polyacrylamide may be added as necessary, but among these, polybulur pyrrolidone is preferable.
  • Added Caro weight of these polymers is from 1 to 40 weight of the entire layer 0/0, and more preferably 10 to 35 wt%. If the amount of polybutylpyrrolidone added is too large, oxygen barrier properties may be insufficient.
  • the surface roughness of the dark color separation wall that is hardly affected by oxygen is reduced.
  • the surface roughness Ra value of the dark color separation wall can be 5 nm or less, preferably 4. Onm or less, more preferably 3.6 nm or less.
  • the surface roughness Ra value of the dark color separation wall is 5 nm or less, it is possible to easily prevent the movement of the colored liquid composition that moves along the surface of the dark color separation wall to the adjacent pixel, This is preferable because it prevents color mixing due to the movement of the colored liquid composition between adjacent pixels.
  • the height h of the dark color separation wall (the highest point of the dark color separation wall is H and the foot G of the perpendicular line on the H force substrate) The distance) is preferably 1.8 m or more, more preferably 1.9 111 to 10 111, still more preferably 2.0 / zm to 7 m, and particularly preferably 2. 5. O / zm or less. 1. More than 10 m or less can prevent color mixing more effectively. If the height is less than 1. Color mixing occurs, and if it exceeds 10 m immediately, it tends to be difficult to form a dark color separation wall.
  • an oxygen-poor atmosphere means an atmosphere with an oxygen partial pressure of 0.15 atm or less, and these are described in detail below. It is.
  • the partial pressure of oxygen is 0.21 atm in the atmosphere (1 atm).
  • (B) It can be achieved by mixing a gas other than air and oxygen (for example, an inert gas such as nitrogen or argon) with 40 vol% or more of the air.
  • the poor oxygen atmosphere in the third embodiment is not particularly limited, and any of the above methods can be used. Therefore, either an inert gas atmosphere or a reduced pressure may be used.
  • the oxygen partial pressure is 0.15 atm or less, 0.1 atm or less is preferable, 0.08 atm or less is more preferable, and 0.05 atm or less is particularly preferable. If the oxygen partial pressure is higher than 0.15 atm, the polymerization on the surface of the separation wall may be inhibited by oxygen and the surface roughness may increase. There is no particular limitation on the lower limit of the oxygen partial pressure. A force that can effectively reduce the oxygen partial pressure to zero by replacing the vacuum or atmosphere with a gas other than air (eg, nitrogen). This is also the preferred method.
  • the oxygen partial pressure can be measured using an oximeter.
  • the inert gas is a general gas such as N, H or CO, or He, Ne or Ar.
  • N is preferred due to safety, availability, and cost issues.
  • the reduced pressure refers to a state of 500 hPa or less, preferably lOOhPa or less.
  • the surface roughness of the dark color separation wall that is difficult to be affected by oxygen because the dark color composition layer is exposed in an oxygen-poor atmosphere. Can be reduced.
  • the surface roughness Ra value of the dark color separation wall can be 5 nm or less, preferably 4. Onm or less, more preferably 3.6 nm or less.
  • Surface roughness Ra of the dark color separation wall When the Ra value is 5 nm or less, it is possible to easily prevent the movement of the colored liquid composition that moves along the surface to the adjacent pixel through the dark color separation wall. This is preferable in terms of preventing color mixing due to movement of the colored liquid composition between adjacent pixels.
  • the height h of the dark color separation wall (the highest point of the dark color separation wall is H and the foot G of the perpendicular line on the H force substrate)
  • the distance is preferably 1.8 m or more, more preferably 1.9 111 to 10 111, still more preferably 2.0 / zm to 7.0 m, particularly preferably 2. 2 m or more and 5.0 m or less. 1. Color mixing can be prevented more effectively when the distance is 8 m or more and 10 m or less. Height is 1.
  • a photosensitive transfer material having a dark color photosensitive resin layer made of a dark color composition on a temporary support and a protective film provided on the layer is prepared. If necessary, an oxygen barrier layer is formed between the dark color photosensitive resin layer and the temporary support.
  • the exposed surface of the dark photosensitive resin layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (lamination). body).
  • laminator those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to increase productivity.
  • the exposure mask surface is performed with the distance between the temporary support and the temporary support appropriately set (for example, 200 m).
  • the exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, and the exposure amount can be appropriately selected (for example, 3 OOmiZcm 2 ). it can.
  • a proximity type exposure machine for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.
  • the exposure amount can be appropriately selected (for example, 3 OOmiZcm 2 ). it can.
  • the temporary support is removed, and development processing is performed using a predetermined processing solution to obtain a patterning image. Then, if necessary, washing processing is performed with water to remove the dark color separation wall. obtain.
  • the developer used for the development processing may be a solution in which a dilute aqueous solution of an alkaline substance is used, and a small amount of an organic solvent miscible with water may be added.
  • Examples of the light source used for light irradiation include medium to ultra high pressure mercury lamps, xenon lamps, metalno lamps, and lid lamps.
  • alkaline substance in the development method examples include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), alkali metal bicarbonate. Salts (eg, sodium bicarbonate, potassium hydrogen carbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal silicates (eg, sodium metasilicate, potassium metasilicate), Examples include tritananolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like.
  • the concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.
  • Examples of the "water-miscible organic solvent” include, for example, methanol, ethanol, 2-prononole-1, propanol, butanol, diacetone ethanol, ethylene glycolol.
  • Preferable examples include dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ⁇ -strength prolatatam and ⁇ ⁇ ⁇ -methylpyrrolidone.
  • the concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass.
  • a known surfactant can be added
  • the developer may be used as a bath solution or a spray solution.
  • methods such as rubbing with a rotating brush or wet sponge in the developer can be combined.
  • the developer temperature is usually preferably from about room temperature to 40 ° C.
  • the development time depends on the composition of the dark color photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration of the organic solvent when added, but is usually about 10 seconds to 2 minutes. If it is too short, the development of the non-exposed area may be insufficient, and the UV absorbance may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the image separation wall shape suitable. In this development step, the separation wall shape is formed as described above.
  • the pH of the developer is preferably 8 to 13.
  • a roller conveyor is installed in the developer tank, and the substrate moves horizontally.
  • the photosensitive resin is preferably formed on the upper surface of the substrate.
  • the inclination angle is preferably 5 ° force 30 °.
  • the dark color separation wall may be formed by using a deviation of the following method of applying a dark color composition or a method using a photosensitive transfer member. .
  • the substrate is heat-treated to stabilize the surface state.
  • the dark color composition dark color photosensitive composition or dark color photopolymerizable composition
  • part of the solvent is dried to eliminate the fluidity of the coating layer, it is pre-betated to obtain a dark colored resin layer (dark color photosensitive resin layer or dark color photopolymerizable resin layer).
  • EBR edge bead remover
  • the coating is not particularly limited, and has a known glass substrate coater having a slit-like nozzle (for example, product name: MH-1600, manufactured by F'S 'Asia Co., Ltd.) or a slit-like nozzle.
  • a glass substrate coater (made by Hirata Kiko Co., Ltd.) can be used.
  • the drying can be performed using a known drying apparatus (for example, VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)).
  • VCD vacuum drying apparatus
  • the prebeta is not particularly limited, but can be achieved by, for example, 120 ° C for 3 minutes.
  • the film thickness of the obtained dark colored resin layer is as described above.
  • the oxygen blocking layer is formed in the same manner on the dark color photosensitive resin layer.
  • the distance between the exposure mask surface and the dark colored resin layer is appropriately set (for example, 200 m). , Expose.
  • the exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, and the exposure amount can be appropriately selected (for example, 3 OOmiZcm 2 ). it can.
  • a patterning image is obtained by developing with a developing solution, and subsequently washed with water as necessary to obtain a dark color separation wall.
  • a shower nozzle or the like Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the dark colored resin layer.
  • a dilute aqueous solution of an alkaline substance is used, but a small amount of an organic solvent miscible with water may be added.
  • Examples of the light source used for light irradiation include medium to ultra high pressure mercury lamps, xenon lamps, metalno lamps, and lid lamps.
  • a photosensitive transfer material having a dark color composition layer on a temporary support and a protective film on the layer is prepared. If necessary, an oxygen barrier layer or a thermoplastic resin layer is formed under the dark color composition layer (between the temporary support and the dark color composition layer).
  • the surface of the exposed dark color composition layer is bonded onto a permanent support (substrate) and laminated by heating and pressurizing through a laminator or the like (laminate).
  • a laminator one appropriately selected from conventionally known laminators, vacuum laminators, etc. can be used, and an auto-cut laminator can also be used for higher productivity.
  • the temporary support is removed, a desired photomask is disposed above the removal surface after the temporary support is removed, ultraviolet light is irradiated from the light source, and a predetermined treatment liquid is used after irradiation.
  • a predetermined treatment liquid is used after irradiation.
  • the developer used for the development process and the light source used for light irradiation the developer and the light source used in the formation using the coating method are similarly used.
  • alkaline substance in the method of applying the dark color composition and the method of using the photosensitive transfer material described later examples include alkali metal hydroxides (for example, sodium hydroxide, sodium hydroxide, etc.). Potassium), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal catenates (eg, sodium silicate, Acid potassium), alkali metal metasilicates (E.g., sodium metasilicate, potassium metasilicate), triethanolamine, jetanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (e.g., tetramethylammonium hydroxide), trisodium phosphate, etc. Can be mentioned.
  • the concentration of alkaline substance is preferably 0.01 to 30% by mass.
  • the pH is preferably 8 to 14.
  • Examples of the "water-miscible organic solvent” include, for example, methanol, ethanol, 2-prononole, 1-propanol, butanol, diacetone-ethanolo, ethyleneglycol-mono monoethanolate, Ethylene glycol-monoethylenoatenole, ethylene glycol-monolemonyl butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ⁇ -force prolatatanes, ⁇ -butyrolatatanes, dimethylformamide, dimethylacetamide, hexamethylphospho Preferred examples include luamide, ethyl lactate, methyl lactate, ⁇ -strength prolatatam and ⁇ ⁇ ⁇ -methylpyrrolidone.
