WO2007094119A1

WO2007094119A1 - Method for fabricating color filter, color filter, and display device having such color filter

Info

Publication number: WO2007094119A1
Application number: PCT/JP2006/325158
Authority: WO
Inventors: Haruhiko Yoshino
Original assignee: Fujifilm Corporation
Priority date: 2006-02-13
Filing date: 2006-12-18
Publication date: 2007-08-23
Also published as: CN101371171B; CN101371171A; KR20080094937A; JPWO2007094119A1; TW200732706A

Abstract

A color filter has at least two pixel groups having different colors from each other on a board, and pixels constituting the pixel group are isolated from each other by a deep color isolation wall. In a method for fabricating the color filter, the process of forming the deep color isolation wall includes the following steps (1) to (3). (1) The step of exposing a layer consisting of a deep color composition so as to make a pattern under a poor oxygen atmosphere (pattern exposure step). (2) The step of forming a deep color isolation wall pattern by developing after the pattern exposure (development step). (3) The step of irradiating and curing the deep color isolation wall pattern with light having an exposure of at least 2500 mJ/cm2 (post-exposure step). This fabrication method enables pixels with a little color mixing and the like to be formed with a high position accuracy and the color filter to be fabricated at a low cost and with a high efficiency. A color filter fabricated by this method and a display device having the color filter are also provided.

Description

Specification

COLOR FILTER MANUFACTURING METHOD, COLOR FILTER, AND DISPLAY DEVICE HAVING THE COLOR FILTER

Technical field

The present invention relates to a method for manufacturing a color filter for a display device, a power color filter obtained by the manufacturing method, and a display device having the same.

Background art

[0002] A color filter for a display device has a structure in which red, green, and blue dot-like images are arranged in a matrix on a substrate such as glass, and the boundary is divided by a dark color separation wall such as a black matrix. is there. As a method for producing such a color filter, conventionally, a substrate such as glass is used as a support. 1) Dyeing method, 2) Printing method, 3) Application of colored photosensitive resin solution, exposure and Colored photosensitive resin solution method (colored resist method) by repeated development (see, for example, JP-A-63-298304, JP-A-63-309916, and JP-A-1-152449). 4) A method of sequentially transferring images formed on a temporary support onto a final or temporary support (for example, JP-A-61-99103, JP-A-61-233704, and JP-A-61). — See publication No. 279802.), 5) A colored layer is formed by applying a pre-colored photosensitive resin solution on a temporary support, and this photosensitive colored layer is transferred directly onto the substrate in sequence, There is a known method (transfer method) for forming a multicolor image by repeating exposure and development for the number of colors. Eg to JP 61- ninety-nine thousand one hundred and two see JP;.). Also known is a method using an ink jet method (for example, see JP-A-8-227012).

[0003] Among these methods, the colored resist method can produce a color filter with high positional accuracy, but it is not advantageous in terms of cost due to a large loss in application of the photosensitive layer resin solution. On the other hand, the ink jet method has a problem that the position accuracy of the pixel is poor, although the loss of the resin liquid is small and advantageous in terms of cost. A color filter manufacturing method has been proposed in which a black matrix (dark color separation wall) that overcomes these problems is formed by the colored resist method, and RGB pixels are manufactured by the inkjet method. When the cross-sectional shape is observed, Since the edges and edges are rounded and each of the inks that are subsequently ejected easily gets over the black matrix, bleeding, protrusion, color mixture with adjacent pixels, and white spots may occur.

In order to prevent these problems, a method for producing a color filter is disclosed which includes a step of irradiating and light-curing a dark color separation wall pattern after development, and a step of heat-treating the photocured dark color separation wall pattern. (For example, see Japanese Patent Application Laid-Open No. 2002-156520.) Force In this method, if the shape of the edge part of the partition wall is rounded or the edge part is rounded immediately (angularly V, etc.), the ink is darkly separated There is still a problem that makes it easier to get over the wall!

[0004] Further, a method for water-repellent treatment of a dark color separation wall by plasma treatment is known! (See, for example, JP-A-2001-343518;). However, even if only the water repellent treatment is applied to the dark-colored separation wall, it is difficult to sufficiently eliminate color mixing with adjacent pixels and white spots.

Patent Document 1: JP-A 63-298304

Patent Document 2: Japanese Patent Laid-Open No. 63-309916

Patent Document 3: JP-A-1 152449

Patent Document 4: JP-A 61-99103

Patent Document 5: Japanese Patent Laid-Open No. 61-233704

Patent Document 6: JP-A 61-279802

Patent Document 7: JP-A-61-99102

Patent Document 8: JP-A-8-227012

Patent Document 9: Japanese Patent Application Laid-Open No. 2002-156520

Patent Document 10: JP 2001-343518 A

Disclosure of the invention

Problems to be solved by the invention

[0005] Accordingly, the present invention provides a color filter manufacturing method capable of forming a color filter with low positional accuracy and high efficiency by forming pixels with low positional accuracy and color mixing, and a color filter obtained by this method, and An object of the present invention is to provide a display device provided with this color filter. Means for solving the problem

[0006] In view of such circumstances, the present inventor has conducted intensive research in order to solve the above problems.

As a result, if a dark color separation wall is formed by the following method, then when forming each pixel by the ink jet method or the like, defects such as bleeding and protrusion of each color ink, color mixture with adjacent pixels, and white spots are caused. It was found that defects can be prevented and a good color filter can be obtained, and the present invention has been completed.

That is, the present invention provides the following manufacturing method and the like.

<1> Production of a color filter having two or more pixel groups exhibiting different colors on a substrate and each pixel constituting the pixel group being separated from each other by a dark color separation wall A method for producing a color filter, characterized in that the step of forming the dark color separation wall includes the following steps (1) to (3).

(1) Process of pattern exposure of dark color composition layer in an oxygen-poor atmosphere (pattern exposure process)

(2) Process of developing after pattern exposure to form dark color separation wall pattern (Development process)

(3) A process of irradiating the dark color separation wall pattern with light with an exposure amount of 2500 mjZcm ² or more (post-exposure process)

[0008] <2> The method according to <1>, wherein the poor oxygen atmosphere is at least one selected from an inert gas atmosphere, a reduced pressure, and a protective layer lowering force capable of blocking oxygen. This is a method for producing a color filter.

<3> The development condition in the development step is that the concentration of an alkaline substance as a developer is

0.1 The use of a dilute aqueous solution of 30% to 30% by mass, development temperature of 22 ° C to 40 ° C, and development time of 10 to 120 seconds. Or a method for producing a color filter according to 2).

<4> The above <1> to <1>, wherein each pixel is formed between the dark color separation walls in a state where at least a part of the upper surface of the dark color separation wall is water-repellent. 3. The method for producing a color filter according to any one of 3>.

<0011><5> The method for producing a color filter as described in <4> above, wherein the means for bringing at least a part of the dark-color separation wall into a water-repellent state is a plasma treatment. so is there.

[0012] <6> The method of forming each pixel between the dark color separation walls is a method in which a colored liquid composition forming each pixel enters between the dark color separation walls by an inkjet method. The method for producing a color filter according to any one of <1> to <5>.

<7> The above-mentioned method, wherein a photosensitive transfer material having at least a layer having a dark color composition force is transferred onto a temporary support, and a dark color separation wall is formed. <1> to <6> The method for producing a color filter according to any one of the above.

<8> A color filter produced by the method for producing a color filter according to any one of <1> to <7>.

<9> The cross-sectional shape of the dark color separation wall formed on the substrate is such that the height from the substrate at the highest height of the dark color separation wall from the substrate is h, and the height from the substrate is 0.8 h. The line parallel to the base plate at the position is L, and the tangent line at the point where L and the dark separation wall touch is L and h.

1 1 2

When the line parallel to the substrate is L, the distance from the intersection with L to the dark separation wall is specified.

3 2 3

The color filter according to <8>, wherein a value obtained by dividing the value d by h is 0.04 or less.

[0015] <10> A display device comprising the color filter according to <9>.

The invention's effect

[0016] According to the present invention, a method for producing a color filter that can produce a color filter with low positional cost and high efficiency while forming a pixel with low positional accuracy and color mixing, etc., and a color filter obtained by this method And a display device including the color filter. Brief Description of Drawings

FIG. 1 is a conceptual diagram showing a cross-sectional shape of a dark color separation wall in the present invention.

FIG. 2A is a conceptual diagram showing a color filter pattern.

FIG. 2B is a conceptual diagram showing a color filter pattern.

FIG. 3A is a conceptual diagram showing a cross-sectional shape of a color filter.

FIG. 3B is a conceptual diagram showing a cross-sectional shape of the color filter.

BEST MODE FOR CARRYING OUT THE INVENTION [0018] 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. The method for producing a color filter is characterized in that the step of forming the dark color separation wall includes the following steps (1) to (3).

[0019] As described above, the dark color separation wall produced by the conventional method may cause defects such as color mixing when the pixel is formed by the ink jet method with a rough cross-sectional shape and the ink gets over the edge immediately. was there. In the present invention, the post-exposure amount is increased to 2500 mjZcm ² or more to maintain the shape after development, that is, the edge shape of the dark color separation wall is maintained in an angular state, so that Overcoming ink can be suppressed and color mixing can be prevented. In this case, as described later, it is preferable that the development is made as strong as possible and the cross-sectional shape of the dark color separation wall after development is changed from a vertical to an inversely tapered shape. Hereinafter, first, the dark color separation wall in the method for producing a color filter of the present invention will be described in detail.

[0020] (Dark color composition)

The dark color separation wall according to the present invention is formed from a dark color composition containing a dark color body. Here, the dark color composition is a composition having a high optical density, and its value when applied to the same thickness as the dark color separation wall to be formed is 2.0 to 10.0. . The optical density of the dark color composition is preferably 2.5 to 6.0, particularly preferably 3.0 to 5.0. In addition, since the dark color composition is preferably cured by a photoinitiating system as described later, the optical density with respect to the exposure wavelength (generally, the ultraviolet region) is also important. That is, the value when applied to the same thickness as the dark color separation wall to be formed is 2.0 to: LO. 0, preferably 2.5 to 6.0, and most preferably 3 0 to 5.0. 2. If it is less than 0, the dark color separation wall shape may not be what is desired. If it exceeds 10.0, the polymerization cannot be started and the dark color separation wall itself is created. It becomes difficult. As long as it has strong properties, even if the dark color in the composition is an organic substance (various dyes such as dyes and pigments) or carbon in various forms, the combined power of these substances can also be obtained. It may be a thing. The dark color is not particularly limited, but a black color is most often used.

