JP2006330690A - Method of manufacturing color filter, color filter, and display device using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a color filter for manufacturing a pixel without mixed color at a low cost, and to provide the color filter and a display device having the color filter. <P>SOLUTION: In the method of manufacturing the color filter having a pixel group comprising a plurality of pixels having two or more colors on a substrate, the pixels are mutually isolated from a deep color separation picture wall. The deep color separation picture wall satisfies the following condition. A photosensitive resin composition for forming the deep color separation picture wall formed on the substrate is relatively scanned and exposed, and thereafter developed to form a separation picture wall. Thereafter the pixels are formed by drop giving of a colored liquid composition. (A) A ratio A<SB>600</SB>/A<SB>500</SB>of absorbance A<SB>600</SB>in 600 nm and absorbance A<SB>500</SB>in 500 nm is 0.7-1.4. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  The 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. As a manufacturing method of such a color filter, conventionally, a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development. Colored photosensitive resin liquid method (colored resist method) (see, for example, Patent Document 1) 4) Method of sequentially transferring images formed on a temporary support onto the final or temporary support 5) Pre-coloring A method in which a colored layer is formed by applying the photosensitive resin liquid on a temporary support, and the photosensitive colored layer is sequentially transferred directly onto the substrate, exposed, and developed for the number of colors. There is known a method (transfer method) for forming a multicolor image by the above method (for example, see Patent Document 2). A method using an ink jet method (see Patent Document 3) is also known.

Among these methods, the colored resist method has high positional accuracy and can produce a color filter, 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 is advantageous in terms of cost with little loss of the resin liquid.
In the case of forming a color filter by the inkjet method, first, a dark color separation wall (black matrix) is formed by using a light exposure mask on a glass substrate to form a dark color separation wall (black matrix), and a colored ink is driven into the pixel. The method of forming is usually used. (For example, see Patent Document 4)
When forming color filter pixels by the ink jet method, the colored ink that has been struck enters the adjacent pixel beyond the dark color separation wall, which may cause so-called color mixing, which was a major problem when using this method . In order to prevent color mixing, there has been a problem in that the display quality deteriorates unless the height of the dark color separation wall is increased to some extent or the cross-sectional shape of the dark color separation wall is not adjusted.
Japanese Patent Laid-Open No. 1-152449 JP-A-61-99102 JP-A-8-227010 JP 2003-337426 A

The dark color separation wall needs to be devised in shape (for example, the radius of curvature of the inner portion of the dark color separation wall) in accordance with the physical properties (viscosity and surface tension) of the ink. That is, when the ink used changes and the physical properties change, it is necessary to change the expensive exposure mask.
An object of the present invention is to provide a method of manufacturing a color filter that manufactures a pixel having no color mixture at low cost. Another object of the present invention is to provide a color filter having pixels with no color mixture. Another object of the present invention is to provide a display device using a color filter having pixels having no color mixture.

In view of the above situation, the present inventors have conducted extensive research and found that the light-separating wall was formed on the substrate while modulating the light based on the image-separating wall image data. By exposing the resin composition layer to relative scanning exposure and then developing it to form a separation wall, the shape of the dark separation wall can be freely changed, resulting in the prevention of color mixing and cost. An effective method was found and the present invention was completed.
That is, the present invention is achieved by the following means.

<1> A method of manufacturing a color filter having a pixel group composed of a plurality of pixels having two or more colors on a substrate, wherein the pixels are separated from each other by a dark color separation wall. The color separation wall satisfies the following condition (A), and the dark color separation wall is formed on the substrate while modulating light based on the separation wall image data. A method for producing a color filter, comprising: subjecting a photosensitive resin composition layer to relative scanning exposure, and thereafter developing to form a separation wall, and then forming the pixels by applying droplets of a colored liquid composition.
(A) The ratio A ₆₀₀ / A ₅₀₀ of the absorbance A _{600 at 600} nm and the absorbance A ₅₀₀ at ₅₀₀ nm is 0.7 to 1.4.

<2> The color according to <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. A method for manufacturing a filter.
<3> The method for producing a color filter as described in <1> or <2> above, wherein the dark color separation wall has an absorbance at 555 nm of 2.5 or more.

<4> The above-mentioned <1> to <3>, wherein the photosensitive resin composition layer for dark color separation walls is formed by the following (1) or (2): The manufacturing method of the color filter as described in any one of.
(1) A photosensitive resin composition containing a colorant is applied to a substrate and dried.
(2) A photosensitive transfer layer containing a colorant is formed by transferring the photosensitive transfer layer to a substrate using a transfer material formed on a temporary support.

<5> The method for producing a color filter according to any one of <1> to <4>, wherein the droplet application is an inkjet method.
<6> A color filter manufactured by the manufacturing method according to any one of <1> to <5>.
<7> A display device comprising the color filter according to <6>.

  In the present invention, the dark color separation wall is subjected to relative scanning exposure on the photosensitive resin composition layer for dark color separation wall formation formed on the substrate while modulating light based on the separation wall image data, and then To develop a separation wall. According to the present invention, since exposure is performed without using an exposure mask, it is possible to provide a method for manufacturing a color filter that can freely change the shape of the dark color separation wall and manufacture pixels without color mixture at low cost. In addition, according to the present invention, a color filter having pixels with no color mixture can be provided by the manufacturing method. Furthermore, according to the present invention, it is possible to provide a display device using a color filter having pixels having no color mixture.

The method for producing a color filter according to the present invention is a method for producing a color filter having a pixel group composed of a plurality of pixels having two or more colors on a substrate, the pixels being separated from each other by a dark color separation wall. In this method, the dark color separation wall is subjected to relative scanning exposure to the dark color separation wall forming photosensitive resin composition layer while modulating light based on the separation wall image data. Then, after developing to form a separation wall, the pixel is formed by applying a droplet of a colored liquid composition.
The dark color separation wall in the present invention is characterized in that the value of “absorbance at 600 nm ÷ absorbance at 500 nm” is in the range of 0.7 to 1.4. This value is preferably in the range of 0.75 to 1.2, and more preferably in the range of 0.77 to 1.15. If the absorbance ratio is out of the above range, the dark color separation wall appears to be colored, which is not preferable.

In order to obtain a color filter with good image quality, the color tone of the dark color separation wall is important in addition to preventing the color mixture between the pixels. Since the side surface of the dark color separation wall is usually not vertical, a color obtained by adding the color of the pixel such as red, blue and green and the color of the dark color separation wall is displayed in the peripheral portion of the pixel. In other words, no matter how pure the color of the pixels such as red, blue, and green, the color tone of the dark color separation wall is not achromatic, and the color tone is not good when viewed on the entire screen.
The dark color separation wall color is preferably jet black, and the color separation wall colorant is, for example, black, such as carbon black, titanium black, graphite, metal compounds (for example, iron oxide, titanium oxide). It is preferable to use a colorant.
However, even what is generally called a black colorant (black pigment or black dye) is not strictly black (absorbance of visible light is equal over the entire wavelength range). For example, even in the case of carbon black, which is a typical black pigment, the color tone varies depending on the preparation method, particle size, structure, etc., but the particle size contributes greatly to this color tone.
About the particle size in this invention, 10-75 nm is preferable, More preferably, it is 12-50 nm, Furthermore, the range of 15-40 nm is preferable. When the particle size is less than 10 nm or exceeds 75 nm, the value of A ₆₀₀ / A ₅₀₀ is not preferable because it is out of the range of 0.7 to 1.4.
The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, This 100 average value is said.

The dark color separation wall is a photosensitive resin composition layer containing a colorant on the substrate (“photosensitive resin composition layer for dark color separation wall” or “dark color photosensitive resin composition layer”). ), The dark color separation wall is subjected to relative scanning exposure on the dark color separation wall forming photosensitive resin composition layer while modulating light based on the separation wall image data. , And then developing. The photosensitive resin composition layer is formed by a method of applying a dark photosensitive resin composition (coating method) or a method of transferring a photosensitive transfer material (transfer method).
Hereinafter, the dark color photosensitive resin composition and the photosensitive transfer material will be described.

[Dark color photosensitive resin composition]
The dark color separation wall on the substrate is formed from a photosensitive resin composition containing a colorant (also referred to as “dark color photosensitive resin composition” or “dark color composition”). Here, the dark color composition is a composition having a high absorbance at 555 nm, and the value thereof is a value when a coating film having a thickness corresponding to the height of the dark color separation wall is formed. 2.5 or more are preferable, 2.5-10.0 are more preferable, 2.5-6.0 are still more preferable, 3.0-5.0 are especially preferable.
In addition, since the dark color composition is preferably cured by a photoinitiating system as described later, the absorbance with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is preferably 2.0 to 10.0, more preferably 2.5 to 6.0 when a coating film having a thickness corresponding to the height of the dark color separation wall is formed. Most preferred is 3.0 to 5.0. If it is less than 2.0, the shape of the separation wall may not be as desired, and if it exceeds 10.0, polymerization cannot be started and it is difficult to produce the separation wall itself.
Hereinafter, the components in the composition will be described.

(Coloring agent)
Specific examples of the colorant used in the present invention include those given the color index (CI) numbers described in the following dyes and pigments.
For the dark color composition of the present invention, organic pigments, inorganic pigments, dyes, and the like can be suitably used. When light-shielding properties are required for the photosensitive resin layer, carbon black, titanium oxide, and iron oxide tetraoxide. In addition to light-shielding agents such as metal oxide powder, 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 preferably dispersed uniformly in the dark color composition.