  • the concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass.
  • a known surfactant can be added, and the concentration of the surfact
  • the developer may be used as a bath solution or a spray solution.
  • methods such as rubbing with a rotating brush or wet sponge in the developer can be combined.
  • the temperature of the developer it is usually preferable that the force near room temperature is 40 ° C.
  • the development time is usually about 10 seconds to 2 minutes, although it depends on the composition of the dark resin layer, the alkalinity and temperature of the developer, and the type and concentration of the organic solvent when added. If it is too short, the development of the unexposed area may be insufficient, and at the same time, the absorbance of ultraviolet rays may be insufficient. If it is too long, the exposed area may be etched. In either case, it is difficult to make the separation wall shape suitable. In this developing process, the image separation wall shape is formed as described above.
  • the pH of the developer is preferably 8-13.
  • a roller conveyor is installed in the developer tank, and the substrate moves horizontally.
  • the dark resin layer is preferably formed on the upper surface of the substrate.
  • the substrate size exceeds 1 meter, when the substrate is transported horizontally, the developer stays near the center of the substrate, and the difference in development between the center of the substrate and the periphery becomes a problem.
  • the substrate is inclined obliquely. Is desirable.
  • the inclination angle is preferably 5 ° force 30 °.
  • Post exposure is preferably performed between development and heat treatment from the viewpoints of controlling the cross-sectional shape of the image, controlling the hardness of the image, controlling the surface roughness of the image, and controlling the film thickness reduction of the image.
  • the light source used for the post-exposure include an ultra-high pressure mercury lamp, a high-pressure mercury lamp, and a metal nitride lamp described in paragraph No. 0074 of JP 2005-3861 A.
  • the substrate is directly irradiated with light from a light source such as an ultra-high pressure mercury lamp, a metal lamp or a ride without using an exposure mask. Implement from both sides as needed.
  • the exposure amount is appropriately adjusted according to the control purpose in the range of the upper surface: 100 to 20 OOnijZ square centimeters and the lower surface: 100 to 2000 nijZ square centimeters.
  • the heat treatment temperature is preferably in the range of 150 ° C to 250 ° C. Below 150 ° C, the hardness is insufficient, and above 250 ° C, the resin is colored and the color purity is poor.
  • the heat treatment time is preferably 10 minutes to 150 minutes. If it is less than 10 minutes, the hardness is insufficient, and if it is more than 150 minutes, the resin is colored and the color purity is deteriorated.
  • the heat treatment may be changed depending on the color. Further, after all colors are formed, a final heat treatment may be performed to stabilize the hardness. In that case, it is preferable in terms of hardness to be carried out at a higher temperature (for example, 240 ° C).
  • the method for producing a color filter according to the first embodiment there is the above-described method of using a photosensitive transfer material having at least a layer made of a dark color composition on a temporary support.
  • a photosensitive transfer material having at least a layer made of a dark color composition on a temporary support.
  • the dark-colored photosensitive resin layer made of the dark-colored composition is protected by the temporary support and thus automatically becomes in an oxygen-poor atmosphere. Therefore, there is an advantage that the current process can be used as it is because it is not necessary to perform the exposure process under an inert gas under reduced pressure.
  • the photosensitive transfer material is obtained by forming a photosensitive resin layer containing the dark color composition as a component by a method such as coating the dark color composition on a temporary support. A protective film is provided as necessary.
  • the oxygen-poor atmosphere referred to in the first embodiment is, for example, a layer having an oxygen transmission rate of 2000 cm 3 / (m 2 'day atm) or less disposed on the photosensitive resin layer. It is preferable that the oxygen permeability is 100 «! 1 3 7 (111 2 '(1 &'&1; 111) or less, even if it is in a state. It should be 50 cmV (m 2 ⁇ day atm) or less. More preferred ,.
  • the oxygen permeability is higher than 2000 cm 3 / (m 2 ′ day atm)
  • oxygen cannot be blocked efficiently, so that the separation wall can be formed in the desired shape. It can be difficult.
  • the method for producing a color filter according to the second embodiment on the temporary support, at least an oxygen blocking layer and a layer made of the dark photosensitive composition in order from the side near the temporary support.
  • a technique (the above-mentioned (1) transfer method) in which a photosensitive transfer material is used.
  • the layer made of the dark photosensitive composition is protected by the oxygen blocking layer, so that it automatically becomes in an oxygen-poor atmosphere. Therefore, it is not necessary to perform the exposure process under an inert gas or under reduced pressure! Therefore, there is an advantage that the current process can be used as it is.
  • a photosensitive transfer material having at least a layer composed of a dark color photopolymerizable composition and, if necessary, a thermoplastic resin layer on a temporary support is used. May be. This is transferred onto a substrate to form a dark color photopolymerizable composition layer on the substrate and exposed in an oxygen-poor atmosphere.
  • a force composed of a flexible substance that is chemically and thermally stable can be appropriately selected.
  • a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyester, or a laminate thereof is preferable.
  • the thickness of the temporary support is suitably 5 to 300 ⁇ m, preferably 20 to 150 ⁇ m. If the thickness is less than 5 ⁇ m, the substrate tends to be easily broken when the substrate before development is peeled off, and if it exceeds 300 m, the resolution tends to decrease.
  • a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • an oxygen barrier layer can be provided between the temporary support for the photosensitive transfer material and the photosensitive resin layer as necessary.
  • the oxygen-blocking layer in the first embodiment is preferably a layer mainly composed of polyethylene, polyvinyl chloride, polybutyl alcohol or the like, and among these, a layer mainly composed of polyvinyl alcohol is preferable. Better ,.
  • polybulal alcohol those having an acidity of 80% or more are preferable.
  • the content of the polybulal alcohol in the oxygen barrier layer of the present invention is preferably 25% by mass to 99% by mass, more preferably 50% by mass to 90% by mass, and particularly preferably 50% by mass to 80% by mass.
  • polymers such as polyvinyl pyrrolidone and polyacrylamide may be added as necessary, but among these, polybulur pyrrolidone is preferable.
  • Added Caro weight of these polymers is from 1 to 40 weight of the entire layer 0/0, and more preferably 10 to 35 wt%. If the amount of polybutylpyrrolidone added is too large, oxygen barrier properties may be insufficient.
  • the photosensitive transfer material may have a thermoplastic resin layer as necessary.
  • the thermoplastic resin layer is composed of at least a resin component that is preferably alkali-soluble, and the resin component has a substantially soft softening point of 80 ° C or less. It is preferable. By providing such a thermoplastic rosin layer, it is possible to exhibit good adhesion to a permanent support in the method for forming a dark color separation wall described later.
  • alkali-soluble thermoplastic resins having a softening point of 80 ° C or less include styrene and methacrylic acid ester copolymer saponified products, vinyltoluene and ethylene toluene.
  • (Meth) acrylic acid ester copolymer saponified products poly (meth) acrylic acid esters, saponified products such as (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and butyl acetate, etc. Can be mentioned.
  • thermoplastic resin layer at least one of the above-mentioned thermoplastic resins can be appropriately selected and used, and the “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, Organic polymers with a softening point of about 80 ° C or less, which are soluble in alkaline aqueous solution, can be used.
  • an organic polymer substance having a soft spot of 80 ° C or higher various plasticizers compatible with the polymer substance can be substantially added to the organic polymer substance.
  • the softening point can be lowered to 80 ° C or lower.
  • these organic polymer substances have various polymers, supercooled substances, and adhesion improvements as long as the actual soft spot does not exceed 80 ° C in order to adjust the adhesive strength with the temporary support.
  • An agent or a surfactant, a release agent, etc. can also be added.
  • plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl di-phosphate bi-phenyl di-phosphate.
  • the protective film may have the same or similar material strength as the temporary support, but it must be easily separated from the photosensitive resin layer.
  • silicone paper, polyolefin, or polytetrafluoroethylene sheet is suitable as the protective film material.
  • the thickness of the protective film is generally 4 to 40 ⁇ , preferably 5 to 30 111 pieces, particularly 10 to 25 111 pieces, particularly preferably 1, 0.
  • Examples of photosensitive transfer material production in the first and second embodiments of the present invention include a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier layer), and a protective film. Show.
  • the photosensitive transfer material of the present invention is obtained by applying a coating solution in which an additive for a thermoplastic resin layer is dissolved on a temporary support (a coating solution for a thermoplastic resin layer) and drying the thermoplastic resin layer. After that, apply a solution of oxygen barrier layer material consisting of a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, dry it, and then apply the coating solution for the dark photosensitive resin layer to the middle
  • a solution of oxygen barrier layer material consisting of a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, dry it, and then apply the coating solution for the dark photosensitive resin layer to the middle
  • the layer (oxygen barrier layer) can be prepared by coating with a solvent that does not dissolve and drying.
  • thermoplastic resin layer and an oxygen barrier layer on the temporary support and a sheet provided with a photosensitive resin layer on a protective film were prepared, and an intermediate layer and a dark color photosensitive resin were prepared. Further, by laminating each other so that the layers are in contact with each other, a sheet having a thermoplastic resin layer provided on the temporary support, and a dark photosensitive resin layer and an oxygen on the protective film are further provided. It can also be produced by preparing a sheet provided with a blocking layer and bonding them together so that the thermoplastic resin layer and the oxygen blocking layer are in contact with each other.
  • the coating in the above production method can be performed by a known coating apparatus or the like, but in the present invention, it is preferably performed by a coating apparatus (slit coater) using a slit nozzle.
  • a coating apparatus slit coater
  • the photosensitive transfer material in the method for producing a color filter according to the third embodiment of the present invention is, for example, a coating solution in which an additive for a thermoplastic resin layer is dissolved on a temporary support (for a thermoplastic resin layer).