Specific examples of the dark color body used for the dark color separation wall include the pigments and dyes described in JP-A-2005-17716, [0038] to [0054], and JP-A 2004-361447. The pigments described in JP-A Nos. [0068] to [0072] and the colorants described in JP-A-2005-17521, [0080] to [0088] can be preferably used.

[0022] Organic pigments, inorganic pigments, dyes, and the like can be suitably used for the dark color composition, and when light-shielding properties are required for the photosensitive resin layer, carbon black, titanium oxide, In addition to light-shielding agents such as metal oxide powder such as iron tetroxide, metal sulfide powder, and metal powder, a mixture of pigments such as red, blue, and green can be used. Known colorants (dyes and pigments) can be used. Among the known colorants, when a pigment is used, it is preferable that the pigment is uniformly dispersed in the dark color composition!

[0023] From the viewpoint of sufficiently shortening the development time, the ratio of the dark color body in the solid content of the dark color composition is preferably 30 to 70% by mass, and preferably 40 to 60% by mass. More preferably, it is more preferably 50 to 55% by mass.

Further examples of the dark black color body include carbon black, titanium carbon, iron oxide, titanium oxide, graphite, and the like. Among these, carbon black is preferable.

[0024] The dark colored body (pigment) is preferably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the dark body and a dispersant in an organic solvent (or vehicle) described later. The vehicle is a portion of a medium that disperses a dark colored body when the paint is in a liquid state, a portion that is liquid and binds to the dark colored body, and hardens the coating film (binder). And a component for dissolving and diluting (organic solvent). There are no particular restrictions on the disperser used to disperse the dark-colored body. For example, it is described in Asakura Kunizo, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, page 438. Well-known dispersers such as a hinder, a roll mill, an atrider, a super mill, a disorno, a homomixer, and a sand mill. Further, the machine described on page 310 of the document. Fine grinding may be performed using frictional force by mechanical grinding.

[0025] The dark color material (pigment) used in the present invention is preferably one having a number average particle diameter of 0.001 to 0.00 from the viewpoint of dispersion stability, and more preferably 0.01 to 0.08 m. preferable. Here, “particle diameter” means the diameter when the electron micrograph image of the particle is a circle of the same area, and “number average particle diameter” is the above-mentioned particle diameter for a large number of particles, This means the average value of 100 pieces.

[0026] The dark color composition preferably contains at least a polymerization initiator and a polyfunctional monomer in addition to a strong dark body. Further, a known additive such as a binder, a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter and the like can be further contained as necessary. Furthermore, it is preferred that the dark color composition is thermoplastic, which preferably becomes soft or tacky at a temperature of at least 150 ° C. Such viewpoint power can be modified by adding a compatible plasticizer.

[0027] As a method for curing the dark color composition, a heat initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are generally used. In the present invention, a dark color separation wall after curing is used. Since it is important to have a shape as described later, it is preferable to use a photoinitiating system. The photopolymerization initiator used here generates an active species that initiates polymerization of the polyfunctional monomer described below by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray (also referred to as exposure). It can be selected as appropriate from known photopolymerization initiators or photopolymerization initiator systems.

For example, trino, romethyl group-containing compounds, atalidine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds Compounds, diazo compounds, and the like.

[0028] Specifically, as described in JP-A-2001-117230, trino, trihalomethyloxazole derivatives substituted with romethyl group or _s -triazine derivatives, described in US Pat. No. 4,239,850 A trihalomethyl group-containing compound such as a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound described in US Pat. No. 4,212,976;

[0029] 9-Fe-Lucridine, 9-Pyridylatridine, 9-Pyrazuracridine, 1,2-Bi (9-Ataridyl) ethane, 1,3 Bis (9-Ataridyl) propane, 1,4 Bis (9-Ataridyl) butane, 1,5 Bis (9-Ataridyl) pentane, 1 , 6 bis (9-Atarizyl) hexane, 1,7 bis (9-Atarizyl) heptane, 1,8 bis (9-Atarizyl) octane, 1,9 bis (9-Atarizyl) ) Nonane, 1, 10 Bis (9-Ataridyl) decane, 1, 11-Bis (9-Ataridyl) undecane, 1,12 Bis (9-Ataridyl) dodecane, etc. —Ataridyl) alkanes, such as alkanes;

[0030] 6- (p-methoxyphenyl) 2, 4 bis (trichloromethyl) s triazine, 6- [p-

(N, N bis (ethoxycarbomethyl) amino) phenol] 1,4 bis (trichloromethyl) -s triazine compounds such as triazine; other, 9, 10 dimethylbenzphenazine, Michler's ketone, benzophenone Z Michler's ketone, hexanolino imidazole / mercaptobenzimidazole, benzyldimethyl ketal, thixanthone / amine, 2, 2'-bis (2,4 dichlorophenol) 1, 4, 4 ', 5, 5'-tetraphenol -Lu 1, 2 'biimidazole.

[0031] Among the above, at least one selected from trino, romethyl group-containing compounds, atalidine compounds, acetophenone compounds, biimidazole compounds, and triazine compounds is 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 useful because they are versatile and inexpensive.

Particularly preferred as a compound containing a trihalomethyl group is 2-trichloromethyl-1- (P-styrylstyryl) 1,3,4-oxadiazole, and as an atalidine compound, 9 —Phenolacridine, 6- [p— (N, N-bis (ethoxycarbomethyl) amino) phenol] — 2, 4 bis (trichloromethyl) —s triazine, 2— (p— Butoxystyryl) 1 5 Trichloromethyl 1 3, 3, 4-oxadiazole-containing compounds such as trihalomethyl groups, and Michler's ketone, 2, 2'-bis (2, 4 diclonal mouth) -4, 4 ', 5, 5'-tetraphenyl 1,2'-biimidazole.

[0032] 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, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition. The total amount is 0.1 quality If the amount is less than%, the photocuring efficiency of the composition may be low and exposure may take a long time.

If the amount exceeds 20% by mass, the developed image pattern may be lost during development, or the pattern surface may be easily roughened.

[0033] 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.

[0034] The mercabtan compound has a benzene ring or a heterocyclic ring as a mother nucleus, and has one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus. (Hereinafter, referred to as “merkabutane-based hydrogen donor”). The amine compound is 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 “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

[0035] Specific examples of the mercaptan-based hydrogen donor include 2 mercaptobenzozoazole, 2 mercaptobenzoxazole, 2 mercaptobenzozoimidazole, 2,5 dimercapto 1,3,4-thiadiazole, 2 mercapto 2 , 5 dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable! /.

[0036] Specific examples of the amine-based hydrogen donor include 4, 4 'bis (dimethylamino) benzophenone, 4, 4'-bis (jetylamino) benzophenone, 4-jetylaminoacetophenone, 4- Examples include dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzozotolyl and the like. Of these, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (jetylamino) benzophenone are preferable, and 4,4′-bis (jetylamino) benzophenone is particularly preferable.

[0037] The hydrogen donor can be used alone or in admixture of two or more, and the formed image is difficult to drop off from the permanent support during development, and the strength and sensitivity are improved. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.

[0038] Specific examples of the combination of the mercabbutane-based hydrogen donor and the amine-based hydrogen donor include 2 mercaptobenzothiazole Z4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole Z4,4'-bis (Jetylamino) benzophenone, 2 mercaptobenzoxazole Z4,4'-bis (dimethylamino) benzophenone, 2mercaptobenzoxazole Z4,4'-bis (jetylamino) benzophenone, and the like. A more preferred combination is 2 mercaptobenzothiazole / 4,4'-bis (jetylamino) benzophenone, 2mercaptobenzoxazole Z4,4'-bis (jetylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzozothiazole / 4, 4 'Bis (jetylamino) benzophenone.

[0039] When the mercabtan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercabtan hydrogen donor (M) to the amine hydrogen donor (A) 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, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition.

[0040] As the polyfunctional monomer of the dark color composition, the following compounds may be used singly or in combination of two or more with other monomers as required. Specifically, tert-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylol property ( (Meth) Atarylate, 2-Ethyl-2-butyl-propanediol Di (meth) acrylate, Pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, Dipentaerythritol Hexa (meth) attaly , Dipentaerythritol penta (meth) acrylate, polyoxyethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) attayllooxychetyl) isocyanurate, 1, 4 diisopropyl benzene, 1,4-dihydroxybenzene di (me ) Atari rate, decamethylene glycol di (meth) Atari rate, styrene, di § Lil fumarate, triallyl trimellitate, lauryl (meth) Atari rate, and (meth) acrylamide, xylylenebis (meth) acrylamide, etc. [0041] Further, a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and hexamethylene diisocyanate, Reactants with diisocyanates such as toluene diisocyanate and xylene diisocyanate can also be used.

Of these, particularly preferred are pentaerythritol tetraatalylate, dipentaerythritol hexaatalylate, dipentaerythritol pentaatalylate, and tris (2-acryloyloxychetyl) isocyanurate.

[0042] The content of the polyfunctional monomer in the dark color composition is the total solid content of the dark color composition.

5 to 80% by mass is preferable with respect to (mass), and 10 to 70% by mass is particularly preferable. When the content is less than 5% by mass, the resistance to the alkaline developer in the exposed portion of the composition may be inferior, and when it exceeds 80% by mass, the tackiness of a dark color composition is obtained. May increase and handleability may be poor.

[0043] (Binder)

The dark color composition may contain a binder as necessary. As the noinder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and As described in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial ester oxalic maleic acid copolymer And the like.

[0044] In addition, cellulose derivatives having a carboxylic acid group in the side chain may also be mentioned. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.

Particularly preferred examples include copolymers of benzyl (meth) atalylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylate, and other Mention may be made of multicomponent copolymers with monomers. These binders having a polar group may be used singly or may be used in the state of a composition used in combination with an ordinary film-forming polymer! The content of the non-colored dark color composition is preferably 20 to 50% by mass and more preferably 24 to 45% by mass with respect to the total solid content (mass) of the layer or composition.

[0045] (Solvent)

The dark color composition may contain a solvent as necessary. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethino ethenore acetate, cyclohexanone, cyclohexanol, methylol isobutyl ketone, ethyl lactate, methyl lactate, strength prolatatum. Etc.