  Specific examples of the known dyes or pigments include the pigments and dyes described in JP-A-2005-17716 [0038] to [0053], and JP-A-2004-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used.

  In the present invention, among the colorants, a black colorant is preferable. Illustrative examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.

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

  The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state. The portion is a liquid that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, page 438, Known dispersers such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.

  The dark composition in the present invention preferably comprises at least a binder (resin, polymer), an initiator, and a monomer in addition to the colorant. Further, if necessary, a known additive such as a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter, and the like can be further contained. Furthermore, the dark color composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

(Binder (resin / polymer))
The binder used in the dark color composition is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 A coalescence etc. can be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. These binder polymers having a polar group may be used alone or in a composition used in combination with a normal film-forming polymer.

(Initiator)
As a method for curing the dark color composition, a thermal initiation system using a thermal initiator and a photoinitiation system using a photoinitiator are generally used. In the present invention, it is preferable to use a photoinitiation system. The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray (also referred to as exposure). It is a compound to be obtained and can be appropriately selected from known photopolymerization initiators or photopolymerization initiator systems.
For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

Specifically, a trihalomethyl group-substituted trihalomethyloxazole derivative or s-triazine derivative described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, A trihalomethyl group-containing compound such as the trihalomethyloxadiazole compound described in Japanese Patent No. 4221976;
9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. Acridine compounds such as bis (9-acridinyl) alkane;
6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazine compounds such as trichloromethyl) -s-triazine; 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

  Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and particularly selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.

  Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole.

  The said initiator may be used independently and may use 2 or more types together. The total amount of the initiator 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. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

  The initiator may be configured with a hydrogen donor. The hydrogen donor is preferably a mercaptan-based compound or an amine-based compound defined below from the viewpoint that sensitivity can be further improved. Here, the “hydrogen donor” refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

  The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-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 “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 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.

  Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.

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

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzobenzone. Thiazole / 4,4′-bis (diethylamino) benzophenone.

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. 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.

(monomer)
As the polyfunctional monomer used in the dark color composition, the following compounds can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.

  Moreover, reaction of a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate with a diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate, and xylene diisocyanate. Things can also be used.

  Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  As content in the dark composition of a polyfunctional monomer, 5-80 mass% is preferable with respect to the total solid (mass) of a dark color composition, and 10-70 mass% is especially preferable. When the content is less than 5% by mass, the resistance to the alkaline developer at the exposed portion of the composition may be inferior, and when it exceeds 80% by mass, the tackiness of the dark color composition increases. Therefore, the handleability may be inferior.

(solvent)
In the dark color composition of the present invention, an organic solvent may be used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

(Surfactant)
In the dark color separation image wall or photosensitive transfer material in the present invention, the dark color composition can be applied to a substrate or a temporary support by using a slit-like nozzle or the like described later. By containing an appropriate surfactant therein, the film thickness can be controlled to be uniform, and coating unevenness can be effectively prevented.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
In addition, 0.001-1 mass% is common, as for content of surfactant with respect to the total solid of a dark color composition, 0.01-0.5 mass% is preferable, and 0.03-0. 3% by mass is particularly preferred.

(UV absorber)
The dark color composition of the present invention may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate series, benzophenone series, benzotriazole series, cyanoacrylate series, nickel chelate series, hindered amine series and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone , Nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebake 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4- Piperidenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine -2-yl] amino} -3-phenylcoumarin and the like.
In addition, 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, preferably 1 to 12% by mass, and particularly preferably 1.2 to 10% by mass. .

(Other)
-Thermal polymerization inhibitor-
Moreover, it is preferable that the dark color composition of this invention contains a thermal-polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.
The content of the thermal polymerization inhibitor with respect to the total solid content of the dark color composition is generally 0.01 to 1% by mass, preferably 0.02 to 0.7% by mass, and 0.05 to 0%. .5% by mass is particularly preferred.
Moreover, in the dark color composition in this invention, the "adhesion adjuvant" described in Unexamined-Japanese-Patent No. 11-133600, other additives, etc. other than the said additive can be contained.

  The thickness of the dark color photosensitive resin composition layer in the present invention is particularly limited depending on the solid content of the dark color photosensitive resin composition and the thickness of the formed dark color separation wall. However, it is generally 1 μm or more, preferably 1.0 to 12 μm, more preferably 1.5 to 10 μm, further preferably 1.8 to 8 μm, and particularly preferably 2 to 6 μm.

[Photosensitive transfer material]
In order to realize the shape of the separation wall in the present invention easily and at low cost, a layer comprising at least a dark color photosensitive resin composition on the temporary support and, if necessary, an oxygen blocking layer are further provided. There are methods (3) and (4) described later in which a dark color photosensitive transfer material (hereinafter also referred to as “photosensitive transfer material”) is used. When a material having an oxygen blocking layer is used, the layer made of the dark color photosensitive resin composition is protected by the oxygen blocking layer and thus automatically becomes in an oxygen-poor atmosphere. Therefore, there is no need to carry out the exposure process under an inert gas or under reduced pressure, so that there is an advantage that the current process can be used as it is.

(Temporary support)
The temporary support in the above photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Dark color photosensitive resin composition layer)
The dark color photosensitive resin composition layer in the above photosensitive transfer material is formed from the dark color composition, and the characteristics such as the shape, the formation method, and the like are the same as those formed by the coating method. The preferred embodiment is also the same.

(Oxygen barrier layer)
In the photosensitive transfer material of the present invention, it is preferable to provide an oxygen blocking layer on the photosensitive resin composition layer formed on the temporary support for the purpose of blocking oxygen during exposure. The oxygen barrier layer has the same physical properties and characteristics as the oxygen barrier layer described in the section of the deep color separation wall described later, and the preferred embodiment is also the same.

(Thermoplastic resin layer)
The photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is preferably alkali-soluble and comprises at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, it is possible to exhibit good adhesion to a permanent support in the dark color separation wall forming method described later.
Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.
For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.
In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.
Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate.

(Protective film)
It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material. The thickness of the protective film is generally 4 to 40 μm, preferably 5 to 30 μm, and particularly preferably 10 to 25 μm.

(Method for producing photosensitive transfer material)
The photosensitive transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which a thermoplastic resin layer additive is dissolved on a temporary support, and drying. Then, a solution of an oxygen barrier layer material composed of a solvent that does not dissolve the thermoplastic resin layer is applied onto the thermoplastic resin layer, dried, and then the dark color photosensitive resin composition layer coating solution is applied to the oxygen barrier layer (intermediate layer). It can be produced by coating and drying with a solvent that does not dissolve. When the thermoplastic resin layer is not provided, the above limitation is not necessary for the solvent of the oxygen blocking layer.
In addition, a sheet provided with a thermoplastic resin layer and an oxygen blocking layer on the temporary support and a sheet provided with a dark photosensitive resin composition layer on a protective film were prepared, and the oxygen blocking layer and the dark photosensitive layer were prepared. Further, by sticking each other so that the photosensitive resin composition layer is in contact with each other, a sheet having a thermoplastic resin layer provided on the temporary support, and a dark photosensitive resin composition layer on the protective film and It can also be produced by preparing a sheet provided with an oxygen blocking layer and bonding them together so that the thermoplastic resin layer and the oxygen blocking layer are in contact with each other.
In addition, although application | coating in the said preparation method can be performed with a well-known coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using a slit-shaped nozzle.

[substrate]
As the substrate (permanent support), 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 transparent synthetic resin film having transparency and good dimensional stability.

[Dark color separation wall]
There is an embodiment in which the dark color separation wall of each pixel is formed by a coating method using the above-mentioned dark color photosensitive resin composition (dark color composition) or a transfer method using a photosensitive transfer material described later. The formation may be performed in an oxygen-poor atmosphere.
Here, under the oxygen-poor atmosphere, the partial pressure of oxygen at the time of photocuring the dark color composition or the dark color composition layer in the present invention is 0.15 atm or less, or an oxygen barrier capable of blocking oxygen. Refers to the layer below, and these are as follows in detail.
Normally, the partial pressure of oxygen is 0.21 atm under the atmosphere (1 atm). Therefore, in order to reduce the partial pressure of oxygen to 0.15 atm or less, (a) the atmosphere at the time of exposure is reduced to 0 0.7 b or less, or (b) a gas other than air and oxygen (for example, an inert gas such as nitrogen or argon) is mixed by 40 vol% or more with respect to air.
The poor oxygen atmosphere in the present invention is not particularly limited, and any of the above methods can be used.
When using the method in which the oxygen partial pressure is 0.15 atm or less, 0.10 atm or less is preferable, 0.08 atm or less is more preferable, and 0.05 atm or less is particularly preferable. When the oxygen partial pressure is higher than 0.15 atm, the surface of the dark color separation wall is not sufficiently cured, and the height of the dark color separation wall may be lower than the target.
There is no particular limitation on the lower limit of the oxygen partial pressure. By substituting the vacuum or atmosphere with a gas other than air (eg, nitrogen), the oxygen partial pressure can be effectively reduced to zero, which is also a preferred method. The oxygen partial pressure can be measured using an oximeter.