  • the coating solution is applied and dried to provide a thermoplastic resin layer, and then a dark color photopolymerizable resin layer coating solution is applied and dried. It is not necessary to provide the thermoplastic resin layer.
  • thermoplastic resin layer on the temporary support and a sheet provided with a photopolymerizable resin layer on a protective film are prepared, and the thermoplastic resin layer and dark color photopolymerization are prepared. It can also be produced by pasting them together so that the hydrophilic resin layers are in contact with each other.
  • the application in the above production method can be performed by a known application apparatus or the like. In the present invention, it is preferable to use a coating apparatus (slit coater) using a slit nozzle.
  • the water-repellent treatment is performed on the separating wall, that is, after at least a part of the separating wall is water-repellent, the droplets of the colored liquid composition are placed between the separating walls. It is preferable to give. This eliminates inconveniences such as droplets (ink) of the colored liquid composition overcoming the separation wall and mixing with the adjacent color when droplets are applied by a method such as inkjet. Therefore, it is preferable.
  • the water repellent treatment a method of applying a water repellent material on the upper surface of the separation wall, a method of newly providing a water repellent layer, a method of imparting water repellency by plasma treatment, a water repellent substance on the separation wall Examples thereof include a kneading method and a method of imparting water repellency with a photocatalyst.
  • a separation wall is prepared by adding fluorine-containing resin (A) to a photoresist obtained from the dark color composition (photosensitive composition or photopolymerizable composition) of the present invention. There is a way to do it.
  • the fluorine-containing resin (A) in the present invention has an Rf group (a) that also has a polyfluoroether structural force represented by the following formula 1 and an acidic group (b), and has an acid value of l to 300 mg KOHZg is preferred.
  • X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and is the same for each unit enclosed by n.
  • Y represents a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or A fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is shown, and n is an integer of 2 to 50.
  • the total number of fluorine atoms in Formula 1 is 2 or more.
  • X is preferably an alkylene group that is fluorinated except for one hydrogen atom having 1 to 10 carbon atoms or a perfluorinated alkyl group having 1 to 10 carbon atoms.
  • X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and is the same or different for each unit surrounded by n
  • Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.
  • the fluorinated resin (A) exhibits good ink repellency.
  • n represents an integer of 2 to 50. n is preferably 2-30, more preferably 2-15. When n is 2 or more, the ink falling property is good. When n is 50 or less, the fluorine-containing resin (A) is a copolymer of a monomer having an Rf group (a) and a monomer having an acidic group (b) or other monomer. In the case of synthesis by the monomer, the compatibility of the monomer becomes good.
  • the total number of carbon atoms in the Rf group (a) having a polyfluoroether structural force represented by the formula 1 is preferably 2 to 50, more preferably 2 to 30. Within this range, the fluorinated resin (A) exhibits good ink repellency, particularly organic repellency.
  • the fluorine-containing resin (A) is synthesized by copolymerization with a monomer having an Rf group (a), a monomer having an acidic group (b), and another monomer, The compatibility of is improved.
  • Y include: -CF, -CFCF, -CFCHF,-(CF) CF,-(CF)
  • p represents an integer of 2 or 3, and is the same group for each unit surrounded by n, q is 1 to An integer of 20, n represents an integer of 2-50.
  • Rf group (a) represented by the formula 2 specifically, CF 0 (CF CF O) CF (n is 2 to
  • Rf groups (a) in the fluorinated resin (A) may all be the same or different.
  • the fluorine atom content in the fluorine-containing resin (A) is preferably 1 to 60%, more preferably 5 to 40%. Within this range, the fluorinated resin (A) exhibits good ink repellency, and the developability of the dark color composition of the present invention is good.
  • the fluorine-containing resin (A) has an acidic group (b).
  • the acidic group (b) is preferably at least one acidic group or a salt thereof in which group power consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group is also selected.
  • the acid value of the fluorinated resin (A) is preferably from 1 to 300 mgKOH / g, more preferably from 5 to 200 mgKOHZ g, and particularly preferably from 10 to 150 mgKOHZg. Within this range, the developability of the dark color composition of the present invention will be good.
  • the acid value is the mass (unit: mg) of potassium hydroxide required to neutralize sorghum lg, and the unit is described as mgKOHZg in this specification.
  • the number average molecular weight of the fluorine-containing resin (A) is preferably 500 or more and less than 20000. 2000 or more
  • the number average molecular weight is measured by gel permeation chromatography using polystyrene as a standard substance.
  • the fluorine-containing resin (A) includes a monomer unit based on a monomer having an ethylenic double bond and the Rf group (a), an ethylenic double bond and the acidic group ( It is preferable that the copolymer has a monomer unit based on a monomer having b) and has an acid value of 1 to 300 mgKOHZg.
  • Examples of the ethylenic double bond include a (meth) atteroyl group, a vinyl group, and a allyl group.
  • R 1 is a hydrogen atom
  • Q 1 represents a single bond or a divalent organic group having 1 to 6 carbon atoms
  • Q 2 represents a divalent organic group having 1 to 6 carbon atoms.
  • QQ 2 may have a cyclic structure.
  • QQ 2 are: -CH 1, -CH CH 1, CH (CH
  • Specific examples of the monomer having the ethylenic double bond and the Rf group (a) include the following.
  • CH C (CH) COOCHCH NHCOOCH CFO (CFCFO) CF (n is 3 to 9)
  • CH C (CH) COOCH CH (OH) CH OCH CF 0 (CF CF O) CF (n is 3 to
  • the content of the monomer unit based on the monomer having the ethylenic double bond and the Rf group (a) in the fluorine-containing resin (A) is preferably 1 to 95 mol% or the like. 5 to 80 mol% is more preferable, and 20 to 60 mol% is more preferable. Within such a range, the fluorine-containing resin has good ink repellency, and the developability of the dark color composition of the present invention is good.
  • a monomer having an acidic group (b) a monomer having a carboxyl group, phenolic Examples thereof include a monomer having a hydroxyl group and a monomer having a sulfonic acid group.
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, bulacetic acid, cutotonic acid, itaconic acid, maleic acid, fumaric acid, kain acid, and salts thereof. These may be used alone or in combination of two or more.
  • Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.
  • one or more hydrogen atoms of these benzene rings are alkyl groups such as methyl group, ethyl group and n-butyl group, alkoxy groups such as methoxy group, ethoxy group and n-butoxy group, halogen atoms and alkyl groups. Examples thereof include haloalkyl groups in which one or more hydrogen atoms of the group are substituted with halogen atoms, nitro groups, cyano groups, and compounds in which amide groups are substituted. These may be used alone or in combination of two or more.
  • Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) aryl sulfonic acid, 2-hydroxy-3- (meth) aryloxypropane sulfonic acid, (meth).
  • the content of the monomer unit based on a monomer having an acidic group (b) in the fluorine-containing ⁇ is preferable that 0.1 to 40 mole 0/0, etc. instrument from 0.5 to 30 moles 0 / 0 preferably more preferred instrument 20 mol 0/0 Gasa et al. Within such a range, the fluorinated resin exhibits good ink repellency and the developability of the dark color composition is good.
  • Other monomers include hydrocarbon-based olefins, butyl ethers, isopropyl ethers, aryl ethers, butyl esters, aryl esters, (meth) acrylic acid esters, (meth) acrylamides. , Aromatic bur compound, chloroforme , Fluorefins, and conjugates.
  • Examples of the functional group that may contain a functional group in these compounds include a hydroxyl group, a carbonyl group, an alkoxy group, and an amide group. Further, it may have a group having a polysiloxane structure. However, monomer units based on these other monomers do not have Rf group (a) and acidic group (b). These may be used alone or in combination of two or more. Particularly, (meth) acrylic acid esters and (meth) acrylamides are preferred because the heat resistance of the coating film formed from the dark color composition of the present invention is excellent.
  • the proportion of monomer units based on other monomers is preferably 80% mol or less, more preferably 70 mol% or less. Within this range, the developability of the dark color composition of the present invention will be good.
  • the fluorinated resin in the present invention comprises a monomer unit based on a monomer having the above ethylenic double bond and Rf group (a), an ethylenic double bond and an acid group (b).
  • Rf group (a) an ethylenic double bond and an acid group (b).
  • b an acid group
  • Rf group (a) and a Z or acidic group (b) It can also be obtained by various modification methods in which a compound having) is reacted.
  • a monomer having an epoxy group is preliminarily copolymerized and then the Rf group is later copolymerized.
  • examples thereof include a method in which (a) is reacted with a compound having a carboxyl group, and a method in which a monomer having an epoxy group is previously copolymerized and then a compound having an Rf group (a) and a hydroxyl group is reacted.
  • Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3, 4-epoxycyclohexylmethyl acrylate.
  • Examples of the compound having an Rf group (a) and a carboxyl group include compounds represented by the following formula 3.
  • p is an integer of 2 or 3
  • q is an integer of 1 to 20
  • n is an integer of 2 to 50.
  • Examples of the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following formula 4. [0127] HOCH— CF — O— (CF — O) — CF... Formula 4
  • p is an integer of 2 or 3
  • q is an integer of 1 to 20
  • n is an integer of 2 to 50.
  • the monomer having a hydroxyl group include bulufenol, 2 hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 3 hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3 Black mouth 2 Hydrovinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethylaryl ether, N-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) Etc.
  • the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain having a terminal hydroxyl group.
  • CH CHOCH C H CH O (C H O)
  • More than one species may be used in combination.
  • acid anhydride examples include phthalic anhydride, 3-methylphthalic anhydride, trimellitic anhydride, and the like.
  • acid anhydride having an ethylenic double bond examples include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene 2,3 dicarboxylic acid, anhydrous 3, 4, 5, 6 —Tetrahydrophthalic acid, cis-l, 2, 3, 6-tetrahydrophthalic acid, Examples include 2-butene 1-ylssinic anhydride.