[0046] (Surfactant)

The dark color composition may contain a surfactant as necessary. When the dark color composition is applied onto a substrate or a temporary support of a photosensitive transfer material described later, a uniform film thickness can be controlled by including a surfactant in the dark color composition. Uneven coating can be effectively prevented. Preferred examples of the surfactant include those described in JP-A-2003-337424 and JP-A-11-133600. As the content in the dark composition surface active agent, and with respect to the total solid content (mass) of the composition is from 0.001 to 1 mass ^_0/0 power S- general, 0 . 01 to 0.5 mass ^_0/0 force S preferably, from 0.03 to 0.3% by weight is particularly preferred.

[0047] (UV absorber)

The dark color composition may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include compounds described in JP-A-5-72724, and compounds such as salicylate, benzophenone, benzotriazole, cyanoacrylate, nickel chelate, and hindered amine.

For example, phenyl salicylate, 4 t-butyl phenol salicylate, 2, 4 zeyl t— butyl felt 3 ′, 5′—di-t— 4′-hydroxybenzoate, 4—t-butyl phenol salicylate, 2 , 4-Dihydroxybenzophenone, 2 Hydroxy-4-methoxybenzophenone, 2 Hydroxy 4-n-Otoxybenzophenone, 2- (2'-Hydroxy 1-5 'methylphenyl) benzotriazole, 2- (2' Hydroxy 3 '—T-Butyl-5'-methylphenol) 5 Chronobenzobenzolazole, Ethyl 2 Cyan 3, 3 Di-di-aryl ester, 2, 2' Hydroxy-4-methoxybenzophenone, Nickel dibutyl di Thiocarbamate, bis (2, 2, 6, 6-tetramethyl-4-pyridine) sebacate, 4-t butylphenol salicylate, phenyl salicylate, 4-hydroxy 2, 2, 6, 6-tetramethylpiperidine condensate Acid bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -ester, 2- [2hydroxy-3,5bis (α, a-dimethylbenzyl) phenol] -2H-benzotriazole, 7- {[4 Black mouth 6 (Jetylamino) 5 Triazine 2-yl] amino} 3 phenol coumarin and the like.

In the case of using an ultraviolet absorber, the content of the ultraviolet absorber with respect to the total solid content of the dark color composition is generally 0.5 to 15% by mass, and preferably 1 to 12% by mass. ˜10 mass% is particularly preferred.

[0048] (Thermal polymerization inhibitor)

The dark composition preferably contains a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-tert-butyl-ρ-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butyl Phenol), 2,2′-methylenebis (4-methyl 6t-butylphenol), 2 mercaptobenzimidazole, phenothiazine and the like.

In the case of using a thermal polymerization inhibitor, the content relative to the total solids in the dark composition 0. A 01-1 mass ^_0/0 power S- general, from 0.02 to 0.7 mass ^_0/0 Force S is preferable, and 0.05 to 0.5% by mass is particularly preferable.

[0049] Further, in addition to the above components, the dark color composition may contain "adhesion aid" described in JP-A-11 133600, other additives, and the like.

[0050] (Dark color separation wall)

The dark color separation wall according to the present invention is formed from the dark color composition. A dark color separation wall separates two or more pixel groups and is generally black, but is not limited to black. The step of forming the dark color separation wall includes at least the following steps (1) to (3).

(1) Process of pattern exposure of dark color composition layer in an oxygen-poor atmosphere (pattern exposure process) (2) Process of developing after pattern exposure to form dark color separation wall pattern (Development process)

Hereinafter, each step will be described.

[0051] (1) Pattern exposure process

In this pattern exposure step, the above-described layer having the dark color composition power is subjected to pattern exposure in an oxygen-poor atmosphere to photocur the dark color composition. Pattern exposure refers to irradiating the dark color composition layer with patterned light through a mask on which an image pattern is formed. In some cases, light irradiation may be performed without using a mask.

Examples of the light source used for the light irradiation include known light sources such as medium to ultra high pressure mercury lamps, xenon lamps, and metal halide lamps. The mask can be appropriately selected from known masks.

Next, the poor oxygen atmosphere at the time of exposure will be described below.

[0052] An oxygen-poor atmosphere in photocuring a strong dark composition means an inert gas, a reduced pressure, and a protective layer capable of blocking oxygen, and these are described in detail below. It is as follows.

[0053] ~ Under inert gas ~

An inert gas is a general gas such as N, H, or CO, or a rare gas such as He, Ne, or Ar.

2 2 2

Say kind. Among these, N is preferably used because of safety, availability, and cost.

2

It is.

[0054] ~ Under reduced pressure ~

Under reduced pressure refers to a state of 500 hPa or less, preferably lOOhPa or less.

[0055] ~ Under a protective layer capable of blocking oxygen ~

The term “under the protective layer capable of blocking oxygen” refers to a state in which the protective layer is formed on the layer made of the dark color composition. Examples of the protective layer capable of blocking oxygen include, for example, polybute ether Z maleic anhydride polymer, ruboxyalkyl cellulose described in JP-A-46-2121 and JP-B-56-40824. Water-soluble salts, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polybulal alcohol, polybulurpyrrolidone, various Reacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and their similar water-soluble salts, styrene-maleic acid copolymers, Maleate rosin, and combinations of two or more of these. Of these, a combination of polybutyl alcohol and polyvinyl pyrrolidone is particularly preferred. Polyuryl alcohol having a hatching rate of 80% or more is preferred. The content of polyvinylpyrrolidone is preferably 1 to 75% by weight, more preferably 1 to 50% by weight, of the alkali-soluble rosin layer solids. It is 10 mass%, More preferably, it is 10-40 mass%.

[0056] As the protective layer capable of blocking oxygen, various films can be used. For example, polyesters such as PET, polyamides such as nylon, ethylene acetate butyl copolymer (EVAs) ) Can also be suitably used. These films may be stretched as necessary, and the thickness is suitably 5 to 300 m, preferably 20 to 150 μm. In the case of producing a dark color separation wall using a photosensitive transfer material, an intermediate layer or a temporary support described later can be suitably used as a protective layer capable of blocking oxygen.

[0057] The oxygen permeability coefficient of the protective layer capable of blocking oxygen produced in this way is preferably 2000 cm ³ Z (m ² · dayatm) or less! /, But is lOOcmV (m ² · dayatm) or less. More preferably, it is most preferably 50 cm ³ Z (m ² · day · atm) or less.

Since the oxygen permeability _{^{^{2000 C m 3 / (m 2}}} 'day' a tm) if more than can not you to block the efficient oxygen, is difficult to hyperchromic Hanarega wall shape below May be.

[0058] (2) Development process

In the main development step, the dark composition layer that has been subjected to pattern exposure in the (1) pattern exposure step is developed using a predetermined developer.

As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but a solution obtained by adding a small amount of water and a miscible organic solvent may be used.

Prior to the development, it is preferable to spray the pure water with a shower nozzle or the like to uniformly wet the surface of the dark color composition layer. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water. [0059] Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal heavy metals. Carbonates (for example, sodium hydrogen carbonate, potassium hydrogen carbonate), alkali metal silicates (for example, sodium silicate, potassium silicate), alkali metal metasilicates (for example, sodium metasilicate, potassium metasilicate), Examples include triethanolamine, dietanolamine, monoethanolamine, morpholine, tetraalkylammonum hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass.

[0060] Examples of the "water-miscible organic solvent" include, for example, methanol, ethanol, 2-prononole, 1-propanol, butanol, diacetoneanolone, ethyleneglycolone monomethinoatenore, Ethylene glycol-monoethylenoatenole, ethylene glycol-monolemonyl butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε — force prolataton, γ-butyrolataton, dimethylformamide, dimethylacetamide, hexamethylphospho Preferable examples include luamide, ethyl acetate, methyl lactate, ε-strength prolatatam, and メチル -methylpyrrolidone. The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

[0061] The developer may be used as a bath solution or a spray solution. When removing the uncured portion of the dark color composition layer, a method such as rubbing with a rotating brush or a wet sponge in the developer can be combined. The temperature of the developer is usually preferably around room temperature (22 ° C) to 40 ° C. The development time depends on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added, but is usually about 10 to 120 seconds. If the development time is too short, the development of the non-exposed area may be insufficient, and the UV absorbance may be insufficient. If the development time is too long, the exposed area may be etched. In either case, it is difficult to make the dark color separation wall shape suitable. It is also possible to add a washing step after the development process. In this development process, the shape of the dark color separation wall is formed as described above.

Development methods include paddle development, shower development, shower & spin development, dip A method such as development can be used.

[0062] The pH of the developer is preferably 8 to 13. A roller conveyor or the like is installed in the developing tank, and the substrate moves horizontally. In order to prevent scratches on the roller conveyor, the photosensitive resin is preferably formed on the upper surface of the substrate. When 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 peripheral portion becomes a problem. In order to avoid this, it is desirable to incline the substrate diagonally. The inclination angle is preferably 5 to 30 °.

[0063] After development, a more uniform development result can be obtained by lightly blowing air on the substrate to remove excess liquid substantially and then performing shower water washing. Also, before washing with water, ultrapure water is ejected with an ultra-high pressure washing nozzle at a pressure of 3 to: LOMPa to remove the residue, thereby obtaining a high-quality image without residue. If the substrate is transported to a subsequent process with water droplets on the substrate, the process will be soiled or stains may remain on the substrate. Therefore, it is preferable to drain the water with an air knife to remove excess water and water droplets.

[0064] In the present invention, as described above, it is preferable to make development as strong as possible in order to change the cross-sectional shape of the dark color separation wall after development from vertical to inverted taper. The development conditions for the “strong development” include a dilute aqueous solution having a concentration of alkaline substance of 0.01 to 30% by mass as the developer, a development temperature of 22 to 40 ° C., and a development time. It is preferred that the condition is 10 to 120 seconds.

The concentration of the alkaline substance, more preferably, 0.5 a 02-25 wt%, more preferably from 0.05 to 20 weight ^_0/0. The development temperature is more preferably 24 to 38 ° C, and further preferably 26 to 35 ° C. The development time is more preferably 15 to L 10 seconds, and still more preferably 20 to L 00 seconds.

In order to achieve the desired `` strong development '', the development intensity varies by changing any one of these types of alkaline substances, their concentration, development temperature, and development time. It is preferable to appropriately set each condition within the above range.