The inert gas refers to a general gas such as N ₂ , H ₂ , or CO ₂ or a rare gas such as He, Ne, or Ar. Among these, N ₂ is preferably used because of safety, availability, and cost.

  The term “under reduced pressure” refers to a state of 500 hPa or less, preferably 100 hPa or less.

As described above, the dark color separation wall of the present invention is formed using the dark color composition, and the following (1) and (2) coating methods, and the following (3) and (4) transfer methods. It is preferable to manufacture by.
That is, (1) the dark color separation wall is exposed to an oxygen-poor atmosphere (oxygen partial pressure of 0.15 atm or less) after the dark color photosensitive resin composition containing the colorant is applied to the substrate and dried. And developed to form.
In addition, (2) the dark color separation wall is formed by applying a dark photosensitive resin composition containing a colorant onto a substrate and drying it, and then in an oxygen-poor atmosphere (on the dark photosensitive resin composition layer, oxygen It is formed by exposure and development in a state in which a blocking layer is provided.
(3) A photosensitive transfer material having a dark color photosensitive transfer layer (dark color photosensitive resin composition layer) formed on a temporary support by the dark color photosensitive resin composition was transferred onto the substrate. Thereafter, it is formed by exposure and development in an oxygen-poor atmosphere (oxygen partial pressure of 0.15 atm or less).
(4) A photosensitive transfer material having a dark color photosensitive transfer layer (dark color photosensitive resin composition layer) formed on a temporary support by the dark color photosensitive resin composition was transferred onto the substrate. Thereafter, it is formed by exposure and development in an oxygen-poor atmosphere (in the state where an oxygen blocking layer is provided on the dark color photosensitive resin composition layer).
The dark color separation wall separates two or more pixel groups and is generally black in many cases, but is not limited to black.

(Oxygen barrier layer)
The oxygen barrier layer referred to in the present invention is a layer having an oxygen permeability of 500 cm ³ / (m ² · day · atm) or less, but the oxygen permeability is 100 cm ³ / (m ² · day · atm) or less. It is preferably 50 cm ³ / (m ² · day · atm) or less.
When the oxygen permeability is higher than 500 cm ³ / (m ² · day · atm), it is difficult to efficiently block oxygen, so that it is difficult to make the separation wall have the desired shape.
Specifically, a layer mainly composed of polyethylene, polyvinylidene chloride, polyvinyl alcohol or the like is preferable, and among these, a layer mainly composed of polyvinyl alcohol is preferable.
The polyvinyl alcohol preferably has a saponification degree of 80% or more. As content of the said polyvinyl alcohol in the oxygen barrier layer of this invention, 25 mass%-99 mass% are preferable, 50 mass%-90 mass% are more preferable, 50 mass%-80 mass% are especially preferable.
Further, polymers such as polyvinyl pyrrolidone and polyacrylamide may be added as necessary, and among them, polyvinyl pyrrolidone is preferable. The addition amount of these polymers is 1-40 mass% of the whole layer, More preferably, it is 10-35 mass%. If the amount of polyvinylpyrrolidone added is too large, oxygen barrier properties may be insufficient.

When a dark composition having a high absorbance as described above is photopolymerized in a poor oxygen atmosphere as described above on the substrate, the exposure amount from the surface of the composition toward the substrate is absorbed by the composition itself. Dampens, resulting in more hardened surfaces. Furthermore, since it is under an oxygen-poor atmosphere, inhibition of polymerization on the surface of the composition is suppressed, and as a result, the surface is further cured.
These values are measured by actually observing the dark color separation wall formed on the substrate vertically by cutting the substrate vertically to expose the cross section and directly observing with a microscope or the like.
By passing through the step of fixing the shape of the separation wall obtained in this way, for example, when used in a color filter, it is difficult for the ink once deposited in the gap to get over the dark separation wall. As a result, it is possible to obtain a good color filter while preventing color mixing with adjacent pixels.

  In the present invention, the height h of the dark color separation wall (the distance between the highest point of the dark color separation wall H and the foot G of the perpendicular line from the H to the substrate) is 1. It is preferably 0 μm or more, more preferably 1.5 μm or more and 10 μm or less, still more preferably 1.8 μm or more and 7.0 μm or less, and particularly preferably 2.0 μm or more and 5.0 μm or less. By setting the thickness to 1.0 μm or more and 10 μm or less, it is possible to prevent color mixing more effectively. If the height is less than 1.5 μm, color mixing may occur. If the height exceeds 10 μm, it is difficult to form a dark color separation wall.

The absorbance at 555 nm of the dark color separation wall of the present invention is preferably 2.5 or more, more preferably 2.5 to 10.0, further preferably 2.5 to 6.0, and 3.0 to 5.0. Is particularly preferred.
By setting the absorbance within the range, a display device with high contrast is obtained, which is preferable. In view of display quality of the display device, the color of the dark color separation wall is preferably black.
The absorbance at 555 nm of the dark color separation wall of the present invention is preferably 2.5 or more, more preferably 2.5 to 10.0, further preferably 2.5 to 6.0, and 3.0 to 5.0. Is particularly preferred.
The absorbance of the dark color separation wall and the absorbance at 555 nm can be measured with a known spectrophotometer. In the present invention, measurement was performed using (device name: UV-2100, manufacturer name: manufactured by Shimadzu Corporation).

(Formation of dark color separation wall)
-Formation of dark color separation wall using dark color composition-
An example of a method for forming a dark color separation wall by applying a dark color composition on a substrate to form a dark color separation image wall will be described below, but the present invention is not limited thereto.
First, after cleaning the substrate, the substrate is heat-treated to stabilize the surface state. After the temperature of the substrate is adjusted, the dark color composition is applied. Subsequently, after part of the solvent is dried to eliminate the fluidity of the coating layer, unnecessary coating solution around the substrate is removed with an EBR (edge bead remover), etc., if necessary, and prebaked to concentrate. A color photosensitive resin composition layer is obtained.

The application is not particularly limited, and can be performed using a known coater for glass substrate having a slit-like nozzle (for example, product name: MH-1600, manufactured by FS Asia Co., Ltd.).
The drying can be performed using a known drying apparatus (for example, VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)).
Although it does not specifically limit as prebaking, For example, it can achieve by making 120 degreeC 3 minutes. The film thickness of the obtained dark color photosensitive resin composition layer is as described above.

Subsequently, the dark color photosensitive resin composition layer obtained above is subjected to relative scanning exposure while modulating light based on the image separation wall image data, and then developed to form the image separation wall.
Although it is preferable to use the poor oxygen atmosphere at the time of exposure, the oxygen partial pressure may be 0.15 atm or less, or an oxygen blocking layer may be provided. The oxygen partial pressure at this time can be measured using an oximeter (G-102 type, manufactured by Iijima Electronics Co., Ltd.).
Hereinafter, the relative scanning exposure will be described in detail.

(Relative scanning exposure)
The exposure method of the present invention includes a method using an ultra high pressure mercury lamp and a method using a laser, but the latter is preferred.
As the laser used in the present invention, known lasers such as an argon laser, a He—Ne laser, a semiconductor laser, a carbon dioxide gas laser, and a YAG laser can be used.
The wavelength of the laser is not particularly limited, but among them, it is preferable to select from a wavelength range of 300 to 500 nm from the viewpoint of the resolution of the dark color separation wall, the cost of the laser device, and the availability, 450 nm is more preferable, and 405 nm is particularly preferable.
The beam diameter of the laser is not particularly limited, but among them, from the viewpoint of the resolution of the dark color separation wall, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
Although it does not specifically limit as energy amount of a laser beam, From a viewpoint of exposure time and resolution, 1-100 mJ / cm < ² > is preferable especially and 5-20 mJ / cm < ² > is more preferable.
In the present invention, it is necessary to spatially modulate laser light according to image data. For this purpose, it is preferable to use a digital micro device which is a spatial light modulation element.

  As the exposure apparatus, for example, exposure can be performed using the following apparatus.

An example of a three-dimensional exposure apparatus using laser light is shown below, but the exposure apparatus in the present invention is not limited to this.
As shown in FIG. 1, the exposure unit includes a flat stage 152 that holds the photosensitive material 150 by adsorbing the photosensitive material 150 to the surface. Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The exposure apparatus is provided with a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the photosensitive material 150 are provided on the other side. The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 2 and 3B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in an approximately matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the photosensitive material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Therefore, as the stage 152 moves, a strip-shaped exposed area 170 is formed for each exposure head 166 in the photosensitive material 150. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed areas 170 are arranged without gaps in the direction orthogonal to the sub-scanning direction. In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice here). Therefore, can not be exposed portion between the exposure area 168 ₁₁ in the first row and the exposure area 168 _12, it can be exposed by the second row of the exposure area 168 ₂₁ and the exposure area 168 ₃₁ in the third row.

Each of the exposure heads 166 _{11 to} 166 _mn is a spatial light modulator that modulates an incident light beam for each pixel according to image data, as shown in FIGS. 4, 5 (A) and (B). A digital micromirror device (DMD) 50 is provided. The DMD 50 is connected to a controller (not shown) including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input image data. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the image data processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 including a laser emitting portion in which an emitting end portion (light emitting point) of an optical fiber is arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order.