  • the compound having a hydroxyl group may be any compound having one or more hydroxyl groups.
  • a compound having one hydroxyl group in the molecule is preferred. These may be used alone or in combination of two or more.
  • the polymer having the reactive site that becomes a fluorine-containing resin or a precursor of the fluorine-containing resin is prepared by dissolving the monomer in a solvent together with a chain transfer agent as necessary and heating. Can be synthesized by a method of reacting and reacting.
  • the blending amount of the fluorinated resin (A) is preferably 0.01 to 50% by mass force S, more preferably 0.1 to 30% by mass, based on the solid content in the dark color composition. 2-10% by weight is particularly preferred. Within this range, the dark color composition exhibits good ink repellency and ink tumbling properties and good developability.
  • a silicone rubber layer is preferably used as the partition wall having ink repellency.
  • the silicone rubber layer coated on the surface layer must have a repulsive effect on the solution and ink used for coloring.
  • a linear organic polysiloxane having a repeating unit of general formula (1) and having a molecular weight of several thousands to several hundreds of thousands is preferred.
  • n is an integer of 2 or more
  • R is an alkyl group having 1 to 10 carbon atoms, a alkenyl group, or a phenyl group.
  • Silicone rubber can be obtained by sparsely cross-linking such a linear organic polysiloxane.
  • the cross-linking agent is V, acetoxy silane, keto xyme silane, alkoxy silane, amino silane, amido silane, alkeni xy silane, etc., used for so-called room temperature (low temperature) curable silicone rubber.
  • room temperature (low temperature) curable silicone rubber When combined with a hydroxyl group at the end, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamide type, and a deketone type silicone rubber are obtained.
  • a small amount of organic tin compound is added to silicone rubber as a catalyst.
  • Various adhesive layers may be used between the photosensitive resin layer and the silicone rubber layer, and aminosilane compounds and organic titanate compounds are particularly preferred.
  • an adhesive component may be added to the silicon rubber layer.
  • An aminosilane compound or an organic titanate compound can also be used as the additive adhesive component.
  • a silicone rubber layer is formed on the substrate on which the separation wall is formed.
  • the exposure for creating the partition wall is performed from the back side of the substrate using the separation wall as a mask, and further, the irradiated UV light is scattered to enlarge the incident light from the size of the transmission part and to be used for the photosensitive resin. Therefore, the portion of the resin that is soluble by photoreaction is larger on the silicone rubber surface side. To do so. After exposure in this way, a partition wall having a silicone rubber surface layer can be produced by developing with an n-heptane Z ethanol mixed solution.
  • Gases containing at least fluorine atoms introduced in this process include CF and C
  • C F octafluorocyclopentene
  • a gas such as oxygen, argon, or helium may be used in combination as necessary.
  • a gas such as oxygen, argon, or helium may be used in combination as necessary.
  • the mixing ratio of O is in the range of 30% or less.
  • a method for generating plasma methods such as low-frequency discharge, high-frequency discharge, and microwave discharge can be used.
  • Conditions such as pressure, gas flow rate, discharge frequency, and processing time during plasma processing are as follows. It can be set arbitrarily.
  • the pressure during the plasma treatment is 10 to: LOOPa is preferred, 20 to 80 Pa force is more preferred, 30 to 50 Pa force is more preferred! / ,.
  • the gas flow rate is preferably 40 to 300 sccm, more preferably 50 to 200 sccm, and even more preferably 60 to 100 sccm.
  • the output is preferably 10 to 100 W, more preferably 20 to 90 W, and even more preferably 30 to 80 W. Processing time depends on the above pressure and output, 20 ⁇ 200sec force S preferred, 20 ⁇ : More preferred than LOOsec, 10 ⁇ 50sec force preferable.
  • water repellent materials such as polytetrafluoroethylene such as fluorine resin, silicon rubber, perfluoroalkyl acrylate, hide mouth carbon acrylate, methyl siloxane, etc.
  • contact angle to the liquid composition is 60 ° or more.
  • the water repellent material is used as it is by dissolving or dispersing in a solvent.
  • the water repellent material As a method for applying the water repellent material, it is possible to select the most suitable method for each material such as slit coat, spin coat, dip coat, roll coat, etc., as long as it does not affect the substrate and the separation wall. is there.
  • UV'O treatment is performed through the separation wall from the back side of the substrate on which the separation wall is formed.
  • Water-repellent material is applied by selectively removing the water-repellent film on portions other than the separation wall or making it hydrophilic (the contact angle with the colorant is more than 30 ° before and after the treatment). It can be done.
  • the patterning method is an optimum method according to the material such as laser ablation, plasma ashing, dry treatment such as corona discharge treatment, and wet treatment using alkali. It is possible to select.
  • a lift-off method or the like is also effective when forming a pattern of a water repellent material on the separation wall.
  • a photocatalyst-containing layer side substrate having a substrate and a photocatalyst-containing layer formed on the substrate, and a separation substrate having a transparent substrate and a wettability changing layer formed on the transparent substrate.
  • a substrate for wall formation is prepared.
  • the photocatalyst-containing layer and the wettability changing layer are arranged so as to have a predetermined gap, and an example For example, using a photomask or the like, a pattern forming process for irradiating the pattern forming the separation wall with energy from a predetermined direction is performed. As a result, a pattern is formed which includes a hydrophilic region where the wettability is changed on the wettability changing layer in the portion irradiated with energy, and a water-repellent region where the energy is not strong.
  • the portion other than the hydrophilic region is a water-repellent region, the fountain solution does not adhere, and the fountain solution can be applied only to the hydrophilic region.
  • a pixel portion forming coating solution or the like for forming the pixel portion is applied between the separating walls by, for example, an ink jet device to form the pixel portion to be a color filter.
  • the pattern forming step in the present invention is water-repellent and ink-philic, and further for forming a separation wall having a wettability changing layer that changes so that the contact angle with water is lowered by the action of a photocatalyst accompanying energy irradiation.
  • a water-repellent region and a hydrophilic region whose wettability is changed by the action of the photocatalyst accompanying energy irradiation are formed on the substrate for forming the partition wall, which will be described later.
  • the hydrophilic region that does not form the colored portion can be protected with the fountain solution, which makes it possible to form a high-definition colored portion.
  • the separation wall forming substrate used in the present invention has water repellency and ink affinity, and further has a wettability changing layer that changes so that the contact angle with water is lowered by the action of a photocatalyst accompanying energy irradiation. If so, the wettability changing layer, which is not particularly limited, may be formed on the transparent substrate.
  • the wettability changing layer used in the present invention is a layer that is water-repellent and ink-philic, and further changes so that the contact angle with water is lowered by the action of a photocatalyst accompanying energy irradiation.
  • the present invention by having the wettability changing layer, it is possible to make the portion irradiated with energy a hydrophilic region and the portion not irradiated with energy as a water repellent region in the above-described pattern formation. It becomes.
  • the region where the colored portion is formed is a water-repellent region, and the region where the colored portion is not formed is a hydrophilic region, so that the hydrophilic region where the colored portion is not formed is protected with dampening water, and the parent of the water-repellent region is thus formed.
  • the ink properties it becomes possible to form colored portions only in the water-repellent region using, for example, oil-based ink as a colored portion forming coating liquid.
  • the critical surface tension of the above-mentioned wettability changing layer before energy irradiation is preferably in the range of 20 mNZm to less than 50 mNZm, and more preferably in the range of 35 mNZm to less than 50 mNZm! /.
  • the wettability changing layer before the energy irradiation can be made a water-repellent region having water repellency and ink affinity.
  • the contact angle between the wettability changing layer and the 70 mNZm liquid before energy irradiation is preferably in the range of 50 ° or more and less than 120 °, particularly 70 ° or more and less than 120 °.
  • dampening water may adhere to the water-repellent region, and the colored part forming process. This is because it becomes difficult to form the colored portion with high definition.
  • the critical surface tension of the wettability change layer whose wettability has changed due to the action of the photocatalyst associated with energy irradiation is in the range of 50 mNZm to less than 75 mNZm, especially 60 mNZm to less than 75 mNZm! / ,.
  • the wettability changing layer whose wettability has been changed by the action of the photocatalyst can be made hydrophilic.
  • the contact angle between the wettability changing layer having changed wettability and the 70 mNZm liquid is preferably in the range of 0 ° to less than 50 °, and more preferably in the range of 0 ° to less than 40 °.
  • the contact angle with the liquid is higher than the above range, the hydrophilicity is insufficient.
  • the liquid may be repelled. This is because the water becomes difficult to protect and it becomes difficult to form a high-definition colored portion.
  • the contact angle with the liquid here refers to the contact angle with a liquid having various surface tensions measured using a contact angle measuring instrument (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.). 30 seconds after the drop was dropped), and the results were obtained or the results were graphed. In this measurement, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used as the liquid having various surface tensions.
  • the wettability changing layer in the present invention contains fluorine in the wettability changing layer, and the fluorine content on the surface of the wettability changing layer irradiates the wettability changing layer with energy.
  • the wettability changing layer may be formed so that, when irradiated, the wettability changing layer is lowered by the action of the photocatalyst as compared to before energy irradiation.
  • fluorine has an extremely low surface energy, so that the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, fluorine content
  • the content of fluorine is small compared to the critical surface tension of the surface of the part! /, The critical surface tension of the part becomes large.
  • the portion with a low fluorine content is a hydrophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern having a small fluorine content and partial force as compared with the surrounding surface forms a hydrophilic region pattern in the water-repellent region.
  • the pattern of the hydrophilic region can be easily formed in the water repellent region by irradiating the pattern with energy.
  • the hydrophilic area that does not form the colored part is protected with dampening water, and the colored part is highly precisely defined only in the water-repellent and ink-repellent water-repellent area. It becomes possible to form.