[0065] (3) Post-exposure process

The dark color separation image wall according to the present invention is formed by performing post exposure after development. Post exposure controls the cross-sectional shape of the image, controls the hardness of the image, It is possible to adjust the surface roughness of the image and control the film thickness reduction of the image.

[0066] The light source used for the post-exposure may be any light source that includes at least one of wavelengths at which the dark color composition has sensitivity. The ultra-high pressure mercury lamp described in paragraph No. 0074 of JP-A-2005-3861 , High pressure mercury lamp, metalno, ride lamp and the like.

Post exposure is preferably performed by directly irradiating the substrate with light from a light source such as an ultra-high pressure mercury lamp or a metal halide without using an exposure mask or the like from the viewpoint of simplification of equipment and power saving.

[0067] Post-exposure is performed on both sides as necessary. The exposure amount, the upper surface: 2500MiZcm ² than on the lower surface: at 2,500 mJ / cm ² or more ranges, depending on the control object, appropriately adjusted. The preferred higher exposure dose, or summer long exposure time too high, since the substrate the substrate temperature becomes too high it may be deformed or post exposure light per one surface, the LOOOOmjZcm ² degree The upper limit is preferable. On the other hand, if the post exposure amount per side is less than 2500 mjZcm ² , the edge of the dark color separation wall is deformed and the ink easily gets over the edge force, and the object of the present invention of preventing color mixing cannot be achieved.

More preferably be exposed on both sides or upper surface with an exposure amount of it is preferably fixture 280 0~5000miZcm ² for exposing a double-sided or top with an exposure amount of 2500~10000mjZcm ^2, exposed on both sides with an exposure amount of 2800~ 5000miZcm ² Most preferably.

[0068] (Photosensitive transfer material)

As a method for realizing the above-mentioned dark color separation wall shape easily and at low cost, there is a method of using a photosensitive transfer material having at least a layer having a dark color composition strength on a temporary support. Further, an intermediate layer capable of blocking oxygen (hereinafter, also simply referred to as “oxygen blocking layer”) may be provided between the temporary support and the layer having the dark color composition force. When such a material is used, since the layer having the dark color composition power is protected by the oxygen blocking layer, it automatically becomes an oxygen-poor atmosphere. For this reason, there is no need to perform the exposure process under inert gas or under reduced pressure, so there is an IJ point where the current process can be used as it is.

Further, a photosensitive transfer material having a layer having at least a dark color composition strength on a temporary support may be used, and the temporary support may be used as “a protective layer capable of blocking oxygen”. In this case, It is possible to reduce the number of processes that do not require the provision of an oxygen blocking layer.

[0069] The photosensitive transfer material described above may have a thermoplastic resin layer as necessary. The strong thermoplastic resin layer is alkali-soluble and contains at least a resin component, and the resin component has a substantial soft point of 80 ° C or less. It is preferable. By providing such a thermoplastic resin layer, good adhesion to a permanent support can be exhibited in the method for forming a dark color separation image wall described later.

[0070] Thermoplastic resins having a soft melting point of 80 ° C or lower include saponified products of ethylene and acrylate copolymer, saponified products of styrene and (meth) acrylate copolymer, and vinyl toluene. (Meth) acrylic acid ester copolymer canes, poly (meth) acrylic acid esters, (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and butyl acetate, etc. Is mentioned.

[0071] In the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, "Plastic Performance Handbook" (Japan Plastic Industry Federation, All Japan Plastic Molding Industry Association) Edited by the Industrial Research Council, published on October 25, 1968), it is possible to use organic polymers that have a soft spot of about 80 ° C or less and are soluble in an alkaline aqueous solution. it can.

[0072] In addition, for 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. In addition, 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. Agents, surfactants, release agents, etc. can also be added.

[0073] Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate. it can.

[0074] As the temporary support in the photosensitive transfer material described above, a force that is chemically and thermally stable and is composed of a flexible substance can be appropriately selected. Specifically, A thin sheet of Freon (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 μm, preferably 20 to 150 μm. If the thickness is less than 5 m, the temporary support tends to be broken when it is peeled off. Also, when exposure is performed through the temporary support, the resolution tends to decrease if the exposure exceeds 300 m.

Among the above specific examples, a biaxially stretched polyethylene terephthalate film is particularly preferable.

[0075] (Intermediate layer (oxygen barrier layer))

As the oxygen blocking layer, it is preferable to use an oxygen blocking film having an oxygen blocking function, which is described as “separation layer” in JP-A-5-72724. In this case, the sensitivity during exposure is increased. In addition, the time load on the exposure machine is reduced and the productivity is improved.

As the oxygen barrier layer, a known medium force that exhibits low oxygen permeability and is preferably dispersed or dissolved in water or an aqueous alkali solution can be appropriately selected. Of these, a combination of polybulal alcohol and polybulurpyrrolidone is particularly preferred.

[0076] (Protective film)

A thin protective film is preferably provided on the resin layer to protect it from contamination and damage during storage. The protective film may have the same or similar material strength as the temporary support, but it must be easily separated from the resin layer. As the protective film material, for example, a sheet of silicone paper, polyolefin or polytetrafluoroethylene is suitable.

[0077] (Substrate)

As the substrate (permanent support) constituting the color filter, a metallic support, a metal-bonded support, glass, ceramic, a synthetic resin film, or the like can be used. Particularly preferred is a glass or a synthetic resin film having transparency and good dimensional stability.

[0078] (Formation of dark separation wall)

Hereinafter, an example of forming a dark color separation image wall using a photosensitive transfer material will be described. On the temporary support, an intermediate layer (oxygen barrier layer), a dark color composition layer, and a cover sheet on the dark color composition layer. A photosensitive transfer material provided with a sheet is prepared. First, after peeling off and removing the cover sheet, the surface of the exposed dark color composition layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate). As the 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.

[0079] Next, peeling is performed between the temporary support and the oxygen barrier layer, and the temporary support is removed. Subsequently, in a state where a desired photomask (for example, a quartz exposure mask) is vertically set above the removal surface after the temporary support is removed, the distance between the exposure mask surface and the oxygen blocking layer is appropriately set (for example, , 200 μm) for exposure. Next, after irradiation, development processing is performed using a predetermined processing solution to obtain a not-tung image. Then, if necessary, wash with water to obtain a dark color separation wall.

[0080] When the temporary support is used as an intermediate layer capable of blocking oxygen, a desired photomask (for example, a quartz exposure mask) is provided above the temporary support while leaving the temporary support (without peeling). ) In an upright position, the distance between the exposure mask surface and the temporary support is appropriately set (for example, 200 μm) and exposed. Next, the temporary support is removed, and development processing is performed using a predetermined processing solution to obtain a patterning image. Then, if necessary, wash with water to obtain a dark color separation wall.

[0081] The exposure can be performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi, Ltd., Techtech Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, and the exposure amount is appropriately set (for example, 300 mjZcm ² ) Can be selected.

[0082] (Development processing)

After the light irradiation, development processing is performed using a predetermined processing solution. The details of the development process are the same as described above.

[0083] (Post exposure)

Post exposure is performed after development. The contents of the post-exposure are the same as described above.

[0084] (Heat treatment)

Furthermore, heat treatment may be performed after post exposure. By performing the heat treatment, the monomer and the cross-linking agent contained in the dark color composition layer of the present invention can be reacted to ensure the hardness of the image. The heat treatment temperature is preferably in the range of 150 to 250 ° C. If it exceeds 150 ° C, the hardness will be insufficient, and if it is less than 250 ° C, the resin will be colored and the color purity will deteriorate. The heat treatment time is preferably 10 to 150 minutes. If it is less than 10 minutes, the hardness is insufficient, and if it exceeds 150 minutes, the shape of the dark color separation wall becomes worse. Further, after forming the colors of all the colored pixels by the method described later, a final heat treatment may be performed to stabilize the hardness. In that case, it is preferable in terms of hardness to carry out at a higher temperature (for example, 240 ° C).

[0085] (Water repellent treatment)

In the present invention, it is preferable that a water-repellent treatment is performed on the dark color separation wall so that at least a part of the dark color separation wall is water-repellent. This is because, when a droplet of a colored liquid composition is subsequently applied between the dark color separation walls by a method such as inkjet, the ink crosses the dark color separation wall and mixes with the adjacent color. This is to eliminate the inconvenience.

Examples of the water repellent treatment include a method of applying a water repellent material on the upper surface of the dark color separation wall, a method of newly providing a water repellent layer, a method of imparting water repellency by plasma treatment, For example, a method of kneading into a painting wall.

[0086] A detailed description of the water repellent treatment will be described below.

(1) <Method of kneading a water-repellent substance into a dark color separation wall>

As a means for preventing “color mixing”, a dark color separation wall is formed using a photoresist obtained from the dark color composition of the present invention containing the fluorine-containing resin (A) described in JP-A-2005-36160. There is a way to make it.

The fluorine-containing resin (A) is a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a), and a monomer unit having an ethylenic double bond and an acidic group (b). It is preferable that the acid value is 1 to 300 mgKOHZg. The Rf group (a) and acidic group (b) have the same definitions as those described in JP-A-2005-36160.

Examples of the ethylenic double bond include a (meth) ataryloyl group, a vinyl group, and a allyl group. Monomers having an ethylenic double bond and an Rf group (a) include CH = CR ¹ COOQ ² Rf

2

, CH = CR ¹ OCOQ ¹ Rf, CH = CR ¹ OQ ¹ Rf, CH = CR ¹ CH OG ^ Rf ゝ CH = 0 ^ 0

2 2 2 2 2

OOQ'NR'SO Rf, CH = CR'COOQ'NR'CORf, CH = CR'COOQ'NR'COO

2 2 2

Q ² Rf, CH Niji! ^ Ji. . . ² . . ¹ ! ^ Etc. Where R ¹ is a hydrogen atom or

2

Q ¹ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and Q ² represents a divalent organic group having 1 to 6 carbon atoms. QQ ² may have a cyclic structure.

[0087] Specific examples of QQ ² include CH—, 1 CH CH—, 1 CH (CH 2) —, 1 CH CH

2 2 2 3 2 2

CH-, One C (CH)-, One CH (CH CH)-, One CH CH CH CH-, One CH (CH

2 3 2 2 3 2 2 2 2 2

CH CH) 1, CH (CH) CH 1, CH (CH CH (CH)) 1, CH CH (OH)

2 3 2 2 3 2 2 3 2 2

CH-, -CH CH NHCOOCH-,-CH CH (OH) CH OCH-, etc.