  The lens system 67 includes a pair of combination lenses 71 that collimate the laser light emitted from the fiber array light source 66 and a pair of combination lenses that correct the light quantity distribution of the collimated laser light to be uniform. 73 and a condensing lens 75 that condenses the laser light whose light intensity distribution is corrected on the DMD. With respect to the arrangement direction of the laser emitting end, the combination lens 73 spreads the light beam at a portion close to the optical axis of the lens and contracts the light beam at a portion away from the optical axis, and with respect to a direction orthogonal to the arrangement direction. Has a function of allowing light to pass through as it is, and corrects the laser light so that the light quantity distribution is uniform.

  Further, on the light reflection side of the DMD 50, lens systems 54 and 58 that form an image of the laser light reflected by the DMD 50 on the scanning surface (exposed surface) 56 of the photosensitive material 150 are arranged. The lens systems 54 and 58 are arranged so that the DMD 50 and the exposed surface 56 are in a conjugate relationship.

  As shown in FIG. 6, the DMD 50 is configured such that a micromirror 62 is supported by a support column on an SRAM cell (memory cell) 60, and a large number of (pixels) (pixels) are formed. For example, the mirror device is configured by arranging 600 × 800 micromirrors in a lattice pattern. Each pixel is provided with a micromirror 62 supported by a support column at the top, and a material having a high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and is entirely monolithic (integrated type). ).

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is inclined within a range of ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. FIG. 7A shows a state in which the micromirror 62 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 62 is tilted to −α degrees in the off state. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 as shown in FIG. 6 according to the image signal, the light incident on the DMD 50 is reflected in the inclination direction of each micromirror 62. .

  FIG. 6 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. On / off control of each micromirror 62 is performed by a controller (not shown) connected to the DMD 50. A light absorber (not shown) is arranged in the direction in which the light beam is reflected by the micromirror 62 in the off state.

  Further, it is preferable that the DMD 50 be arranged with a slight inclination so that the short side thereof forms a predetermined angle θ (for example, 1 ° to 5 °) with the sub-scanning direction. 8A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 8B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.

In the DMD 50, a number of micromirror arrays in which a large number (for example, 800) of micromirrors are arranged in the longitudinal direction are arranged in a short direction (for example, 600 sets). As shown, by tilting the DMD 50, the pitch P ₁ of the scanning trajectory (scan line) of the exposure beam 53 by each micromirror becomes narrower than the pitch P ₂ of the scanning line when the DMD 50 is not tilted, greatly increasing the resolution. Can be improved. On the other hand, since the tilt angle of the DMD 50 is very small, the scan width W ₂ when the DMD 50 is tilted and the scan width W ₁ when the DMD 50 is not tilted are substantially the same.

  Further, the same scanning line is overlapped and exposed (multiple exposure) by different micromirror rows. In this way, by performing multiple exposure, it is possible to control a minute amount of the exposure position and to realize high-definition exposure. Further, joints between a plurality of exposure heads arranged in the main scanning direction can be connected without a step by controlling a very small amount of exposure position.

  Note that the same effect can be obtained by arranging the micromirror rows in a staggered manner by shifting the micromirror rows by a predetermined interval in a direction orthogonal to the sub-scanning direction instead of inclining the DMD 50.

  As shown in FIG. 9A, the fiber array light source 66 includes a plurality of (for example, six) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. Yes. The other end of the multimode optical fiber 30 is coupled with an optical fiber 31 having the same core diameter as the multimode optical fiber 30 and a cladding diameter smaller than the multimode optical fiber 30, as shown in FIG. A laser emission portion 68 is configured by arranging emission ends (light emission points) of the optical fiber 31 in a line along a main scanning direction orthogonal to the sub-scanning direction. As shown in FIG. 9D, the light emitting points can be arranged in two rows along the main scanning direction.

  As shown in FIG. 9B, the emission end of the optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. Further, a transparent protective plate 63 such as glass is disposed on the light emitting side of the optical fiber 31 in order to protect the end face of the optical fiber 31. The protective plate 63 may be disposed in close contact with the end surface of the optical fiber 31 or may be disposed so that the end surface of the optical fiber 31 is sealed. The light emitting end portion of the optical fiber 31 has a high light density and is likely to collect dust and easily deteriorate. However, by disposing the protective plate 63, it is possible to prevent the dust from adhering to the end face and to delay the deterioration.

  Here, in order to arrange the output ends of the optical fibers 31 with a small cladding diameter in a line without any gaps, the multi-mode optical fibers 30 are stacked between two adjacent multi-mode optical fibers 30 at a portion with a large cladding diameter. The exit ends of the optical fibers 31 coupled to the stacked multi-mode optical fibers 30 are the two exit ends of the optical fibers 31 coupled to the two adjacent multi-mode optical fibers 30 in the portion where the cladding diameter is large. They are arranged so that they are sandwiched between them.

  For example, as shown in FIG. 10, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. Here, the multimode optical fiber 30 and the optical fiber 31 are step index optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 25 μm, NA = 0.2, and transmission of the incident end face coating. The ratio is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 25 μm, and NA = 0.2.

  In general, in laser light in the infrared region, propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the clad diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, more preferably 60 μm or less. Preferably, it is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

  The laser module 64 includes a combined laser light source (fiber light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, which are arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have a common oscillation wavelength (for example, 405 nm), and all the maximum outputs are also common (for example, 100 mW for a multimode laser and 30 mW for a single mode laser). As the GaN semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 nm to 450 nm may be used.

  As shown in FIGS. 12 and 13, the above-described combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and a wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 13, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens 17 is numbered among the plurality of collimator lenses. is doing.

  FIG. 14 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 14).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a direction parallel to the active layer and a divergence angle in a direction perpendicular to, for example, 10 ° and 30 °. A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. Each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 20 is formed by cutting a region including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in a horizontal direction and short in a direction perpendicular thereto. Is formed. The condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

Next, the operation of the exposure apparatus will be described.
In each exposure head 166 of the scanner 162, laser beams B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  Here, a condensing optical system is configured by the collimator lenses 11 to 17 and the condensing lens 20, and a multiplexing optical system is configured by the condensing optical system and the multimode optical fiber 30. That is, the laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has low output, so a desired output cannot be obtained unless multiple rows are arranged. Since the light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled one-on-one, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, as described above, an output of about 1 W can be obtained with the six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 is 0.0081 mm ² (0.325 mm × 0.025 mm). Therefore, the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), and the luminance can be increased about 80 times compared with the conventional case. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared with the conventional one.

  Here, with reference to FIGS. 15A and 15B, the difference in the depth of focus between the conventional exposure head and the exposure head according to the present invention will be described. The diameter of the light emission region of the bundled fiber light source of the conventional exposure head is 0.675 mm, and the diameter of the light emission region of the fiber array light source of the exposure head according to the present invention is 0.025 mm. . As shown in FIG. 15A, in the conventional exposure head, since the light emitting area of the light source (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 increases, and as a result, the light enters the scanning surface 5. The angle of the light beam increases. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 15B, in the exposure head according to the present invention, the diameter of the light emitting area of the fiber array light source 66 is small in the sub-scanning direction, so that the light flux that passes through the lens system 67 and enters the DMD 50 As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. DMD is a reflective spatial modulation element, but FIGS. 15A and 15B are developed views for explaining the optical relationship.

  Image data corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This image data is data representing the density of each pixel constituting the image by binary values (whether or not dots are recorded).

  The stage 152 that has adsorbed the photosensitive material 150 to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the photosensitive material 150 is detected by the detection sensor 164 attached to the gate 160 when the stage 152 passes under the gate 160, the image data stored in the frame memory is sequentially read out for a plurality of lines. A control signal is generated for each exposure head 166 based on the image data read by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micro mirror of the DMD 50 is in an on state forms an image on the exposed surface 56 of the photosensitive material 150 by the lens systems 54 and 58. Is done. In this way, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the photosensitive material 150 is exposed in pixel units (exposure area 168) that is approximately the same number as the number of pixels used in the DMD 50. Further, when the photosensitive material 150 is moved at a constant speed together with the stage 152, the photosensitive material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is formed for each exposure head 166. It is formed.

  As shown in FIGS. 16A and 16B, in the DMD 50, 600 sets of micromirror rows in which 800 micromirrors are arranged in the main scanning direction are arranged in the sub-scanning direction. Thus, only a part of the micro mirror rows (for example, 800 × 100 rows) is controlled to be driven.

  As shown in FIG. 16A, a micromirror array arranged at the center of the DMD 50 may be used, and as shown in FIG. 16B, the micromirror array arranged at the end of the DMD 50 is used. May be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror rows. Get faster. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

  For example, when only 300 sets are used in 600 micromirror rows, modulation can be performed twice as fast per line as compared to the case of using all 600 sets. Further, when only 200 sets of 600 micromirror arrays are used, modulation can be performed three times faster per line than when all 600 sets are used. That is, an area of 500 mm in the sub-scanning direction can be exposed in 17 seconds. Further, when only 100 sets are used, modulation can be performed 6 times faster per line. That is, an area of 500 mm in the sub-scanning direction can be exposed in 9 seconds.

  The number of micromirror rows to be used, that is, the number of micromirrors arranged in the sub-scanning direction is preferably 10 or more and 200 or less, and more preferably 10 or more and 100 or less. Since the area per micromirror corresponding to one pixel is 15 μm × 15 μm, when converted to the use area of DMD50, an area of 12 mm × 150 μm or more and 12 mm × 3 mm or less is preferable, and 12 mm × 150 μm or more and 12 mm A region of × 1.5 mm or less is more preferable.