  • the fluorine content contained in the wettability changing layer containing fluorine includes the fluorine content in the hydrophilic region formed by irradiating energy and having a low fluorine content.
  • the fluorine content of the non-water-repellent region is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.
  • dampening water can be easily applied only to the hydrophilic region, and the colored portion can be formed with high definition by applying the colored liquid composition for forming the colored portion only to the water repellent region. It becomes possible. This rate of decrease is based on weight.
  • Various commonly used methods can be used to measure the fluorine content in such a wettability changing layer.
  • X-ray Photoelectr on Spectroscopy ESCA (Electron spectroscopy for Shimicai Analv sis).
  • ESCA Electron spectroscopy for Shimicai Analv sis.
  • a method capable of quantitatively measuring the amount of fluorine on the surface, such as fluorescent X-ray analysis and mass spectrometry, is not particularly limited.
  • the material used for such a wettability changing layer is a material whose wettability is changed by the photocatalyst in the photocatalyst-containing layer opposed to the wettability of the above-described wettability changing layer, that is, by photoirradiation.
  • Specific examples include organopolysiloxanes, which are not particularly limited as long as they have a main chain that is difficult to be degraded or decomposed by the above action.
  • the organopolysiloxane power is preferably an organopolysiloxane containing a fluoroalkyl group.
  • Such organopolysiloxanes include, for example, ⁇ 1> an organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane, etc. by a sol-gel reaction, etc. ⁇ 2> water repellent properties
  • organopolysiloxanes such as organopolysiloxanes cross-linked with reactive silicones having excellent oil repellency.
  • X represents an alkoxyl group, a acetyl group or a halogen.
  • n is an integer from 0 to 3.
  • organopolysiloxane which is one or more hydrolyzed condensates or cohydrolyzed condensates of the silicon compound represented by
  • the number of carbon atoms of the group represented by Y is preferably within the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. It is preferable.
  • organopolysiloxanes containing a fluoroalkyl group can be preferably used.
  • Specific examples include one or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes.
  • known fluorine-based silane coupling agents can be used.
  • the water repellency of the non-energy-irradiated portion of the wettability changing layer is greatly improved. It becomes possible to prevent adhesion of water.
  • the above substances are ink-philic, it is possible to apply oil-based ink or the like as a colored portion forming coating liquid for forming colored portions. Further, dampening water can be attached to the hydrophilic region as the energy irradiation portion.
  • Examples of the reactive silicone of ⁇ 2> include compounds having a skeleton represented by the following general formula (2).
  • n is an integer of 2 or more
  • R 1 and R are each a substituted or unsubstituted alkyl, alkaryl, aryl or cyanoalkyl group having 1 to 10 carbon atoms.
  • those having R 1 and R 2 carbyl groups are preferred because the surface energy becomes the smallest, and it is preferred that the methyl group is 60% or more by molar ratio.
  • the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
  • a stable organosilicone compound that does not undergo a crosslinking reaction such as dimethylpolysiloxane may be mixed.
  • the force that can use various materials such as organopolysiloxane in the wettability changing layer as described above includes fluorine in the wettability changing layer as described above. This is effective for forming a wettable pattern. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily degraded or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.
  • the wettability changing layer in the invention may further contain a surfactant.
  • hydrocarbons such as NIKKOL BL, BC, BO, and BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Ink Chemical Industry Co., Ltd. MegaFac F-141, 144, Neos Co., Ltd., Fategent F-200, F251, Daikin Industries Co., Ltd. Dudyne DS-401, 402, Threeem Co., Ltd. FC—170, 176, etc.
  • An on-surfactant can be used, and a cationic surfactant, a char-on surfactant, and an amphoteric surfactant can also be used.
  • the wettability changing layer may include polybutanol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene monomer, epoxy resin, Phenolic resin, polyurethane, melamine resin, polycarbonate, polychlorinated butyl, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyacetic acid butyl, polyester, polybutadiene, polybenzimidazole, poly An oligomer such as acrylic nitrile, epichlorohydrin, polysulfide, polyisoprene, a polymer, or the like can be contained.
  • Such a wettability changing layer is prepared by dispersing the above-described components in a solvent together with other additives as necessary to prepare a coating solution, and coating the coating solution on a transparent substrate. Can be formed.
  • the solvent to be used alcohol-based organic solvents such as ethanol and isopropanol are preferable.
  • the coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating.
  • the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
  • the wettability changing layer used in the present invention may be a self-supporting material as long as it is formed of a material whose surface wettability can be changed by the action of a photocatalyst. It can also be a material that does not have self-supporting properties!
  • “having self-supporting property” means that it can exist in a tangible state without other supporting materials.
  • the wettability changing layer is a self-supporting material, it is possible to use, for example, a commercially available resin film having a material strength that can become the wettability changing layer, which is advantageous in terms of cost. It can be said.
  • the film formed from the above-mentioned material has a self-supporting property, it is possible to use this material.
  • polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polybulufluoride Acetal resin, nylon, ABS, PTFE, methatal resin, phenol resin, polyvinylidene fluoride, polio Examples include ximethylene, polybutyl alcohol, polyvinyl chloride, polyethylene terephthalate, and silicone.
  • the wettability changing layer in the present invention is preferably a wettability changing layer having no self-supporting property.
  • the wettability changing layer formed of the material that greatly changes the wettability described above usually has few self-supporting materials! Because.
  • the action of the photocatalyst in the photocatalyst-containing layer is used to oxidize and decompose the organic group that is a part of the above-described component, thereby By changing the wettability to make it hydrophilic, it is possible to make a big difference in wettability with the non-energy-irradiated part.
  • the wettability changing layer used in the present invention is not particularly limited as long as the wettability changing layer is changed by the action of the photocatalyst as described above, but does not particularly contain a photocatalyst. A layer is preferred.
  • a photocatalyst when a photocatalyst is contained in the wettability changing layer, if the work is performed in a bright place in the dampening water coating process or colored part forming process described later, the sensitivity is increased by dampening water.
  • the wettability of the wettability changing layer is changed by the action of the photocatalyst, and it may be difficult to form a colored portion with high definition.
  • the photocatalyst is not contained in the wettability changing layer, it is not necessary to worry about the above-mentioned problems. Therefore, it is possible to produce a color filter with a simple apparatus, and then color When used as a filter, it is a force that can be used without problems for a long time without having to worry about being affected by the passage of time.
  • the water repellent treatment method using a plasma is particularly preferred because of its "simpleness of the process" and the viewpoint power.
  • the method for producing a color filter of the present invention is the production of the dark color separation wall on the substrate.
  • a colored liquid composition for forming pixels of two or more colors is formed in the space between the dark color separation walls formed on the substrate in the development process.
  • a plurality of pixels having two or more colors are formed.
  • the means for fixing the shape of the dark color separation wall before forming each pixel in this way is not particularly limited, and examples thereof include the following.
  • the heat treatment here refers to heating a substrate having a dark color separation wall in an electric furnace, a dryer or the like, or irradiating an infrared lamp.
  • the exposure amount in the case of performing 1) above, 500 ⁇ 3000MjZcm 2 if the atmosphere, good Mashiku is 1000 ⁇ 2000MiZcm 2
  • the heating temperature when the same 2) perform a 50 to 120 ° C, preferably about 70 to 100 ° C, and the heating time is about 10 to 40 minutes.
  • the temperature is lower than 50 ° C, there is a concern that the dark color separation wall will not harden, and when the temperature is higher than 120 ° C, there is a concern that the dark color separation wall shape will collapse.
  • a heating step of performing heat treatment (so-called beta treatment) is provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated.
  • the heating temperature and time depend on the composition of the dark color composition and the thickness of the formed layer, but generally from about 120 ° C to about 120 ° C from the viewpoint of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. About 10 minutes to about 120 at 250 ° C U, prefer to heat for a minute.
  • the pattern shape of the color filter formed in this way is not particularly limited.
  • the color filter has a general black matrix shape, such as a stripe shape, a lattice shape, or even a delta arrangement. It may be a shape.
  • an ink jet system used in the present invention there are a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is ejected intermittently using a piezoelectric element, and an ink is intermittently heated by using its foaming.
  • Various methods such as a method of injecting the ink can be employed.
  • the ink used may be oily or water-based.
  • the coloring material contained in the ink can be used for both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability.
  • a coating-type colored ink (colored resin composition, for example, described in JP-A-2005-3861 [0034] to [0063]) and JP-A-10-195358 are used for producing known color filters. [0009]
  • the ink jet composition described in [0026] can also be used.
  • thermosetting resin is widely used as a component that is cured by heating, and examples of components that are cured by energy rays include those obtained by adding a photoinitiator to an attalylate derivative or a metatalylate derivative.
  • attalylate derivatives those having a plurality of attalyloyl groups and methacryloyl groups in the molecule are more preferred.
  • a water-soluble one can be preferably used, and even a poorly water-soluble one can be used after being emulsified.
  • the dark color composition containing a colorant such as a pigment as mentioned above in the section of dark color composition> can be used as a suitable one.
  • thermosetting ink for color filters containing at least a binder and a bifunctional to trifunctional epoxy group-containing monomer is also preferably used. Can do.
  • the color filter according to the present invention is a color filter in which pixels are formed by an inkjet method.
  • the filter is preferably a three-color filter by spraying RGB three-color inks.
  • This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.
  • an overcoat layer may be provided on the entire surface to improve solvent resistance or flatness.
  • the overcoat layer can protect the solidified layers of the inks R, G, and B and can flatten the surface, but it is preferably not provided from the viewpoint of increasing the number of steps.
  • Examples of the resin (OC agent) forming the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Among them, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually mainly composed of acrylic resin, and has excellent adhesion. An acrylic resin composition is desirable.