2 2 2 2 2 2 2

The Q ¹ may be a single bond. Above all, from the viewpoint of ease of synthesis, -CH-,-C

2

H 2 CH—, 1 CH 2 CH (OH) CH 1 is preferred.

2 2 2 2

[0088] Specific examples of the monomer having an ethylenic double bond and an Rf group (a) include the following.

CH = CHCOOCH CF O (CF CF O) CF (n is 3 to 9), CH = CHCOOCH

2 2 2 2 2 η- 1 3 2 2

CF (CF) O (CF CF (CF) O) CF (n is 2 to 6), CH = CHCOOCH CF (CF)

3 2 3 n-1 6 13 2 2 3

0 (CF CF (CF) O) CF (n is 2 to 6).

2 3 n-1 3 7

CH = C (CH) COOCH CH NHCOOCH CF O (CF CF O) CF (n is 3 to 9

2 3 2 2 2 2 2 2 n-1 3

), CH = C (CH) COOCH CH NHCOOCH CF (CF) O (CF CF (CF) O) C

2 3 2 2 2 3 2 3 n-1 3

F (n is 2 to 6), CH = C (CH) COOCH CH NHCOOCH CF (CF) O (CF CF (

7 2 3 2 2 2 3 2

CF) 0) CF (n is 2-6).

3 n-1 6 13

CH = C (CH) COOCH CH (OH) CH OCH CF O (CF CF O) CF (n is 3

2 3 2 2 2 2 2 2 n-1 3

~ 9), CH = C (CH) COOCH CH (OH) CH OCH CF (CF) O (CF CF (CF) O

2 3 2 2 2 3 2 3

) CF (n is 2-6), CH = C (CH) COOCH CH (OH) CH OCH CF (CF) 0 (n-1 6 13 2 3 2 2 2 3

CF CF (CF) O) CF (n is 2 to 6).

2 3 n-1 3 7

[0089] The content of the monomer unit based on the monomer having an ethylenic double bond and the Rf group (a) in the fluorinated resin (A) is preferably 1 to 95%. 5 to 80% is more preferable. 20 to 60% is more preferable. When the content of the monomer unit is within this range, the fluorine-containing resin (A) Good ink repellency is exhibited, and the developability of the photosensitive composition of the present invention is improved.

[0090] Examples of the monomer having an acidic group (b) include a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, a sulfonic acid group, and a monomer having a hydroxyl group. .

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, bulacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These may be used alone or in combination of two or more.

[0091] Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, 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.

[0092] Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth). Acrylic acid—2-Sulfoethyl, (Meth) acrylic acid—2-Sulfopropyl, 2-Hydroxy—3-— (Meth) Atalyloxypropane sulfonic acid, 2 -— (Meth) acrylamide—2-methylpropane sulfonic acid, or Those salts are mentioned. These may be used alone or in combination of two or more.

[0093] Monomers 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-hydroxy hexyl (meth) acrylate, 4-hydroxy cyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl vinylateolene, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl Aryl ether, N-hydroxymethyl (Meth) acrylic Amides, N, N-bis (hydroxymethyl) and the like can be mentioned.

[0094] Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH = CHOCH C H CH O (C H O) H (

2 2 6 10 2 2 4 g where g is 1 to: an integer of LOO, and so on. ), CH = CHOC H 0 (C H O) H, CH =

2 4 8 2 4 g 2

CHCOOC H 0 (C H O) H, CH = C (CH) COOC H 0 (C H O) H, CH = C

2 4 2 4 g 2 3 2 4 2 4 g 2

HCOOC H 0 (C H O) (C H O) H (where h is 0 or 1 to: an integer of LOO, k is

2 4 2 4 h 3 6 k

1 ~: LOO integer, h + k is 1 ~: L00. same as below. ), CH = C (CH) COOC

twenty three

H O (C H O) (C H O) H and the like can be mentioned. These may be used alone or in combination of two or more.

2 4 2 4 h 3 6 k

The above may be used together.

[0095] The content of the monomer unit based on the monomer having an acidic group (b) in the fluorinated resin (A) is preferably 0.1 to 40%, and more preferably 0.5 to 30%. 1-20% more preferred V, more preferred. Within such a range, the fluorine-containing resin (A) exhibits good ink repellency and the developability of the photosensitive composition is good.

[0096] The fluorine-containing resin (A) has a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a), an ethylenic double bond, and an acidic group (b). And a monomer having no Rf group (a) and no acidic group (b) (hereinafter referred to as “other monomers”). May have a monomer unit based on.

Other monomers include hydrocarbon-based olefins, butyl ethers, isopropyl ethers, allylic ethers, butyl esters, allylic esters, (meth) acrylic acid esters, (meth) acrylamides, aromatic Group bur compounds, chlororefhins, fluorefhins, conjugates and the like. These compounds may contain functional groups such as a hydroxyl group, a carbonyl group, an alkoxy group, and an amide group. Moreover, you may have group which has a polysiloxane structure. However, monomer units based on these other monomers should not have Rf group (a) and acidic group (b). These may be used alone or in combination of two or more. In particular, (meth) acrylic acid esters and (meth) acrylamides are preferred because the heat resistance of the coating film formed from the photosensitive resin composition of the present invention is excellent.

[0097] In the fluorinated resin (A), the proportion of monomer units based on other monomers is 80%. 70% or less is more preferable. Within such a range, the developing property of the photosensitive composition of the present invention will be good.

The fluorine-containing resin (A) in the present invention comprises a monomer unit based on the monomer having the ethylenic double bond and the Rf group (a), an ethylenic double bond and an acidic group (b And a monomer having an Rf group (a) in a polymer having a reactive site and a Z or acidic group ( It can also be obtained by various modification methods in which a compound having b) is reacted.

[0098] As various modification methods for reacting a polymer having a reactive site with a compound having an Rf group (a), for example, a monomer having an epoxy group is preferentially copolymerized, and an Rf group is later formed. (a) a method of reacting a compound having a carboxyl group, a method of co-polymerizing monomers having an epoxy group and then reacting a compound having an Rf group (a) and a hydroxyl group, etc. Can be mentioned.

Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3, 4 epoxy cyclohexyl methyl acrylate.

[0099] Examples of the compound having an Rf group (a) and a carboxyl group include compounds represented by the following formula 3.

HOOC-C F O— (C F −0) C F… Formula 3

p-1 2 (p-l) p 2p n-1 q 2q + l

In Formula 3, p is an integer of 2 or 3, q is an integer of 1 to 20, and n is an integer of 2 to 50.

[0100] Examples of the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following formula 4.

HOCH -C F O— (C F -0) C F… Formula 4

2 p-1 2 (p-l) p 2p n-1 q 2q + l

In Formula 4, p is an integer of 2 or 3, q is an integer of 1 to 20, and n is an integer of 2 to 50.

[0101] As various modification methods for reacting a polymer having a reactive site with a compound having an acidic group (b), for example, a monomer having a hydroxyl group is preliminarily copolymerized and then an acid anhydride is reacted. The method of letting it be mentioned. In addition, there may be mentioned a method in which an acid anhydride having an ethylenic double bond is copolymerized in advance and a compound having a hydroxyl group is reacted later.

[0102] Specific examples of the monomer having a hydroxyl group include bulufenol, 2 hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 3 hydroxypropyl (meth) ) Atarylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl Glycol mono (meth) acrylate, 3-chloro 2-hydroxy vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethylaryl ether, N-hydroxymethyl (meth) acrylamide, N , N-bis (hydroxymethyl) and the like.

[0103] Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH = CHOCH C H CH O (C H O) H (

2 4 8 2 4 g 2

CHCOOC H 0 (C H O) H, CH = C (CH) COOC H 0 (C H O) H, CH = C

2 4 2 4 g 2 3 2 4 2 4 g 2

HCOOC H 0 (C H O) (C H O) H (where h is 0 or 1 to: an integer of LOO, k is

2 4 2 4 h 3 6 k

1 ~: LOO integer, h + k is 1 ~: L00. same as below. ), CH = C (CH) COOC

twenty three

2 4 2 4 h 3 6 k

The above may be used together.

[0104] Specific examples of the acid anhydride include phthalic anhydride, 3-methylphthalic anhydride, trimellitic anhydride, and the like.

Examples of acid anhydrides having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, cis —L, 2, 3, 6-tetrahydrophthalic acid, 2-butene-1-yl succinic anhydride, and the like.

[0105] The compound having a hydroxyl group may be any compound having one or more hydroxyl groups. Specific examples of the above-mentioned monomer having a hydroxyl group, ethanol, 1-propanol, 2-propanol , Alcohols such as 1-butanol and ethylene glycol, cellsolves such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol And carbitols such as 2- (2-butoxyethoxy) ethanol. A compound having one hydroxyl group in the molecule is preferred. These may be used alone or in combination of two or more. Use it.

[0106] The fluorine-containing resin (A) is a polymer having the reaction site that is a precursor of the fluorine-containing resin (A). It can be synthesized by a method in which it is dissolved in and heated, and a polymerization initiator is added to react.

The acid value of the fluorinated resin (A) is preferably 1 to 300 mgKOHZg, more preferably 5 to 200 mgKOHZg, and particularly preferably 10 to 150 mgKOHZg. Within this range, the developability of the photosensitive composition of the present invention will be good. The acid value is the mass (unit: mg) of potassium hydroxide required to neutralize sorghum lg. In this specification, the unit is described as mgKOH Zg.

[0107] The number average molecular weight of the fluorinated resin (A) is preferably 500 or more and less than 20000, more preferably 2000 or more and less than 15000. Within this range, the developability of the photosensitive composition of the present invention is good. The number average molecular weight is measured by a gel permeation chromatography method using polystyrene as a standard substance.

The blending amount of the fluorinated resin (A) is preferably 0.01 to 50%, more preferably 0.1 to 30%, and more preferably 0.2 to 10% based on the solid content in the photosensitive composition. Particularly preferred. Within this range, the photosensitive composition exhibits good ink repellency and ink tumbling properties and good developability.

[0108] (2) <Method of providing a water repellent layer>

As a means for preventing “color mixing”, there is a method of producing a partition wall having ink repelling properties at a position matching the dark color separation wall on the substrate on which the dark color separation wall is formed.