  If the number of micromirror rows to be used is within the above range, as shown in FIGS. 17A and 17B, the laser light emitted from the fiber array light source 66 is made into substantially parallel light by the lens system 67, and the DMD 50 Can be irradiated. It is preferable that the irradiation area where the laser beam is irradiated by the DMD 50 coincides with the use area of the DMD 50. When the irradiation area is wider than the use area, the utilization efficiency of the laser light is lowered.

  On the other hand, the diameter of the light beam condensed on the DMD 50 in the sub-scanning direction needs to be reduced according to the number of micromirrors arranged in the sub-scanning direction by the lens system 67, but the number of micromirror rows to be used. Is less than 10, it is not preferable because the angle of the light beam incident on the DMD 50 increases and the depth of focus of the light beam on the scanning surface 56 becomes shallow. Further, the number of micromirror rows to be used is preferably 200 or less from the viewpoint of modulation speed. DMD is a reflective spatial modulation element, but FIGS. 17A and 17B are developed views for explaining the optical relationship.

  When the sub scanning of the photosensitive material 150 by the scanner 162 is completed and the rear end of the photosensitive material 150 is detected by the detection sensor 164, the stage 152 is moved along the guide 158 by the driving device (not shown) on the most upstream side of the gate 160. Returned to the origin at the point, and again moved along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  As described above, the exposure unit (exposure apparatus) according to the present invention includes a DMD in which 800 sets of micromirrors arranged in the main scanning direction are arranged in 600 sets in the subscanning direction. Since the controller controls so that only a part of the micromirror rows are driven, the modulation speed per line becomes faster than when all the micromirror rows are driven. This enables high-speed exposure.

The exposure with the ultra-high pressure mercury lamp is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), and the exposure amount can be appropriately selected (for example, 300 mJ / cm ² ). Further, the oxygen partial pressure at this time can be measured using the oximeter.

Next, it develops with a developing solution, a patterning image is obtained, and if necessary, it wash-processes and obtains a deep color separation wall.
Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the dark color photosensitive resin 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.

  Examples of the alkaline substance in the method of applying the dark color composition and the method of using a photosensitive transfer material described later include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, carbonic acid). Sodium, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, metasilicate) Sodium, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . 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.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin composition layer, methods such as rubbing with a rotating brush or a wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, although depending on the composition of the photosensitive resin composition layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the separation wall shape suitable. In this developing step, the separating wall shape is formed as described above.

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 in the vicinity of the center of the substrate, and a 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 °.
In addition, it is preferable to spray pure water before development and moisten the photosensitive resin layer because a uniform development result is obtained.

  Further, after development, if air is lightly blown onto the substrate to remove excess liquid substantially and then shower water washing is performed, a more uniform development result is obtained. Further, when the residue is removed by spraying ultrapure water with a pressure of 3 to 10 MPa with an ultrahigh pressure washing nozzle before washing with water, a high-quality image without residue can be obtained. If the substrate is transported to a subsequent process with water droplets attached thereto, the process is soiled or stains remain on the substrate. Therefore, it is preferable to remove excess water and water droplets by draining with an air knife.

  In addition to the exposure and development steps, steps such as post-exposure and heat treatment may be performed as the dark color separation wall producing step of the present invention. As the step, the steps described in paragraph numbers [0067] to [0074] of JP-A-2005-3861 can be suitably used.

  Further, in order to prevent color mixing when applying the droplets, the dark color separation wall is subjected to an ink repellent treatment on at least a part of the upper surface of the dark color separation wall in a state of being water repellent. Each pixel is preferably formed between the dark color separation walls. Here, the part of the upper surface of the dark color separation wall refers to at least a part of the surface on the dark color separation wall opposite to the surface of the dark color separation wall that contacts the substrate. .

  As for the ink repellent treatment, for example, (1) a method of kneading an ink repellent substance on a dark color separation wall (for example, see JP-A-2005-36160), (2) a method of newly providing an ink repellent layer (See, for example, JP-A-5-241101), (3) A method for imparting ink repellency by plasma treatment (see, for example, JP-A-2002-62420), (4) Upper surface of a dark color separation wall In particular, there is a method of applying an ink repellent material (for example, see Japanese Patent Application Laid-Open No. 10-123500). In particular, (3) an ink repellent treatment by plasma is performed on a dark color separation wall formed on a substrate. The method is preferred.

Hereinafter, the water repellent treatment will be described in detail.
(1) <Method of kneading a water-repellent substance into the separation wall>

Hereinafter, the water repellent treatment will be described in detail.
(1) <Method of kneading a water-repellent substance into the separation wall>
As a means for preventing “color mixing”, there is a method of producing a separation wall using a photoresist obtained from the dark color composition of the present invention containing the fluororesin (A).
The fluorine-containing resin includes a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a), and a single unit based on a monomer having an ethylenic double bond and an acidic group (b). It is a copolymer containing a monomer unit, and it is preferable that an acid value is 1-300 mgKOH / g.
Examples of the ethylenic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group.
As monomers having an ethylenic double bond and an Rf group (a), CH ₂ = CR ¹ COOQ ² Rf, CH ₂ = CR ¹ OCOQ ¹ Rf, CH ₂ = CR ¹ OQ ¹ Rf, CH ₂ = CR ¹ CH ₂ OQ ¹ Rf, CH ₂ = CR ¹ COOQ ² NR ¹ SO ₂ Rf, CH ₂ = CR ¹ COOQ ² NR ¹ CORf, CH ₂ = CR ¹ COOQ ² NR ¹ COOQ ² Rf, CH ₂ = CR ¹ COOQ ² OQ ¹ Rf, and the like. However, R ¹ is a hydrogen atom or a methyl group, Q ¹ is a divalent organic group single bond or a 1 to 6 carbon atoms, Q ² is a divalent organic group having 1 to 6 carbon atoms, respectively. Q ¹ and Q ² may have a cyclic structure.

Specific examples of _{^{Q 1, Q 2, -CH 2}} -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - _{CH (CH 2 CH 3) -} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 2 CH 2 CH 3) -, - CH 2 (CH 2) 3 CH 2 -, - CH (CH 2 CH (CH ₃ ) ₂ ) —, —CH ₂ CH (OH) CH ₂ —, —CH ₂ CH ₂ NHCOOCH ₂ —, —CH ₂ CH (OH) CH ₂ OCH ₂ — and the like. Q ¹ may be a single bond. Of these, —CH ₂ —, —CH ₂ CH ₂ —, and —CH ₂ CH (OH) CH ₂ — are preferred from the viewpoint of ease of synthesis.

Specific examples of the monomer having an ethylenic double bond and an Rf group (a) include the following.
_{CH 2 = CHCOOCH 2 CF 2 O} (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = CHCOOCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n _-1 C ₆ F ₁₃ (n is _{2~6), CH 2 = CHCOOCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6).
_{CH 2 = C (CH 3)} COOCH 2 CH 2 NHCOOCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH _{2 CF (CF 3) O (} CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is _{2~6), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH 2 CF (CF 3 _{) O (CF 2 CF (CF} 3) O) n-1 C 6 F 13 (n is 2-6).
_{CH 2 = C (CH 3)} COOCH 2 CH (OH) CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH ₂ CH (OH) CH ₂ OCH ₂ CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₆ F ₁₃ (n is 2 to 6), CH ₂ ═C (CH ₃ ) COOCH _{2 CH (OH) CH 2 OCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6).

  The content of the monomer unit based on the monomer having an ethylenic double bond and Rf group (a) in the fluororesin is preferably 1 to 95%, more preferably 5 to 80%, and more preferably 20 to 20%. 60% is more preferable. Within such a range, the fluororesin exhibits good ink repellency and the developability of the photosensitive composition of the present invention is good.

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, vinyl acetic 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.

  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 an alkyl group such as a methyl group, an ethyl group or an n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group, a halogen atom or an alkyl group. Examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, a haloalkyl group, a nitro group, a cyano group, or an amide group. These may be used alone or in combination of two or more.

  Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) 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) acryloxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, or salts thereof. These may be used alone or in combination of two or more.

  Specific examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydro Shimechiru (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (where g is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) g H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) g H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) g H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _k H (where h is 0 or an integer from 1 to 100, k is an integer from 1 to 100, h + k is from 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) h (C 3 H 6 O) k H and the like. These may be used alone or in combination of two or more.

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

Monomer based on monomer unit based on monomer having fluorine-containing resin having ethylenic double bond and Rf group (a), and monomer having ethylenic double bond and acidic group (b) In the case of a copolymer having a body unit, it has a monomer unit based on a monomer having no Rf group (a) and acidic group (b) (hereinafter referred to as “other monomer”). You may do it.
Other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides, aromatic Examples include vinyl compounds, chloroolefins, fluoroolefins, and conjugated dienes. These compounds may contain a functional group, and examples thereof include 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 do not have an Rf group (a) and an 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 preferable because they are excellent in heat resistance of a coating film formed from the photosensitive resin composition of the present invention.

  In the fluororesin, the proportion of monomer units based on other monomers is preferably 80% or less, and more preferably 70% or less. Within this range, the developability of the photosensitive composition of the present invention will be good.