  • overcoat layer examples include those described in paragraphs [0018] to [0028] of JP-A-2003-287618, and commercially available overcoat agents such as “Optoma I SS 6699G” manufactured by JSR. It is done.
  • Examples of the display device of the present invention include display devices such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device.
  • display devices such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device.
  • Examples of display devices and explanation of each display device refer to “Electronic display devices (Akio Sasaki, published by Industrial Research Institute, Ltd. 1990)”, “Display devices (written by Junaki Ibuki, Industrial Books Co., Ltd.) Issue year)).
  • a liquid crystal display device is particularly preferable.
  • Liquid crystal display devices are described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”.
  • the liquid crystal display device to which the present invention can be applied There are no particular restrictions on the liquid crystal display device to which the present invention can be applied.
  • Applicable to display devices is particularly effective for a color TFT liquid crystal display device.
  • a color TFT liquid crystal display device is described in, for example, “Karaichi TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field drive 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 Technology and Latest Trends in Toba Research Center (Research Division of Toray Research Center 2001)”.
  • the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a knock light, a spacer, and a viewing angle compensation film.
  • the black matrix of the present invention can be applied to a liquid crystal display device composed of these known members.
  • “'94 Liquid Crystal Display Peripheral Materials' Chemicals” Kelvano Shima, CMC Co., Ltd., 1994)
  • the color filter 1 of the present invention can be applied to a TV, personal computer, liquid crystal projector, game machine, mobile phone or other portable terminal, digital camera, car navigation system or the like without particular limitation.
  • a 16 ⁇ m thick polyethylene terephthalate film (Tetron (registered trademark) G2 manufactured by Teijin DuPont Films Ltd.) was applied onto a temporary support using a slit nozzle and the following dark composition K1 was applied and dried. It was. In this way, the dry film thickness is 2.2 ⁇ m on the temporary support.
  • a dark photosensitive resin layer of m was provided, and finally a protective film (12 m thick polypropylene film) was pressure-bonded.
  • dark photosensitive transfer material K1 a dark photosensitive transfer material in which the temporary support and the dark photosensitive resin layer became a solid body was produced, and the sample name was named dark photosensitive transfer material K1.
  • the dark color composition first remove the carbon black dispersion and propylene glycol monomethyl ether acetate in the amounts described in the dark color composition K1 formulation below, mix at a temperature of 24 ° C ( ⁇ 2 ° C) and 150 rpm.
  • Triazine and Surfactant 1 are removed and added in this order at a temperature of 25 ° C ( ⁇ 2 ° C) and at a temperature of 40 ° C ( ⁇ 2 ° C). Obtained by stirring at 150 rpm for 30 minutes.
  • Carbon black (Negex35 manufactured by Degussa) 13. 1%
  • a glass detergent solution adjusted to 25 ° C is sprayed on an alkali-free glass substrate with a shower for 20 seconds while washing with a rotating brush with nylon bristles.
  • the silane coupling solution N- ⁇ (amino Ethyl))-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.
  • KOH KOH
  • CDK-1 Fuji Film Elect Kokuku Materials Co., Ltd.
  • ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and post exposure was performed at an exposure amount of 2000 mJ / cm 2 in the atmosphere at 220 ° C for 30 minutes.
  • Caro Heat treatment was performed to obtain a separation wall having an optical density of 4.5.
  • the surface roughness of the separation wall thus obtained was measured with a contact film thickness meter (Tencor stylus type surface roughness meter P10, JIS B0601).
  • the surface roughness value Ra was 6. Onm.
  • the height of the painting wall was 2. O / zm.
  • optical density (hereinafter also referred to as “transmission optical density”) of the separation wall in the examples and comparative examples of the present invention was measured as follows.
  • the transmission optical density of the sample was measured at 555 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100) (OD). Separately, measure the transmission optical density of the glass substrate in the same way (OD), and subtract OD from OD as the transmission optical density of the dark separation wall.
  • a spectrophotometer manufactured by Shimadzu Corporation, UV-2100
  • the substrate on which the separation wall was formed was subjected to plasma water repellency treatment under the following conditions using a force sword coupling type parallel plate type plasma treatment apparatus.
  • a pigment a polymer dispersant and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels (also simply referred to as “ink”).
  • R red
  • the solvent ethyl ethoxypropionate is the standard solution shown in the wet test specified in JIS-K6768!
  • the contact angle (0) was measured, and the contact angle to the surface of the specimen with a critical surface tension of 30 mNZm was 18 ° and the contact to the surface of the specimen with a critical surface tension of 70 mNZm was obtained from the Zisman plot graph. The angle was 0 °.
  • neopentyldaricol diglycidyl ether which is the second epoxy resin, has a contact angle of 37 ° with respect to the surface of a specimen having a critical surface tension of 30 mNZm in the same test, and has a critical surface.
  • the contact angle with respect to the surface of a test piece with a tension of 70 mNZm was 0 ° C.
  • green (G) is the same as in the case of the red (R) pixel portion colored ink composition, except that the same amount of CI pigment green 36 is used instead of CI pigment red 254 in the above yarn A colored ink composition for red pixels was prepared.
  • a colored ink composition for pixels was prepared.
  • the ink composition is ejected to a desired concentration using an ink jet recording apparatus, and R, G, and B pixels described above, within the region separated by the separation wall of the image forming substrate obtained above (concave portion surrounded by the convex portion)
  • the ink composition is ejected to a desired concentration using an ink jet recording apparatus, and R, G
  • a color filter composed of the pattern B was prepared.
  • the black matrix and each pixel were completely cured by betaing the color filter after image coloring in a 230 ° C oven for 30 minutes.
  • the ink constituting each pixel of the color filter obtained in this manner was tightly fit in the gap between the image separation walls, and no defects such as color mixing with adjacent pixels were found.
  • a transparent electrode of ITO Indium Tin Oxide was further formed by sputtering on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above.
  • a glass substrate was prepared as a counter substrate, and was patterned using an etching resist for the PVA mode on the transparent electrode of the color filter substrate and the counter substrate, respectively.
  • the ITO resistance of the color filter on which this ITO was formed was measured (Mitsubishi Yuka “Loresta”; sheet resistance was measured by the four-probe method), and it was 12 ⁇ .
  • a photo spacer was provided in a portion corresponding to the upper part of the separation wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
  • an epoxy resin sealant is printed at a position corresponding to the outer periphery of the black matrix that surrounds the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was heat treated to cure the sealant.
  • a polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained.
  • a backlight of a cold cathode tube was constructed and placed on the back surface side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.
  • Example A1 A temporary support used in Example A1 was changed to a polyethylene terephthalate film having a thickness of 50 ⁇ m (Tetron (registered trademark) G2 manufactured by Tijin DuPont Films Co., Ltd.) in the same manner as in Example A1.
  • Tetron registered trademark
  • G2 manufactured by Tijin DuPont Films Co., Ltd.
  • the ink constituting each pixel has a dark color separation wall gap.
  • the ITO resistance of the color filter was measured (Mitsubishi Yuka “Mouth Resta”; sheet resistance was measured by the four-probe method), and it was 17 ⁇ / mouth. The results are shown in Table 1.
  • Example A1 except that the plasma water repellency treatment was changed to the following method, the same procedure as in Example A1 was performed to produce a color separation wall and a ITO color filter with a transparent electrode, and the same evaluation was performed. The results are shown in Table 1.
  • Example A1 the temporary support was peeled off, then the distance between the exposure mask surface and the dark photosensitive resin layer was set to 200 m, and the pattern exposure method was changed to Example A1. Similarly, color separation filters and ITO color filters with transparent electrodes were prepared and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example A1 the following “dry etching process” was added prior to the plasma water repellency treatment, in the same manner as in Comparative Example A1, but the separation wall and ITO color electrode with a transparent electrode were used. Luthers were produced and evaluated in the same manner. The results are shown in Table 1.
  • a force sword coupling type parallel plate plasma processing apparatus is applied to the above-mentioned substrate (substrate with a separation wall) on which a separation wall is formed.
  • a dry etching process was performed under the following conditions.
  • Example A1 As in Example A1, after coloring the R, G, and B pixels, when beta was applied under the same conditions, the ink overcame the separation wall, resulting in color mixing with adjacent pixels. Further, when the ITO resistance was measured in the same manner as in the example, it was 24 ⁇ / mouth. The results are shown in Table 1.
  • the color filter was visually observed with an optical microscope from the pixel forming side in the thickness direction, and color mixing was evaluated.
  • the evaluation criteria for color mixing is color mixing when there is color mixing in the pixels, and when 100 pixels in the color filter (optical element) are observed, ink remains on the upper surface of the dark color separation wall. Yes, if not, no color mixing.
  • the color filters of Examples A1 to A3 each had a low ITO resistance value that mixed colors.
  • the power filter of Comparative Examples A1 to A2 color mixing was observed and the ITO resistance value was low. From the viewpoint of ITO resistance, the lower the ITO resistance, the better.
  • the alkali-free glass substrate was cleaned with a UV cleaning device, brushed with a cleaning agent, and then ultrasonically cleaned with ultrapure water.
  • the substrate was heat treated at 120 ° C for 3 minutes to stabilize the surface state.
  • a glass substrate coater with a slit-shaped nozzle (manufactured by FS Asia Co., Ltd., trade name: MH-1600) is made of the following composition.
  • Color Photosensitive composition K1 was applied.
  • VCD vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • a photosensitive layer K1 was obtained.
  • the dark color photosensitive composition is first weighed in the amount of carbon black dispersion and propylene glycol monomethyl ether acetate described in the dark color photosensitive composition K1 formulation below, and mixed at a temperature of 24 ° C ( ⁇ 2 ° C). And then stirred for 10 minutes at 150 rpm, and then methylethylketone, binder P-l, hydroquinone monomethyl ether, DPHA solution, 2, 4 bis (trichloromethyl) 6- [4 '-( ⁇ , N bisethoxycarboromethyl) ) Amino 1 3'—Mouth Mole] —s Triazine and surfactant are removed and added in this order at a temperature of 25 ° C ( ⁇ 2 ° C) and a temperature of 40 ° C ( ⁇ 2 Obtained by stirring for 30 minutes at 150 rpm at ° C).