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, and is not limited to this, but the number of molecular weights having the following repeating units: It is mainly composed of thousands to hundreds of thousands of linear organic polysiloxanes.

[0109] [Chemical 1]

One o '

[0110] Here, n is an integer of 2 or more, and R is an independent alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a phenyl group. Silicone rubber can be obtained by sparsely bridging such a linear organic polysiloxane. The cross-linking agent is acetoxy silane, ketoxime silane, alkoxy silane, amino silane, amido silane, alkoxy silane, or the like used for so-called room temperature (low temperature) curable silicone rubber. In combination with each other, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamid type, and a deketone type silicone rubber. A small amount of organic tin compound is added to the silicone rubber as a catalyst. In order to bond the photosensitive resin layer and the silicone rubber layer, various adhesive layers may be used between the layers, and aminosilane compounds and organic titanate compounds are particularly preferably used. Instead of providing an adhesive layer between the photosensitive resin layer and the silicone rubber layer, an adhesive component can be added to the silicone rubber layer. As this additional adhesive component, aminosilane compounds and organic titanate compounds can be used.

[0111] The exposure for producing the partition wall is performed from the back side of the substrate using the dark color separation wall as a mask.

After exposure in this manner, the partition wall having a silicone rubber surface layer can be produced by developing with an n_heptane / Z ethanol mixture.

[0112] (3) <Method of imparting water repellency by plasma treatment> As a means for preventing “color mixing”, there is a method of performing water repellency treatment by plasma on a substrate on which a dark color separation wall is formed.

Gases containing at least fluorine atoms introduced in this process include CF, C

Four

HF, C F, SF, C F, C F force Use at least one selected halogen gas

3 2 6 6 3 8 5 8

preferable. In particular, C F (octafluorocyclopentene) has zero ozone depletion potential.

5 8

At the same time, the atmospheric life is longer than conventional gas (CF: 50,000 years, 3200 years).

4 4 8

Very short. Therefore, the global warming potential is 90 (100-year integrated value with CO = 2).

2

Compared to other gases (CF: 6500, C F: 8700), the ozone layer and global environmental protection are very small.

4 4 8

It is extremely effective for protection and is desirable for use in the present invention.

[0113] Further, as the introduced gas, a gas such as oxygen, argon, helium or the like may be used in combination as necessary. In this process, the above CF, CHF, C F, SF, C F, and C F forces are selected.

4 3 2 6 6 3 8 5 8 One or more selected halogen gases, o

By using a gas mixed with 2, it is possible to control the degree of ink repellency on the surface of the dark color separation wall processed in this step. However, if the mixing ratio of O exceeds 30% in the mixed gas, the oxidation reaction by O

twenty two

The response becomes dominant and the effect of improving ink repellency is hindered. Also, O mixing ratio is 30%

2

If it exceeds, the damage to rosin becomes remarkable. For this reason, when using the mixed gas, it is necessary to use it within the range where the mixing ratio of O is 30% or less.

2

As a method for generating plasma, methods such as low frequency discharge, high frequency discharge, and microwave discharge can be used, and conditions such as pressure, gas flow rate, discharge frequency, and processing time during plasma processing should be set arbitrarily. Can do.

[0114] (4) <Method of applying water repellent material to the upper surface of dark color separation wall>

As a means for preventing “color mixing”, there is a method in which a water repellent material is applied to the entire surface of a substrate on which a dark color separation wall is formed.

As a material having water repellency, fluorine resin such as polytetrafluoroethylene, silicone rubber, perfluoroalkyl acrylate, hydrated carbon acrylate, methylsiloxane, etc. There is no particular limitation as long as the contact angle to the agent is 60 ° or more.

The water-repellent material is applied by a method that does not affect the substrate, dark color separation wall, etc. If so, it is possible to select the most suitable method for each material, such as slit coating, spin coating, dip coating, and roll coating.

[0115] After coating, UVO treatment is performed from the back side of the substrate through the dark color separation wall.

Three

The water-repellent film on the outer part is selectively removed or hydrophilized (the contact angle with the colorant after the treatment is made 30 ° or more smaller than before the treatment).

If the water-repellent material can be removed or hydrophilized, the patterning method depends on 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 the optimum method. If it is possible to pattern the water repellent material on the dark color separation wall, the lift-off method or the like is also effective.

[0116] Among the water repellent treatment methods (1) to (4) described above, (3) the water repellent treatment method using a plasma is particularly preferred because of its “simpleness of process” and viewpoint power.

[0117] (Formation of each pixel)

Next, a colored liquid composition (hereinafter also simply referred to as “ink”) for forming each pixel of RGB is caused to enter the voids of the dark color separation wall formed in the developing step. As a method for allowing the colored liquid composition to enter the deep color separation wall voids, a known method such as an ink jet method or a stripe finger coating method can be used, which is preferable from the viewpoint of ink jet method power and cost. The stripe Giesa coating method is a method in which droplets are applied onto a substrate using a gear having a fine droplet discharge hole and a stripe pixel is formed. Details of the inkjet method will be described later.

[0118] Regarding the ink jet method used for forming each pixel, a method of thermally curing ink, a method of photocuring, a method of forming a transparent image-receiving layer on a substrate in advance, and ejecting forcefully, etc. A known method can be used.

[0119] It is preferable to provide a heating step (so-called beta treatment) after forming each pixel. That is, a substrate having a photopolymerized layer by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The temperature and time of heating depend on the composition of the photosensitive dark color composition and the thickness of the layer formed, but generally from about 120 to about 120 from the viewpoint of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. About 10 ~ at 250 ° C It is preferable to heat for about 120 minutes.

[0120] The pattern shape of the color filter formed in this way is not particularly limited, but it is a stripe shape or a lattice shape, which is a general black matrix shape (see Fig. 2B). May be present (see Figure 2A).

[0121] (Inkjet method)

As 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 can be either oily or water-based. The coloring material contained in the ink can be either a dye or a pigment, and the use of a pigment is more preferable from the viewpoint of durability. In addition, a coating-type colored ink (colored resin composition, for example, described in JP-A-2005-3861 [0034] to [0063]) or JP-A-10-195358 is used for producing a known color filter. The inkjet composition described in [0009] to [0026] can also be used.

[0122] In the ink of the present invention, a component that is cured by heating or a line of energy such as ultraviolet rays may be added in consideration of a step after coloring. Various thermosetting resin is widely used as the component that is cured by heating, and examples of the component that is cured by energy rays include those obtained by adding a photoinitiator to an attalylate derivative or a metatalylate derivative. . In particular, when heat resistance is taken into consideration, those having a plurality of attalyloyl groups or metatalylyl groups in the molecule are preferred. These attalylate derivatives or metatalylate derivatives are preferably water-soluble. Even those that are sparingly soluble in water can be used after emulsification.

In this case, an ink containing a colorant such as a dark color body (pigment) listed in the item of the dark color composition> can be used as a preferable one.

As the ink that can be used in the present invention, a thermosetting ink for a color filter containing at least a binder and a bifunctional or trifunctional epoxy group-containing monomer can also be used as a suitable ink.

[0123] The color filter of the present invention is a color filter in which pixels are formed by an inkjet method. It is preferable to spray three colors of RGB to form a three-color filter.

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.

[0124] (Overcoat layer)

After the color filter is manufactured, an overcoat layer may be provided on the entire surface to improve resistance. The overcoat layer protects the solidified layer of inks G and B, and can flatten the surface. However, it is preferable not to provide from the viewpoint of increasing the number of steps.

[0125] Examples of the resin (OC agent) forming the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, from the point of excellent transparency in the visible light region, from the point that the resin of the photocurable composition for color filters usually has acrylic resin as the main component, and excellent adhesion. An acrylic resin composition is desirable. Examples of the overcoat layer include those described in paragraph Nos. 0018 to 0028 of JP-A-2003-287618. Commercially available overcoat agents include “Optoma 1 SS6699GJ” manufactured by JSR. It is done.

[0126] Next, the color filter of the present invention will be described. The color filter of the present invention is a color filter manufactured by the above-described method for manufacturing a color filter of the present invention, and the cross-sectional shape of the dark color separation wall formed on the substrate is the dark color separation image. The height of the substrate strength at the point where the height of the substrate strength of the wall is the highest is h, the line parallel to the substrate at a position of 0.8 h from the substrate is L, L and the dark separation wall touches Tangent line at point parallel to substrate at L, h

1 1 2

When the straight line is L, the value d defined by the distance to the dark color separation wall with the intersection force as L is h.

3 2 3

The value divided by is less than 0.04.

In other words, the cross-sectional shape of the dark color separation wall formed on the substrate is the height from the substrate at the point where the height of the substrate strength of the dark color separation wall is the highest as shown in FIG. The line parallel to the substrate at the position 0.8h from the substrate is L, and the tangent line at the point where L and the dark separation wall touch is L, h

1 1 2 When the line parallel to the substrate at L is L, from the intersection of L to the dark color separation wall The value defined by the distance of d divided by h is 0.04 or less.

[0127] When the dark color composition described above is photopolymerized in a poor oxygen atmosphere as described above on the substrate, the surface force of the layer having the composition force is absorbed by the composition itself toward the substrate. Since the exposure amount of the light is attenuated, the surface is hardened as a result. In addition, since it is in an oxygen-poor atmosphere, inhibition of polymerization by oxygen on the surface of the layer having compositional power is suppressed, and as a result, the surface is further cured. Due to these two contributions, in the cross-sectional shape of the dark color separation wall formed on the substrate, the height from the substrate at the point where the height of the dark color separation wall from the substrate is the highest is 0 from the substrate. A line parallel to the base plate at 8h

1, L is the tangent at the point where L and the dark separation wall meet

1 2, h position When the line parallel to the board is L, it is defined by the distance from the intersection of L to the dark color separation wall.

3 2 3

Value d divided by h is 0.04 or less. These values are measured by actually observing the dark-colored separation wall formed on the substrate by cutting the substrate vertically and exposing the cross section directly with a microscope. By passing through the process of fixing the shape of the dark color separation wall obtained in this way, the ink once deposited in the gap gets over the dark color separation wall. As a result, bleeding, protrusion, color mixing with adjacent pixels, white spots, and the like are prevented, and a good color filter can be obtained. The value of dZh is preferably 0.04 or less, more preferably 0.038 or less, and particularly preferably 0.035 or less. FIG. 2 shows an embodiment of a color filter suitable for forming a dark color separation wall having the above-described shape. In these color filters, pixels having no color mixture can be obtained by forming the dark color separation wall in the above-described shape.