  The fluororesin in the present invention is a monomer unit based on a monomer having the above ethylenic double bond and Rf group (a), and a single unit having an ethylenic double bond and an acidic group (b). In addition to being obtained by synthesizing a copolymer containing monomer units based on a monomer, a compound having an Rf group (a) and / or a compound having an acidic group (b) in a polymer having a reactive site It can also be obtained by various modification methods to be reacted.

As various modification methods for reacting a compound having an Rf group (a) with a polymer having a reactive site, for example, a monomer having an epoxy group is copolymerized in advance, and then an Rf group (a) and a carboxyl group are later included. Examples thereof include a method of reacting a compound and a method of previously copolymerizing an epoxy group-containing monomer and then reacting a compound having an Rf group (a) and a hydroxyl group.
Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the compound having an Rf group (a) and a carboxyl group include compounds represented by the following formula 3.
_{HOOC-C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 3
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.

Examples of the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following formula 4.
_{HOCH 2 -C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 4
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.

  Examples of various modification methods for reacting a polymer having a reactive site with a compound having an acidic group (b) include a method in which a monomer having a hydroxyl group is copolymerized in advance and then an acid anhydride is reacted. Moreover, the method of making the acid anhydride which has an ethylenic double bond copolymerize previously, and making the compound which has a hydroxyl group react later is mentioned.

  Specific examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydro Shimechiru (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (where g is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) g H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) g H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) g H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _k H (where h is 0 or an integer from 1 to 100, k is an integer from 1 to 100, h + k is from 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) h (C 3 H 6 O) k H and the like. These may be used alone or in combination of two or more.

Specific examples of the acid anhydride include phthalic anhydride, 3-methylphthalic anhydride, trimellitic anhydride, and the like.
Specific examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6 anhydride -Tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, etc. are mentioned.

  The compound having a hydroxyl group may be a compound having one or more hydroxyl groups. Specific examples of the monomer having a hydroxyl group shown above, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol and ethylene glycol; cellsolves such as 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol; 2- (2-ethoxyethoxy) ethanol; And carbitols such as (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.

The polymer having the above-mentioned reaction site which becomes a fluorine-containing resin or a precursor of the fluorine-containing resin is dissolved by dissolving the monomer in a solvent together with a chain transfer agent as necessary, and reacted by adding a polymerization initiator. It can be synthesized by the method.
The acid value of the fluororesin is preferably 1 to 300 mgKOH / g, more preferably 5 to 200 mgKOH / g, and particularly preferably 10 to 150 mgKOH / g. 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 1 g of the resin, and the unit is described as mgKOH / g in this specification.

The number average molecular weight of the fluororesin is preferably 500 or more and less than 20000, and 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 using polystyrene as a standard substance by gel permeation chromatography.
The blending amount of the fluororesin (A) is preferably from 0.01 to 50%, more preferably from 0.1 to 30%, particularly preferably from 0.2 to 10%, based on the solid content in the photosensitive composition. . Within such a range, the photosensitive composition exhibits good ink repellency and ink tumbling properties and good developability.

(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 repellency at a position matching the separation wall on the substrate on which the separation wall is formed.
It is preferable to use a silicone rubber layer as the partition wall having ink repellency. The silicone rubber layer coated on the surface layer is required to have a repulsive effect on the solution and ink used for coloring, and is not limited to this, but the molecular weight having the following repeating units: It is mainly composed of several thousand to several hundred thousand linear organic polysiloxanes.

  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 cross-linking such a linear organic polysiloxane. The cross-linking agent is acetoxysilane, ketoxime silane, alkoxysilane, aminosilane, amidosilane, alkenoxysilane, etc. used for so-called room temperature (low temperature) curable silicone rubber, and usually has a terminal end as a linear organic polysiloxane. In combination with a hydroxyl group, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamide type, and a deketone type silicone rubber are obtained. Further, a small amount of an organic tin compound or the like is added to the silicone rubber as a catalyst. In order to bond the photosensitive resin layer and the silicone rubber layer, various types of adhesive layers may be used between the layers, and aminosilane compounds and organic titanate compounds are particularly preferable. Instead of providing an adhesive layer between the photosensitive resin layer and the silicone rubber layer, an adhesive component may be added to the silicone rubber layer. As this additional adhesive component, an aminosilane compound or an organic titanate compound can be used.

  The exposure for producing the partition wall is performed from the back side of the substrate using the separation wall as a mask, and further, the irradiation UV light is scattered to expand the incident light from the size of the transmission part and to act on the photosensitive resin. The portion of the resin that is solubilized by reaction is made larger on the silicone rubber surface layer side. After exposure in this manner, a partition wall having a silicone rubber surface layer can be prepared by developing with an n-heptane / ethanol mixture.

(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 with plasma on a substrate on which a separation wall is formed.
As the gas containing at least fluorine atoms to be introduced in this step, one or more halogen gases selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ and C ₅ F ₈ are used. It is preferable. In particular, C ₅ F ₈ (octafluorocyclopentene) has an ozone depleting ability of 0, and at the same time, has an atmospheric lifetime (CF ₄ : 50,000 years, C ₄ F ₈ : 3200) as compared with conventional gases. It is very short with 98 years. Therefore, the global warming potential is 90 (100-year integrated value with CO ₂ = 2), which is very small (CF ₄ : 6500, C ₄ F ₈ : 8700) compared to conventional gases, and the ozone layer and the global environment. It is extremely effective for protection and is desirable for use in the present invention.

Further, as the introduced gas, a gas such as oxygen, argon, or helium may be used in combination as necessary. In this step, when a mixed gas of at least one halogen gas selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ and O ₂ is used, It becomes possible to control the degree of ink repellency on the surface of the image separation wall processed in this step. However, in the mixed gas, the oxidation reaction mixture ratio by O ₂ exceeds 30% of O ₂ is dominant, because the ink repellency enhancing effect is prevented, also, O ₂ mixing ratio is more than 30% When the mixed gas is used, it is necessary to use the mixed gas with an O ₂ mixing ratio of 30% or less.
In addition, plasma generation methods such as low frequency discharge, high frequency discharge, and microwave discharge can be used. Conditions such as pressure, gas flow rate, discharge frequency, and processing time during plasma processing are arbitrarily set. can do.

(4) <Method of applying a water repellent material to the upper surface of the 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 separation wall is formed.
Water repellent materials such as fluoropolymers such as polytetrafluoroethylene, silicon rubber, perfluoroalkyl acrylate, hydrocarbon acrylate, methyl siloxane, etc. are generally considered to be water repellent materials and have a contact angle of 60 ° or more to the colorant. If it is a thing, it will not specifically limit.
As a method for applying the water repellent material, it is possible to select the most suitable method for each material such as slit coat, spin coat, dip coat, roll coat, etc., as long as it does not affect the substrate, the separation wall, etc. is there.

Next, UVO ₃ treatment is performed from the back side of the substrate through the separation wall, and the water-repellent film other than the separation wall is selectively removed or hydrophilized (contact angle with the colorant is 30 ° before and after the treatment). (There is an opening above).
If the water repellent material can be removed or hydrophilized, the patterning method can be selected according to the material, such as laser ablation, plasma ashing, dry treatment such as corona discharge treatment, and wet treatment using alkali. Is possible. Further, if it is possible to pattern the water repellent material on the separating wall, a lift-off method or the like is also effective.

  Among the water repellent treatment methods (1) to (4) above, (3) the water repellent treatment method using plasma is particularly preferable from the viewpoint of “simpleness of the process”.

-Formation of dark color separation walls using photosensitive transfer material-
First, after peeling off and removing the protective film of the photosensitive transfer material described above, the surface of the exposed dark color photosensitive resin composition layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like. (Laminated body). 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 further increase the productivity.

Next, the temporary support is removed, the maskless exposure is irradiated above the removal surface after the temporary support is removed, and development is performed using a predetermined processing solution after the irradiation to obtain a patterning image. In accordance with the above, washing with water is performed to obtain a dark color separation wall.
As for the details of the developer and maskless exposure used in the development processing, the developer and maskless exposure in the formation using the coating method can be used in the same manner.

[Pixel]
The pixel and the colored liquid composition in the present invention will be described in the section of “Color filter manufacturing method” described later.

[Overcoat layer]
After creating the color filter by forming the colored region (colored pixel) and the dark color separation wall as described above, the colored region and the dark color separation wall are covered to cover the entire surface for the purpose of improving the durability. A coat layer can be formed.

The overcoat layer can protect colored areas such as R, G, and B, and dark color separation walls, and can flatten the surface. However, it is preferable not to provide from the point which the number of processes increases.
An overcoat layer can be comprised using resin (OC agent), and acrylic resin composition, an epoxy resin composition, a polyimide resin composition etc. are mentioned as resin (OC agent). Among them, the acrylic resin composition is desirable because it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually mainly composed of an acrylic resin and has excellent adhesion. . Examples of the overcoat layer include those described in paragraphs [0018] to [0028] of JP-A No. 2003-287618, and commercially available overcoat agents such as Optomer SS6699G manufactured by JSR.