  • an oxygen blocking layer coating solution having the following composition was applied onto the photosensitive layer K1 and dried to provide an oxygen blocking layer P1 having a film thickness of 1.6 microns.
  • Proximity type exposure machine with ultra-high pressure mercury lamp manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.
  • the substrate and mask quartz exposure mask with image pattern standing vertically
  • exposure mask surface The distance between the oxygen barrier layer P1 and the oxygen barrier layer P1 was set to 200 m, and pattern exposure was performed with an exposure amount of 70 mjZc m 2 .
  • pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark photosensitive layer K1, and then a KOH-based developer (KOH, containing a nonionic surfactant, trade name) : CDK-1, Fujifilm Elect Mouth-X Materials Co., Ltd.) at 80 ° C. for 23 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterning image.
  • KOH KOH-based developer
  • ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and the exposure amount was 2000 m in the atmosphere.
  • Post-exposure was performed at J / cm 2 and a heat treatment at 220 ° C.
  • This transmission optical density was measured at 555 nm (OD) using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100). Separately, the transmission optical density of the glass substrate was measured by the same method (OD).
  • the value obtained by subtracting OD from OD was the transmission optical density of the dark color separation wall.
  • the substrate on which the separation wall was formed was subjected to plasma water repellency treatment under the following conditions using a force sword coupling type parallel plate type plasma treatment apparatus.
  • a pigment a polymer dispersant and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.
  • the solvent ethyl ethoxypropionate is the standard solution shown in the wetting test specified in JIS-K6768!
  • the contact angle 30 seconds after contact with the droplet ( 0) and the contact angle with respect to the surface of the test piece with a critical surface tension of 30 mNZm obtained from the Zisman plot graph is 18 ° and the contact angle with respect to the surface of the test piece with a critical surface tension of 70 mNZm is 0 °.
  • neopentyldarlicol diglycidyl ether which is the second epoxy resin, has a contact angle of 37 ° with respect to the surface of a specimen having a critical surface tension of 30 mNZm in the same test, and has a critical surface.
  • the contact angle with respect to the surface of a test piece with a tension of 70 mNZm was 0 ° C.
  • blue (B) coloring for the pixel is the same as the coloring ink composition for red pixel except that CI pigment blue 15: 6 is used in the same amount instead of CI pigment red 254 in the above yarn An ink composition was prepared.
  • a transparent electrode of ITO Indium Tin Oxide
  • ITO Indium Tin Oxide
  • the ITO resistance of the color filter on which this ITO was formed was measured (Mitsubishi Yuka “Loresta”; sheet resistance was measured by the four-probe method), and was 12 ⁇ / mouth.
  • a photospacer was provided at a portion corresponding to the upper part of the separation wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
  • an epoxy resin sealant is printed at a position corresponding to the outer periphery of the black matrix that surrounds the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was heat treated to cure the sealant.
  • a polarizing plate 111 ⁇ 2-2518 made by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained.
  • a backlight of a cold cathode tube was constructed and placed on the side of the liquid crystal cell on which the polarizing plate was provided to form a liquid crystal display device.
  • thermoplastic resin layer having the following formulation HI On a 75 ⁇ m-thick polyethylene terephthalate film temporary support, using a slit nozzle, a coating solution for a thermoplastic resin layer having the following formulation HI was applied and dried. Next, an intermediate layer coating solution comprising the above-mentioned formulation P1 was applied and dried. Further, the dark color photosensitive composition K1 was applied and dried.
  • a layer was provided, and finally a protective film (12 m thick polypropylene film) was pressure-bonded.
  • a dark photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a black (K) dark photosensitive resin layer was prepared, and a sample was prepared.
  • the name is dark photosensitive transfer material K1.
  • thermoplastic resin layer prescription HI> • methanol
  • a glass cleaning solution adjusted to 25 ° C was sprayed onto a non-alkali glass substrate with a shower for 20 seconds while washing with a rotating brush with nylon bristles.
  • the silane coupling solution N— ⁇ (aminoethyl) ⁇ —aminopropyltrimethoxysilane, 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the substrate and mask are used with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp.
  • a proximity-type exposure machine manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.
  • the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 m, and pattern exposure was performed at an exposure dose of 70 miZcm 2 .
  • the ink constituting each pixel of the color filter obtained in this manner fits exactly in the gap between the dark color separation walls, and defects such as color mixing with adjacent pixels had great power. This is presumably because the wettability of the ink on the surface of the separation wall was unexpectedly reduced by using the present invention.
  • the ITO resistance of the color filter was measured (Mitsubishi Yuka “Mouth Resta”; sheet resistance was measured by the four-probe method) and found to be 10 ⁇ / mouth.
  • a separation wall and a color filter with a transparent electrode made of ITO were prepared and evaluated in the same manner as in Example B1, except that the thickness of the intermediate layer was 0.4 m. The results are shown in Table 2. Ra was 3.5 nm, and the height of the separation wall was 2. O / z m.
  • a separation wall and a color filter with a transparent electrode of ITO were prepared in the same manner as in Example B1. Evaluation was performed. The results are shown in Table 2. Ra is 4.7 nm, and the height of the separation wall is 2.0 ⁇ m.
  • a fluorosurfactant (manufactured by Sumitomo 3M, Fluorad FC-430) is added in advance to the substrate on which the separation wall is formed in an amount of 0.5% by weight (based on the solid content of the photosensitive resin).
  • a certain alkali-soluble photosensitive resin (Hexostiapan, positive photoresist AZP4210) to a thickness of 2 ⁇ m using a slit-like nozzle, and in a hot air circulating dryer at 90 ° C For 30 minutes Heat treatment was performed.
  • the surface energy inside and outside the pixel after the formation of the water-repellent resin layer was 10 to 15 dyneZcm outside the pixel (on the resin layer) and 55 dyneZcm before and after the pixel (on the glass substrate).
  • Example B1 except that the plasma water repellency treatment was not performed, a separation wall and a color filter with a transparent electrode made of ITO were prepared in the same manner as in Example B1, and the same evaluation was performed.
  • a separation filter and a color filter with a transparent electrode made of ITO were produced by performing the same treatment and operation as in Example B1 except that the oxygen blocking layer of Example B1 was used, and the same evaluation was performed.
  • the optical density of the dark color separation wall thus obtained was 4.5.
  • Ra was 8. Onm, and the height of the separation wall was 2. O / z m.
  • Comparative Example B1 a separation wall and a color filter with a transparent electrode made of ITO were prepared in the same manner as in Comparative Example B1 except that the following “dry etching treatment” was added before the plasma water repellency treatment. was evaluated.
  • the color filters of Examples B1 to B5 had little or no color mixing, and the ITO resistance value was low. In the color filters of Comparative Examples Bl to B2, color mixing was observed.
  • the ITO resistance value is preferably as low as possible from the viewpoint of showing good display characteristics. Further, from comparison between Example B5 and Example B1, it was found that the combined use of the oxygen blocking layer and the water repellent treatment in the present invention not only prevented color mixing but also had an effect on ITO resistance.
  • the alkali-free glass substrate was cleaned with a UV cleaning device, brushed with a cleaning agent, and then ultrasonically cleaned with ultrapure water.
  • the substrate was heat treated at 120 ° C for 3 minutes to stabilize the surface state.
  • the dark color photopolymerizable composition is first weighed in the amount of carbon black dispersion and propylene glycol monomethyl ether acetate described in the dark color photopolymerizable composition formulation below, and mixed at a temperature of 24 ° C ( ⁇ 2 ° C).
  • Carbon black (Negex35 manufactured by Degussa) 13. 1%
  • KOH containing a non-ionic surfactant, trade name: CDK-1, Fujifilm Elect Mouth-X Materials Co., Ltd.
  • a KOH developer KOH, containing a non-ionic surfactant, trade name: CDK-1, Fujifilm Elect Mouth-X Materials Co., Ltd.
  • a KOH developer KOH, containing a non-ionic surfactant, trade name: CDK-1, Fujifilm Elect Mouth-X Materials Co., Ltd.
  • ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, post-exposure was performed at an exposure amount of 2000 mJ / cm 2 in the atmosphere, and 220 ° C for 30 minutes.
  • a beta treatment was performed to obtain a separation wall with an optical density of 4.5.
  • the surface roughness of the separation wall thus obtained was measured with a contact film thickness meter (Tencor's stylus type surface roughness meter P10). Ra was 3.5 microns and the separation wall height was 2. .
  • a force sword coupling parallel plate type plasma processing device is applied to the substrate on which the separation wall is formed.
  • the plasma water repellency treatment was performed under the following conditions.
  • a pigment a polymer dispersant and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a colored ink composition for red (R) pixels.
  • the solvent ethyl ethoxypropionate is the standard solution shown in the wetting test specified in JIS-K6768!
  • the contact angle 30 seconds after contact with the droplet ( 0) and the contact angle with respect to the surface of the test piece with a critical surface tension of 30 mNZm obtained from the Zisman plot graph is 18 ° and the contact angle with respect to the surface of the test piece with a critical surface tension of 70 mNZm is 0 °.
  • neopentyldarlicol diglycidyl ether which is the second epoxy resin, has a contact angle of 37 ° with respect to the surface of a specimen having a critical surface tension of 30 mNZm in the same test, and has a critical surface.
  • the contact angle with respect to the surface of a test piece with a tension of 70 mNZm was 0 ° C.
  • G green
  • the same amount of CI Pigment Green 36 is used instead of CI Pigment Red 254 in the above-described yarn, except that the same amount of CI Pigment Green 36 is used.
  • a colored ink composition was prepared.