An example of the cross-sectional shape of the dark color separation wall of the color filter of the present invention is shown in FIG. 3A. Figure 3A is exaggerated, but it is clear that the ink is less likely to get over the shape with rounded edges as shown in Figure 3B. In FIGS. 3A and 3B, 11 indicates a pixel region, 12 indicates a dark color separation wall, and 13 indicates a substrate.

[0128] [Display device]

The display device of the present invention includes the color filter of the present invention described above, and examples of such display devices include display devices such as liquid crystal display devices, plasma display display devices, EL display devices, and CRT display devices. . For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Industrial Research Co., Ltd. 1990) Line) ”,“ Display devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989) ”and the like.

Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 199)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. A color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field 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 the latest trends in the market (issued by Toray Research Center, Research and Research Division 2001)”.

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

[0130] [Target use]

The color filter of the present invention can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile terminals such as mobile phones, digital cameras, car navigation systems, and the like without any particular limitation.

(Example)

[0131] The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, unless otherwise specified, “%” and “part” represent “% by mass” and “part by mass”, and the molecular weight represents the weight average molecular weight.

[0132] [Preparation of dark color composition]

The dark color composition K1 is prepared by the following procedure. That is, first, K pigment dispersion 1 and propylene glycol monomethyl ether acetate (MMPG AC, manufactured by Daicel Chemical Industries, Ltd. (hereinafter also using the same manufacturer's materials)) in the amounts shown in Table 1 are weighed and the temperature Mix at 24 ° C (± 2 ° C) and stir at 150 RPM for 10 minutes. Next, the amounts of methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4 bis (trichloromethyl) 6- [4 '-(N, N ethoxycarboromethyl) amino in the amounts shown in Table 1 3′—Bromophenyl] —s Triazine and Surfactant 1 are removed, and added in this order at a temperature of 25 ° C. (± 2 ° C.) to obtain a temperature of 40 ° C. (± 2 ° C.). Stir at 150 RPM for 30 minutes. The amounts shown in Table 1 are parts by mass, and more specifically, the composition is as follows!

[0133] <K pigment dispersion 1>,

• Carbon black (Negex35, Degussa) 13. 1%

, Dispersant (Compound 1 below) 0.65%

[0134] [Chemical 2]

Compound 1

[0135] 'Polymer (benzyl metatalylate Z methacrylic acid = 72Z28 molar ratio Random copolymer, molecular weight 37,000) 6. 72%

'Propylene glycol monomethyl ether acetate 79. 53%

[0136] <Binder 2>

'Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio

Random copolymer, molecular weight 38,000) 27%

'Propylene glycol monomethyl ether acetate 73%

[0137] <DPHA solution>

Dipentaerythritol hexaatalylate

(Polymerization inhibitor MEHQ 500ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DP HA) 76%

Propylene glycol monomethyl ether acetate 24%

[Surfactant 1]

, The following structure 1 30%

• Methyl ethyl ketone 70%

[0139] [Chemical 3] Structure 1

(n = 6, x = 55 y = 5,

Mw = 33940, Mw / M n = 2.55

(PO: propylene oxide, EO: ethylene oxide)

[0140] [Table 1] Vague color composition K1

K pigment dispersion 1

twenty five

(Car pump rack)

Propylene glycol monomethyl ether acetate 8.0 Methyl ethyl ketone 53 Binder 2 9.1 Hydroquinone monomethyl ether 0.002

DPHA solution 4.2

2, 4 One bis (trichloromethyl) one 6- [4 'one (N, N-diethoxyca

Luponylmethyl) amino-3'-bromophenyl] s-0.16

Triazine

Surface activity percent 1 0.044

(Mass)

[0141] [Example 1]

(Formation of dark color separation wall)

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.

After cooling the substrate and adjusting the temperature to 23 ° C, it was prepared as described above using a glass substrate coater (manufactured by FAS Asia Co., Ltd., trade name: MH-1600) with a slit nozzle. The dark color composition K1 was applied. Subsequently, VCD (vacuum drying equipment, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used to dry part of the solvent for 30 seconds to eliminate the fluidity of the coating layer. m dark color composition layer K1 was obtained.

With a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and dark color The distance between the photosensitive layers K1 was set to 200 m, and pattern exposure was performed at an exposure amount of 300 mjZcm ² in a nitrogen atmosphere.

[0142] Next, pure water was sprayed using a shower nozzle to uniformly wet the surface of the dark color composition layer K1. After that, shower development was performed with a KOH developer (0.04 mass% KOH aqueous solution) at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Continue to super Residue was removed by spraying pure water with an ultra-high pressure washing nozzle at a pressure of 9.8 MPa. After that, post exposure was performed from the top with an exposure dose of 2500 miZcm ^{2 using an} exposure machine with an ultra-high pressure mercury lamp manufactured by Usio Electric Co., Ltd., model number: UVL-8000-N, and an optical density of 3. 9 dark color separation walls were obtained. The exposure amount was adjusted as follows. That is, a light meter (UV-350) manufactured by Oak Manufacturing Co., Ltd. is placed on the substrate, sent to the exposure apparatus, and the exposure dose when the distance between the exposure mask and the measurement apparatus is 10 cm The exposure was adjusted to

[Plasma water repellency treatment]

Plasma water repellency treatment was performed on the substrate on which the dark color separation wall was formed using a force sword coupling type parallel plate type plasma treatment apparatus under the following conditions.

Gas used: CF

Four

Gas flow rate: 80sccm

Pressure: 40Pa

RF power: 50W

Processing time: 30sec

[0144] Preparation of colored ink for one pixel

Of the following components, first, 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 this 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.

• Pigment (C.I. Pigment Red 254) 5 parts

• Polymer dispersant (AVECIA Solsperse 24000) 1 part

'Binder (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

Random copolymer, molecular weight 37,000) 3 parts

• 1st epoxy resin (Novolac type epoxy resin,

Yuka Shell Epicoat 154) 2 parts

• Second epoxy resin (neopentyldaricol diglycidyl ether) 5 parts , Curing agent (trimellitic acid) 4 parts

. Solvent: 3 parts of ethyl ethoxypropionate 80 parts

[0145] In the same manner as in the case of the colored ink composition of the red pixel portion, the same amount of CI pigment green 36 was used instead of CI pigment red 254 in the above thread formation, and the green (G) pixel wear A color ink composition was prepared.

In the same manner as the colored ink composition for red pixels, except that the same amount of CI pigment blue 15: 6 was used instead of CI pigment red 254 in the above composition, a colored ink composition for blue (B) pixels Was prepared.

[0146] Next, using the above-described colored inks for G and B pixels, within the area separated by the dark color separation wall of the color filter substrate obtained above (concave part surrounded by the convex part) In addition, an ink composition was ejected to a desired density using an ink jet recording apparatus, and a color filter having R, G, and B pattern powers was produced. The image-colored color filter was beta-treated in a 230 ° C oven for 30 minutes to completely cure the black matrix and each pixel.

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 by the above method. Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode of the color filter substrate and on the counter substrate, respectively.

[0148] A photospacer was provided in a portion corresponding to the upper part of the dark color separation wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.

After that, an epoxy resin sealant is printed at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and at the same time, a liquid crystal for PVA mode is dropped. After bonding with the counter substrate, the bonded substrate was heat-treated to cure the sealant. A polarizing plate HLC2-2518 made by Sanritz 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 back surface of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

[Example 2]

In the formation of the dark separation wall in Example 1, the post-exposure conditions were changed as shown in Table 2. A color filter and a liquid crystal display device were produced in the same manner as in Example 1 except that.

[0150] [Example 3]

(Production of dark photosensitive transfer material K1)

On a 75 μm-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 having the following formulation P1 was applied and dried. Further, the dark color composition K1 was applied and dried. In this way, a thermoplastic resin layer having a dry film thickness of 14., an intermediate layer having a dry film thickness of 1. and a dark colored composition layer having a dry film thickness of 2 m are formed on the temporary support. Finally, a protective film (12 m thick polypropylene film) was pressure-bonded. Thus, a dark photosensitive transfer material was produced in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the dark composition layer were integrated. The sample name of this dark color photosensitive transfer material is K1.

[0151] <Coating solution for thermoplastic resin layer: Formula HI>

• methanol

• Propylene glycol monomethyl ether acetate 6.36 parts

• Methyl ethyl ketone 52. 4 parts

• Methyl methacrylate / 2--ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55Zll. 7/4. 5/28. 8, molecular weight = 10 Ten thousand, Tg 70. 5. 83 parts

• Styrene Z acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63Z37, average molecular weight = 10,000, Tg 100. 13. 6 parts

• 2, 2-bis [4- (methacryloxypolyethoxy) phenol] propane (manufactured by Shin-Nakamura Engineering Co., Ltd.) 9. 1 part

• Surfactant 1 0.54 parts

[0152] Coating solution for intermediate layer: Formulation Pl>

• PVA205 (Polybulol alcohol, manufactured by Kuraray Co., Ltd.,

(Oxidation degree = 88%, polymerization degree 550) 32.2 parts • Polyvinylolpyrrolidone (Apis' Japan, K-30) 14. 9 parts

'Distilled water 524 parts

• Methanore 429 咅

[0153] The alkali-free glass substrate was washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C for 20 seconds with a shower, and washed with pure water. Then, a silane coupling solution (N-β (aminoethinole) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: ΚΒΜ603, manufactured by Shin-Etsu Chemical Co., Ltd.) was showered 2 Sprayed for 0 seconds and washed with pure water shower. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

The cover film is removed from the dark color light-sensitive transfer material K1 produced by the above production method on the obtained silane coupling treated glass substrate, and the surface of the dark color composition layer exposed after the removal and the silane coupling Laminate (Hitachi Industries Co., Ltd. (Lamic II type)) using a laminator (Hitachi Industries (LamicII type)) and heated at 100 ° C for 2 minutes, rubber roller temperature 130 ° C, Lamination was performed at a linear pressure of 100 NZcm and a conveyance speed of 2.2 mZ. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. After peeling off the temporary support, the exposure mask with the substrate and mask (quartz exposure mask with image pattern) standing vertically with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. The distance between the surface and the dark color photosensitive resin composition layer was set to 200 m, and pattern exposure was performed at an exposure amount of 70 mj / cm ² .