[Color filter manufacturing method]
(Formation of each pixel)
The color filter manufacturing method of the present invention has a pixel group consisting of a plurality of pixels having two or more colors on a substrate, and the pixels are isolated from each other by the dark color separation wall. These pixels are formed by applying droplets of a colored liquid composition.
That is, droplets of a colored liquid composition for forming pixels of two or more colors (for example, RGB pixels) are applied to the gaps between the dark color separation walls formed on the substrate in the development step. Thus, a plurality of pixels having two or more colors are formed by intruding into the gaps in the dark color separation wall.
As a method for applying the colored liquid composition as a droplet and allowing it to enter the separation wall void, a known method such as an ink jet method or a stripe Geyser coating method can be used, and the ink jet method is preferable in terms of cost. The stripe Geyser coating method is a method of forming stripe-like pixels by applying droplets onto a substrate using a Geyser with fine droplet ejection holes.

In addition, before forming each pixel in this way, the shape of the dark color separation wall may be fixed, and the means is not particularly limited, but includes the following.
That is, 1) re-exposure after development (sometimes referred to as post-exposure), and 2) heat treatment (baking) at a relatively low temperature after development. The heat treatment here refers to heating a substrate having a dark color separation wall in an electric furnace, a dryer or the like, or irradiating an infrared lamp.

  Regarding the ink jet method used for forming each pixel, a known method such as a method of thermally curing ink, a method of photocuring, or a method of performing droplet ejection after forming a transparent image receiving layer on a substrate in advance is used. be able to.

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

  The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

(Inkjet method)
The ink jet system used in the present invention includes 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 foam. Various methods such as a method of injecting the ink can be employed.
The ink used may be oily or water-based. The coloring material contained in the ink can be used for both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability. Further, a coating-type colored ink (colored resin composition, for example, described in JP-A-2005-3861 [0034] to [0063] and [0076] to [0078]), which is used for producing a known color filter, Inkjet compositions described in Kaihei 10-195358 [0009] to [0026], JP-A No. 2004-339332, and JP-A No. 2002-372615 can also be used.
In consideration of the process after coloring, a component that is cured by heating or that is cured by energy rays such as ultraviolet rays can be added to the ink in the present invention. Various thermosetting resins are widely used as components that are cured by heating, and examples of components that are cured by energy rays include those obtained by adding a photoinitiator to an acrylate derivative or a methacrylate derivative. In particular, in view of heat resistance, those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and even those that are sparingly soluble in water can be used after being emulsified.
In this case, the photosensitive resin composition containing a colorant such as a pigment, as mentioned in the section <Deep color composition>, can be used as a suitable one.

  Further, 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 to trifunctional epoxy group-containing monomer can also be used as a suitable ink.

The color filter in the present invention is preferably a color filter in which pixels are formed by an inkjet method, and it is preferable to form three color filters by spraying RGB three color inks.
This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.

[Display device]
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).
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 1994)”. 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. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation 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 and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

[Target use]
The present invention can be applied to a use such as a portable terminal such as a television, a personal computer, a liquid crystal projector, a game machine, and a mobile phone, a digital camera, and a car navigation system without particular limitation.

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these. Unless otherwise specified, “%” and “part” represent “% by mass” and “part by mass”, and “molecular weight” means “mass average molecular weight”.

[Preparation of dark color photosensitive composition]
The dark color photosensitive composition is first weighed in the amount of carbon black dispersion and propylene glycol monomethyl ether acetate described in the following dark color photosensitive composition formulation, mixed at a temperature of 24 ° C. (± 2 ° C.) and 150 RPM for 10 minutes. Stir and then methyl ethyl ketone, binder P-1, hydroquinone monomethyl ether, DPHA solution, 7- [2- [4- (3-hydroxymethylpiperidino) -6-diethylamino] triazylamino] -3-phenylcoumarin 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole and Surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.). It is obtained by stirring at 150 RPM for 30 minutes at ° C (± 2 ° C).

<Dark color photosensitive composition formulation>
Carbon black dispersion (carbon black particle size 20 nm) 23 parts Propylene glycol monomethyl ether acetate 8.0 parts Methyl ethyl ketone 53 parts Binder P-1 9.1 parts Hydroquinone monomethyl ether 0.002 parts DPHA liquid 4. 5 parts 7- [2- [4- (3-hydroxymethylpiperidino) -6-diethylamino] triazylamino] -3-phenylcoumarin 0.75 parts 2-trichloromethyl-5- (p-styryl) Styryl) -1,3,4-oxadiazole 0.16 parts Surfactant 1 0.055 parts

<Carbon black dispersion>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (see below) 0.80%

-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
・ Propylene glycol monomethyl ether acetate 79.38%

<Binder P-1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

<DPHA solution>
・ Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD
DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%

<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

[Example 1]
(Formation of dark color separation wall)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further 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., the dark color photosensitive resin composition was prepared with a glass substrate coater (manufactured by FAS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. The object was applied. Subsequently, after 1 part of the solvent was dried for 30 seconds with a VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove the fluidity of the coating layer, it was pre-baked at 120 ° C. for 3 minutes to obtain a dark color with a thickness of 2.4 μm. A photosensitive resin composition layer was obtained.

Subsequently, this sample was exposed by the following method using the following apparatus.
<Exposure device>
As shown in FIGS. 1 to 17, a fiber array light source 66 capable of emitting 405 nm laser light and an incident laser beam (output 10 mJ / cm ² , 1 / e ² diameter 10 μm) are modulated in accordance with image data. It has a digital micromirror device (DMD) 50 that is a spatial light modulation element, a data processing unit and a mirror drive control unit, and a controller (not shown) connected to the DMD and a laser beam reflected by the DMD are connected to the exposed surface. An exposure head (exposure unit according to the present invention) 166 is configured to be provided with a lens system 54 for imaging, and is controlled by a controller (not shown) to be moved relative to a surface to be exposed in a direction crossing a predetermined direction. An exposure apparatus provided was prepared.

<Exposure>
Next, exposure with a laser beam having a wavelength of 405 nm was performed with an energy amount of 40 mJ / cm ² using the exposure apparatus configured as described above to obtain a dark color separation wall pattern. The exposure was performed in a nitrogen atmosphere by nitrogen purge. The oxygen partial pressure was measured using Iijima Electronics Co., Ltd. oxygen meter G-102 type.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark color photosensitive resin composition layer, and then a KOH developer (KOH, containing nonionic surfactant, trade name: CDK) -1, manufactured by Fuji Film Electronics Materials Co., Ltd. diluted 100 times with pure water) at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, followed by heat treatment at 220 ° C. for 30 minutes, and a dark color separation wall having the shape shown in FIG. Got.

[Plasma water repellency treatment]
Plasma water repellency treatment was performed on the substrate on which the dark color separation wall was formed using a cathode coupling type parallel plate plasma processing apparatus under the following conditions.
Gas used: CF ₄ gas flow rate: 80 sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

(Pixel formation)
Next, using an ink jet apparatus, each of R, G, and B inks was applied to the gaps between the black matrix pattern-like separation walls and colored.
In this ink, among the following components, first, a pigment, a polymer dispersant and a solvent are mixed, and a pigment dispersion is obtained using a three roll and bead mill. The pigment dispersion is sufficiently stirred with a dissolver or the like. While adding other materials little by little, R (red) ink 1 was prepared. At this time, the viscosity of the R (red) ink 1 was 7.5 cPs. The viscosity of the red ink was measured at a temperature of 20 ° C. using a viscosity measuring device VIBROVISCOMETER CJV5000 (manufactured by A & D).
<Composition of R ink 1>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 3 parts ・ First epoxy resin (novolak type epoxy resin) Epicoat 154 manufactured by Yuka Shell
2 parts, 2nd epoxy resin (neopentyl glycol diglycidyl ether) 5 parts, curing agent (trimellitic acid) 4 parts, solvent: 80 parts ethyl 3-ethoxypropionate

Further, C.I. I. Pigment Red 254 instead of C.I. I. G (green) ink 1 was prepared in the same manner as in the R ink except that the same amount of pigment green 36 was used. Further, C.I. I. Pigment Red 254 instead of C.I. I. B (blue) ink 1 was prepared in the same manner as in the R ink except that the same amount of pigment blue 15: 6 was used.
The color filter after pixel coloring was baked in an oven at 230 ° C. for 30 minutes, whereby both the black matrix and each pixel were completely cured to obtain a color filter.

[Evaluation]
(Evaluation of blackness of dark color separation wall)
A measurement sample thin film layer having an OD of 3.0 or less was formed on a glass plate in the same manner as in the method of creating a dark color separation wall except that the entire surface of the sample was exposed without using an exposure mask. The absorbance of this sample in the wavelength region of 450 nm to 650 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100). Values of 500 nm and 600 nm were obtained from this chart and calculated by the following formula. However, the absorbance of the glass substrate was separately measured by the same method (OD ₀ ), and the values obtained by subtracting the respective OD ₀ values were taken as the absorbance at 600 nm and the absorbance at 500 nm, respectively. Next, using a contact type surface roughness meter P-10 (manufactured by KLA Tencor Co., Ltd.), the film thickness of the measurement sample was measured, and it was prepared in the example from the relationship between the absorbance and the film thickness of the measurement result. The absorbance of the thick color separation wall was calculated.
Blackness = absorbance at 600 nm / absorbance at 500 nm (evaluation of absorbance at 555 nm)
A measurement sample thin film layer having an OD of 3.0 or less was formed on a glass plate in the same manner as in the method of creating a dark color separation wall except that the entire surface of the sample was exposed without using an exposure mask. Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100), the absorbance of this sample at a wavelength of 555 nm was measured (OD), and the absorbance of the glass substrate was separately measured by the same method (OD ₀ ). _The value obtained by subtracting ₀ was defined as the absorbance at 555 nm of the dark color separation wall. Next, using a contact type surface roughness meter P-10 (manufactured by KLA Tencor Co., Ltd.), the film thickness of the measurement sample was measured, and it was prepared in the example from the relationship between the absorbance and the film thickness of the measurement result. The absorbance of the thick color separation wall was calculated.