  • blue (B) coloring for the pixel is the same as the coloring ink composition for red pixel except that CI pigment blue 15: 6 is used in the same amount instead of CI pigment red 254 in the above yarn An ink composition was prepared.
  • a transparent electrode of ITO Indium Tin Oxide
  • ITO Indium Tin Oxide
  • the ITO resistance of the color filter on which this ITO was formed was measured (Mitsubishi Yuka “Loresta”; sheet resistance was measured by the four-probe method), and was 14 ⁇ / mouth.
  • a photospacer was provided at a portion corresponding to the upper part of the separation wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
  • an epoxy resin sealant is printed at a position corresponding to the outer periphery of the black matrix that surrounds the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After alignment, the bonded substrates are heat treated to The glue was cured. A polarizing plate 111 ⁇ 2-2518 made by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and placed on the side of the liquid crystal cell on which the polarizing plate was provided to form a liquid crystal display device.
  • a force error filter was created and evaluated in the same manner. The results are shown in Table 3.
  • the height of the separation wall was 2. O / z m.
  • the oxygen partial pressure was measured using an oxygen meter G-102 manufactured by Iijima Electronics.
  • a separation wall and a color filter were prepared in the same manner as in Example C1 except that the photosensitive layer K1 of Example C1 was changed to the following K2, and the same evaluation was performed.
  • the height of the separation wall was 2. O ⁇ m.
  • the results are shown in Table 3.
  • Example C4 A separation wall and a color filter with a transparent electrode made of ITO were prepared and evaluated in the same manner as in Example C1, except that the plasma water repellency treatment method was changed to the following method. The results are shown in Table 3.
  • Example C1 except that the plasma water repellency treatment was not performed, a separation wall and a color filter with a transparent electrode made of ITO were prepared in the same manner as in Example C1, and the same evaluation was performed.
  • a separation wall and a color filter were prepared in the same manner as in Example C1, except that the exposure process in the nitrogen atmosphere of Example C1 was changed to the exposure process under atmospheric pressure (oxygen partial pressure 0.21 atm). The same evaluation was performed.
  • the oxygen partial pressure was measured using an oxygen meter G-102 manufactured by Iijima Electronics.
  • Example C1 The step of exposing in the nitrogen atmosphere of Example C1 was changed to a step of exposing under atmospheric pressure (oxygen partial pressure of 0.21 atm), and before the plasma water repellent treatment, the following “dry etching” was performed.
  • a separation filter and a color filter with a transparent electrode made of ITO were prepared in the same manner as in Example C1 except that “treatment” was added, and the same evaluation was performed.
  • This transmission optical density was measured at 555 nm (OD) using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100). Separately, the transmission optical density of the glass substrate was measured by the same method (OD).
  • the value obtained by subtracting OD from OD was the transmission optical density of the dark color separation wall.
  • the color filters of Examples C1 to C5 have no color mixture or little color mixture, and the ITO resistance value is small. It was low.
  • the color filters 1 of Comparative Examples C1 to C2 have mixed colors, and the ITO resistance value is it was high.
  • the ITO resistance value is preferably as low as possible from the viewpoint of showing good display characteristics.
  • the method includes a step of forming a separation wall, and a step of applying a droplet of a colored liquid composition between the separation walls to form each pixel between the separation walls.
  • a method for producing a color filter comprising:
  • the step of forming the separation wall includes a step of transferring a photosensitive transfer material having at least a layer made of a photosensitive composition on a temporary support onto a substrate ⁇ 1>
  • ⁇ 3> The method for producing a color filter according to ⁇ 2>, wherein the photosensitive composition is a photopolymerizable composition.
  • ⁇ 4> The liquid droplet according to any one of ⁇ 1> to ⁇ 3>, wherein the liquid droplets are applied between the separation walls in a state where at least a part of the separation walls is water-repellent. Manufacturing method of color filter.
  • ⁇ 5> The method for producing a color filter according to ⁇ 4>, wherein at least a part of the separation wall is made water-repellent by plasma treatment.
  • the height of the separating wall is from 1.8 m to 10 m ⁇ 1>
  • ⁇ 8> A color filter produced by the production method according to any one of ⁇ 1> to ⁇ 7>, wherein the separation wall has a surface roughness Ra value of 6 nm or less.
  • a liquid crystal display device comprising the color filter according to ⁇ 8>.
  • a liquid crystal display device comprising the liquid crystal display element according to ⁇ 9>.
  • the method includes a step of forming a separation wall, and a step of applying a droplet of a colored liquid composition between the separation walls to form each pixel between the separation walls.
  • the step of forming the separation wall includes a step of transferring a photosensitive transfer material having at least a layer made of a photosensitive composition and an oxygen-blocking film onto a temporary support.
  • the step of forming the separation wall includes a step of applying a coating liquid containing a photosensitive composition on a substrate to form a photosensitive composition coating film, and applying an oxygen blocking film thereon. 11. The method for producing a color filter as described in 11> above.
  • the height of the separating wall is 1.8 m or more and 10 m or less.
  • the optical density of the separating wall is 2.5 or more and 10 or less.
  • the photosensitive composition is a photopolymerizable composition.
  • Liquid crystal display device comprising the color filter according to ⁇ 20> ⁇ 19>.
  • a liquid crystal display device comprising the liquid crystal display element according to ⁇ 20>.
  • a method of manufacturing a color filter that has two or more pixel groups exhibiting different colors on a substrate and each pixel constituting the pixel group is separated from each other by a dark color separation wall.
  • the method includes a step of forming a separation wall, and a step of applying a droplet of a colored liquid composition between the separation walls to form each pixel between the separation walls.
  • the height of the separating wall is 1.8 m or more and 10 m or less.
  • the optical density of the separating wall is from 2.5 to 10 22>
  • ⁇ 28> The method for producing a color filter according to any one of ⁇ 22> to ⁇ 27>, wherein the dark color photopolymerizable composition contains a bisimidazole compound as a photopolymerization initiator.
  • the bisimidazole compound strength 2,2′-bis (o black-mouthed phenol) —4, 4 ′, 5,5 ′ tetraphenylbisimidazole A manufacturing method of one filter.
  • Liquid crystal display device comprising the color filter described in ⁇ 31> ⁇ 30>.
  • Liquid crystal display device comprising the liquid crystal display element according to ⁇ 32> ⁇ 31>.

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Abstract

La présente invention concerne un procédé de production d’un filtre de couleur comprenant un substrat et deux ou plus de deux groupes de pixels différents les uns des autres en matière de couleur de développement placés sur le substrat, les pixels constituant les groupes de pixels étant séparés les uns des autres par des parois de séparation de couleur profonde. Le procédé comprend les étapes de formation des parois de séparation, d’application d’une composition de liquide coloré sur les parties entre les parois de séparation pour former des pixels entre les parois de séparation. Le procédé est caractérisé en ce que l’étape de formation des parois de séparation comprend les étapes de stratification d’un matériau de transfert photosensible sur un substrat et d’exposition du matériau de transfert photosensible de sorte qu’un support temporaire pour le matériau de transfert photosensible reste en place ; ou en ce que l’étape de formation des parois de séparation comprend les étapes de formation d'une couche d'une composition photosensible sur un substrat et d'exposition de la couche de composition photosensible de sorte qu’une couche protectrice d'oxygène se forme sur la couche de composition photosensible ; ou en ce que l'étape de formation de la paroi de séparation comprend les étapes de formation d’une couche d'une composition photopolymérisable de couleur profonde sur un substrat et d'exposition de la couche d’une composition photopolymérisable de couleur profonde sous une atmosphère pauvre en oxygène. La présente invention concerne également un filtre de couleur obtenu par ce procédé, un élément d'affichage à cristaux liquides comprenant ce filtre de couleur, et un dispositif d'affichage à cristaux liquides comprenant un tel élément d'affichage à cristaux liquides.
PCT/JP2006/308045 2005-04-15 2006-04-17 Procédé de production d’un filtre de couleur, filtre de couleur, élément d’affichage à cristaux liquides, et dispositif d’affichage à cristaux liquides WO2006112439A1 (fr)

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WO2007148689A1 (fr) * 2006-06-20 2007-12-27 Toppan Printing Co. , Ltd. Substrat pourvu d'une cloison et son procédé de production
JP2009175501A (ja) * 2008-01-25 2009-08-06 Dainippon Printing Co Ltd カラーフィルタの製造方法
US9417522B2 (en) 2013-12-27 2016-08-16 Jsr Corporation Photosensitive resin composition and method for producing resist pattern
KR20190025007A (ko) * 2016-09-27 2019-03-08 후지필름 가부시키가이샤 드라이 에칭용 조성물, 키트, 패턴 형성 방법 및 광학 필터의 제조 방법

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JP2001343518A (ja) * 2000-06-02 2001-12-14 Canon Inc 光学素子とその製造方法
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* Cited by examiner, † Cited by third party
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WO2007148689A1 (fr) * 2006-06-20 2007-12-27 Toppan Printing Co. , Ltd. Substrat pourvu d'une cloison et son procédé de production
JP5526543B2 (ja) * 2006-06-20 2014-06-18 凸版印刷株式会社 隔壁パターン付き基板およびその製造方法
JP2009175501A (ja) * 2008-01-25 2009-08-06 Dainippon Printing Co Ltd カラーフィルタの製造方法
US9417522B2 (en) 2013-12-27 2016-08-16 Jsr Corporation Photosensitive resin composition and method for producing resist pattern
KR20190025007A (ko) * 2016-09-27 2019-03-08 후지필름 가부시키가이샤 드라이 에칭용 조성물, 키트, 패턴 형성 방법 및 광학 필터의 제조 방법
KR102219156B1 (ko) 2016-09-27 2021-02-23 후지필름 가부시키가이샤 드라이 에칭용 조성물, 키트, 패턴 형성 방법 및 광학 필터의 제조 방법

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