[0154] Next, triethanol amine developing solution (triethanolamine § Min 30 mass ^_0/0 containing, trade name: T - PD2, manufactured by Fuji Photo Film Co., 12 times with pure water (T-PD2 1 The solution obtained by diluting 11 parts by mass of pure water with 11 parts by mass) was developed with shower at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, air was blown onto the upper surface of the substrate to drain the liquid, and then pure water was sprayed for 10 seconds in a shower to clean the pure water, and air was blown to reduce the liquid pool on the substrate.

[0155] Continuing, carbonate Na based developer (sodium bicarbonate 0.38 mol Z l, sodium carbonate 0.47 molar Z l, dibutyl sodium naphthalene sulfonate 5 wt ^_0/0, § Containing a Yuon surfactant, antifoaming agent, stabilizer, product name: TCD1, Fuji Photo Film Co., Ltd. diluted 5 times with pure water) at 29 ° C for 30 seconds, cone type nozzle Shower development was performed at a pressure of 0.15 MPa, and the dark color composition layer was developed to obtain a patterning image.

[0156] Subsequently, a detergent (trade name: T SD3 manufactured by Fuji Photo Film Co., Ltd.) diluted 10-fold with pure water was sprayed in a shower at 33 ° C for 20 seconds with a cone-type nozzle pressure of 0.02 MPa. Further, the image formed by the rotating brush having nylon bristles was rubbed to remove the residue to obtain a dark color separation wall.

Thereafter, the substrate was also subjected to post-exposure with an exposure force of 3000 mjZcm ² using an exposure machine having an ultrahigh pressure mercury lamp manufactured by Usio Electric Co., Ltd., model number: UVL-8000-N. Thereafter, heat treatment was performed at 220 ° C. for 15 minutes.

[0157] Next, water repellent treatment was performed by the following method.

[Water repellent treatment by coating method]

0.5% by mass (based on the solid content of the photosensitive resin) containing a fluorosurfactant (Sumitomo 3M, Florad FC-430) in advance on the substrate with the dark color separation wall Attached to the Al force resoluble soluble photosensitive resin (Hexist Shapan Co., Ltd., positive photoresist AZP4210) is applied using a slit nozzle to a film thickness of 2 / zm, and a hot air circulating dryer Heat treatment was performed at 90 ° C for 30 minutes.

Then, an exposure amount of ^{110nj / cm 2 (38mW / cm} 2 X 2. 9 seconds), exposed through a dark Hanarega wall from the back surface of the substrate formed with the dark Hanarega wall, inorganic alkaline developing solution (Hexist Japan Co., Ltd., AZ400K Developer, 1: 4) Immerse and shake for 80 seconds, then rinse in pure water for 30 to 60 seconds, and water-repellent grease layer on dark color separation wall By forming the surface energy difference between the inside and outside of the pixel. 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 around 55 dyne / cm inside the pixel (on the glass substrate).

[0158] Next, after coloring the R, G, and B pixels in the same manner as in Example 1, the color filter was beta-cured in an oven at 230 ° C for 30 minutes to completely cure both the black matrix and each pixel. .

[0159] The ink constituting each pixel of the color filter obtained in this way is inserted into the dark color separation wall gap. Defects such as hang-ups, blurs, protrusions, color mixing with adjacent pixels, and white spots were also powerful. 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 by the above method.

[0160] [Example 4]

A color filter and a liquid crystal display device were produced in the same manner as in Example 1 except that the post-exposure conditions were changed as shown in Table 2 in the formation of the dark color separation wall in Example 3.

[0161] [Example 5]

In the formation of the dark color separation wall in Example 3, the dark color photosensitive transfer material K1 was changed to the following dark color photosensitive transfer material K2, and the conditions for the post exposure are shown in Table 2. A dark color separation wall was prepared in the same manner as in Example 3 except that the conditions were changed (upper surface 3 OOOnj / cm ² + lower surface 3000 mj / cm ² ).

[0162] [Production of dark photosensitive transfer material K2]

The dark color composition K1 was applied onto a temporary support of 16 μm thick polyethylene terephthalate film (Tetron G2 manufactured by Teijin DuPont Films Ltd.) using a slit nozzle and dried. In this way, a dark photosensitive resin layer having a dry film thickness of 2. O / z m is provided on the temporary support, and finally a protective film (thickness: 12111 polypropylene film) is pressed.

In this way, a dark photosensitive transfer material in which the temporary support and the dark photosensitive resin layer became a solid body was produced. The sample name of this dark color photosensitive transfer material was K2.

[0163] [Comparative Example 1]

A color filter and a liquid crystal display device were produced in the same manner as in Example 1 except that in the pattern exposure step of Example 1, instead of performing exposure in a nitrogen atmosphere, pattern exposure was performed in the atmosphere.

[0164] [Comparative Example 2]

A color filter and a liquid crystal display device were produced in the same manner as in Example 1 except that the post-exposure conditions were changed as shown in Table 2 in the formation of the dark color separation wall in Example 1.

[0165] [Confirm shape] The substrates with dark color separation walls obtained in the examples and comparative examples were cut vertically with the substrates to expose the cross section, and directly observed with a microscope or the like. Lines parallel to the substrate at the position of 0.8 h, where h is the height of the dark color separation wall at the highest height of the dark color separation wall from the substrate, L, L

L is the tangent at the contact point between 1 and the dark separation wall, and L is the line parallel to the substrate at h.

1 2 3, the intersection force with L is also defined as the distance to the dark separation wall d. Table 2 shows the measurement results.

twenty three

Show.

[0166] [Measurement of ITO resistance]

The ITO resistance of the color filter with ITO obtained in the examples and comparative examples was measured by “Mouth Resta” manufactured by Mitsubishi Chemical Corporation; sheet resistance by a four-probe method. Table 2 shows the measurement results.

[0167] [Evaluation of color mixture]

The color mixture was evaluated by observing with an optical microscope from the substrate and the pixel forming side in the thickness direction. Any 100 pixels in the optical element were observed to confirm the presence or absence of color mixing, and evaluated according to the following evaluation criteria. Table 2 shows the evaluation results.

[Evaluation criteria]

A: There is no color mixing at all.

B: There are less than 5 color combinations.

C: The color mixture is 5 or more and less than 10.

D: 10 or more colors are mixed.

[0168] [Table 2] Post-exposure evaluation Dark color separation wall h d

Anoxic atmosphere ^ Water repellent treatment

Act Exposure d / h

Forming amount

Exposure surface

(mJ / cm ² ) Color mixing Example 1 Application method N ₂ atmosphere Plasma 2500 Top 1.6 0,059 0.037 12 B Example 2 Application method N ₂ atmosphere Plasma 2900 Top 1.7 0.062 0.036 13 B Example 3 Oxygen barrier

Transfer method Application 2600 Upper surface 1.5 0,05 0.033 11 B Oxygen blockage

Example 4 For oxygen barrier layer

Transfer method Application 3000

Oxygen block by upper surface 1.5 0.049 0.033 10 A Example 5 Temporary support

Transfer method Application 3000 surface-side 1.5 0.043 0.029 11 A Oxygen block

Comparative example 1 Application method No silicon blocking Application 2500 Top surface 1,7 0.14 0.082 24 D Comparative example 2

Transfer method Application 2400 Upper surface 1.7 0.059 0.035 13 C Oxygen shut off by 13 C [0169] From Table 2, in Examples 1 to 5, the parameter dZh related to the shape of the dark color separation wall could be set to 0.04 or less. In Examples 1 to 5, the ejected ink was difficult to get over the dark color separation wall, and there was little or no color mixing of the pixels, and good results were obtained. On the other hand, in Comparative Example 1 where pattern exposure was not performed in an oxygen-poor atmosphere, the dZh exceeded 0.04, and color mixing was observed. In Comparative Example 2 in which the amount of post-exposure was 2400 mjZcm ² , a slight color mixture was confirmed.

Explanation of symbols

[0170] 1 Dark color separation wall

2 Board

11 pixel area

12 Dark color separation wall

13 Board

Claims

Claims [1] A color filter having two or more pixel groups exhibiting different colors on a substrate and each pixel constituting the pixel group being separated from each other by a dark color separation wall. It is a manufacturing method, Comprising: The process of forming the said deep color separation wall includes the process of following (1)-(3), The manufacturing method of the color filter characterized by the above-mentioned.

[2] The collar according to claim 1, wherein the poor oxygen atmosphere is at least one selected from an inert gas atmosphere, a reduced pressure, and a protective layer lowering force capable of blocking oxygen. A method for manufacturing a filter.

[3] The development conditions in the development step are as follows: a dilute aqueous solution having an alkaline substance concentration of 0.05 to 20% by mass as a developer, a development temperature of 26 ° C. to 35 ° C., and 2. The method for producing a color filter according to claim 1, wherein the image time is from 20 to LOO seconds.

[4] The color filter according to claim 1, wherein each pixel is formed between the dark color separation walls in a state in which at least a part of the upper surface of the dark color separation wall has water repellency. Production method.

[5] The method for producing a color filter according to [4], wherein the means for bringing at least a part of the dark color separation wall into a water-repellent state is a plasma treatment.

[6] The method of forming each pixel between the dark color separation walls is a method of causing the colored liquid composition forming each pixel to enter between the dark color separation walls by an inkjet method.

1. A method for producing a color filter according to 1.

[7] The method according to claim 1, wherein a photosensitive color transfer material having at least a layer having a dark color composition strength is transferred onto a temporary support to form a dark color separation wall. The manufacturing method of the color filter as described.

[8] A color filter manufactured by the method for manufacturing a color filter according to [1].

[9] The cross-sectional shape of the dark color separation wall formed on the substrate is such that the height from the substrate at the point where the height of the dark color separation wall from the substrate is the highest is 0.8 h from the substrate. The line parallel to the substrate at the position is L, and the tangent line at the point where L and the dark color separation wall are in contact with the substrate at the position of L and h.

1 1 2

When the parallel line is L, the value specified by the distance from the intersection with L to the dark color separation wall

3 2 3

9. The color filter according to claim 8, wherein a value obtained by dividing d by h is 0.04 or less.

10. A display device comprising the color filter according to claim 8.