(Evaluation of height)
The height of the dark color separation wall was measured using a tactile surface roughness meter P-10 (manufactured by KLA Tencor).

(Evaluation of color mixture between pixels (1))
The obtained color filter was visually observed with a 200 × optical microscope to examine the presence or absence of color mixture between pixels. 1000 pixels were observed and divided into the following ranks. The results are shown in Table 1. Allowable are those of A rank and B rank.
Rank A: No color mixing B Rank: Color mixing 1 to 3 places C Rank: Color mixing 4 to 10 places D Rank: Color mixing 11 places or more

(Evaluation of color mixture between pixels (2))
The obtained color filter is visually observed with a 200 × optical microscope from the side opposite to the side where the pixels are formed on the substrate (the side that becomes the viewer side when the panel is formed), and the presence or absence of color mixture between the pixels is examined. It was. 2,000 pixels were observed and divided into the following ranks. The results are shown in Table 1. Allowable are those of A rank and B rank.
Rank A: No color mixing B Rank: Color mixing 1-6 places C Rank: Color mixing 7-20 places Rank D: Color mixing 21 places or more

(Evaluation of white spots between pixels)
The obtained color filter is observed with a 200 × optical microscope from the surface opposite to the side where the pixels are formed on the substrate (the surface that becomes the observer side when the panel is formed), and white spots (ink adheres to the pixels). Evaluation was made on the part that was not done).
The observation of white spots was performed at arbitrary 100 points in the pixel that had a convex corner toward the dark color separation wall.
Rank A: There are no white spots.
B rank: There are less than 5 white spots.
C rank: Color loss is 5 or more and less than 10.
D rank: 10 or more white spots.

[Example 2]
In Example 1, a dark color separation wall having the shape shown in FIG. 18B was obtained in the same manner as in Example 1 except that the laser light exposure pattern was changed to that shown in FIG.
A color filter was produced for this sample in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
≪Preparation of photosensitive resin transfer material≫
On the 75 μm thick polyethylene terephthalate film temporary support, the following thermoplastic resin layer, oxygen barrier layer (intermediate layer) and dark photosensitive resin composition layer are provided in order from the temporary support, and protection is provided thereon. A film (12 μm thick polypropylene film) was pressure-bonded to obtain a photosensitive resin transfer material.

(Formation of thermoplastic resin layer)
The following coating solution for a thermoplastic resin layer was applied using a slit nozzle so that the dry film thickness was 14.5 μm and dried at 100 ° C. for 3 minutes to obtain a thermoplastic resin layer.
<Coating liquid formulation for thermoplastic resin layer>
Methanol 11.1 parts Propylene glycol monomethyl ether acetate 6.4 parts Methyl ethyl ketone 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55) /11.7/4.5/28.8, molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts · Surfactant 1 0.54 parts

(Formation of oxygen barrier layer (intermediate layer))
The following oxygen barrier layer (intermediate layer) coating solution was applied onto the above-mentioned thermoplastic resin layer using a slit nozzle so that the dry film thickness was 1.6 μm and dried at 100 ° C. for 3 minutes. A barrier layer (intermediate layer) was formed.
<Prescription of coating solution for oxygen barrier layer (intermediate layer)>
Polyvinyl alcohol 2.1 parts (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
-Polyvinylpyrrolidone 0.95 part (PVP, K-30; made by ASP Japan)
・ Methanol 44 parts ・ Distilled water 53 parts

(Formation of dark photosensitive resin composition layer)
A dark color photosensitive resin composition of Example 1 was applied to the upper intermediate layer using a slit-like nozzle so that the dry film thickness was 2.2 μm, and dried at 100 ° C. for 3 minutes. A functional resin composition layer was formed.

≪Dark color separation wall formation≫
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

  After peeling off the protective film of the photosensitive resin transfer material, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries (Lamic II type)), rubber roller temperature 130 ° C., linear pressure 100 N / Cm and a conveyance speed of 2.2 m / min were laminated to form a dark photosensitive resin composition layer.

  Next, the sample was exposed in the same manner as in Example 1.

Next, a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film 10 times with pure water) It was subjected to shower development at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier layer.
Subsequently, sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: T-CD1, manufactured by Fuji Photo Film, diluted 5 times with pure water) was used for shower development at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the dark photosensitive resin composition layer.
Subsequently, using detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film)”, 33 ° C., 20 seconds, cone type nozzle pressure 0 Residue was removed with a rotating brush having a shower and nylon bristles at 0.02 MPa, and a pattern image was obtained, and then the substrate was further post-irradiated with light of 500 mJ / cm ² from the resin layer side with an ultrahigh pressure mercury lamp. After the exposure, heat treatment was performed at 220 ° C. for 15 minutes to obtain a dark color separation wall having the shape shown in FIG.

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) of a fluorosurfactant (Sumitomo 3M, Florad FC-430) is previously added onto the substrate on which the dark color separation wall is formed. An alkali-soluble photosensitive resin (Positive photoresist AZP4210, manufactured by Hoechst Shapan Co., Ltd.) is applied using a slit-like nozzle so as to have a film thickness of 2 μm, and is heated at 90 ° C. for 30 minutes in a hot air circulating dryer. The heat treatment was performed.
Next, the substrate was exposed from the back of the substrate on which the separation wall was formed with an exposure amount of 110 mJ / cm ² (38 mW / cm ² × 2.9 seconds) through the dark separation wall, and an inorganic alkali developer (Hoechst Japan Co., Ltd.) Made by AZ400K Developer, 1: 4), and then rinsed in pure water for 30-60 seconds to form a water-repellent resin layer on the dark-colored separation wall. The surface energy difference was provided. The surface energy inside and outside the pixel after forming the water-repellent resin layer is 10 to 15 dyn / cm (10 to 15 × 10 ⁻³ N / m) outside the pixel (on the resin layer), and 55 dyn / in the pixel (on the glass substrate). It was around cm (55 × 10 ⁻³ N / m).
A color filter was produced for this sample in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

-3
[Reference Example 1]
In Example 1, a color filter was prepared in the same manner as in Example 1 except that the dark color separation wall formation was changed to the following mask exposure, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

-4
<Mask exposure>
In 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 the dark color The distance between the photosensitive resin composition layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² . The exposure was performed in a nitrogen atmosphere with a nitrogen purge. However, the mask shape is the shape shown in FIG.

[Reference Example 2]
In Example 1, dark color separation wall formation was performed by mask exposure similar to that of Reference Example 1 above, and a color filter was prepared in the same manner as in Example 1 except that the ink formulation was changed to the following formulation: Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
<Composition of R ink 2>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 7 parts ・ First epoxy resin (novolak type epoxy resin) Epicoat 154 manufactured by Yuka Shell Co.)
3 parts ・ Curing agent (trimellitic acid) 4 parts ・ Solvent: 80 parts ethyl 3-ethoxypropionate In this ink, first of all, the pigment, the polymer dispersant and the solvent are mixed, and the three-roll A bead mill was used to obtain a pigment dispersion, and while the pigment dispersion was sufficiently stirred with a dissolver or the like, other materials were added little by little to prepare R (red) ink 2. At this time, the viscosity of the R (red) ink 2 was 11 cPs.
Further, C.I. I. Pigment Red 254 instead of C.I. I. G (green) ink 2 was prepared in the same manner as the R ink except that the same amount of pigment green 36 was used. Further, C.I. I. Pigment Red 254 instead of C.I. I. B (blue) ink 2 was prepared in the same manner as in the R ink except that the same amount of pigment blue 15: 6 was used.

[Reference Example 3]
In Example 1, dark color separation wall formation was performed by mask exposure similar to that of Reference Example 1 above, and a color filter was prepared in the same manner as in Example 1 except that the ink formulation was changed to the following formulation: Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
<Composition of R ink 3>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 8.5 parts ・ First epoxy resin (novolak type) Epoxy resin, Epicoat 154 manufactured by Yuka Shell
1.5 parts ・ Curing agent (trimellitic acid) 4 parts ・ Solvent: 80 parts ethyl 3-ethoxypropionate In this ink, first of all, the pigment, polymer dispersant and solvent are mixed. Using this roll and a bead mill, a pigment dispersion was obtained. While the pigment dispersion was sufficiently stirred with a dissolver or the like, other materials were added little by little to prepare R (red) ink 3. The viscosity of R (red) ink 3 at this time was 14 cPs.
Further, C.I. I. Pigment Red 254 instead of C.I. I. G (green) ink 3 was prepared in the same manner as in the R ink except that the same amount of pigment green 36 was used. Further, C.I. I. Pigment Red 254 instead of C.I. I. B (blue) ink 3 was prepared in the same manner as in the R ink except that the same amount of pigment blue 15: 6 was used.

[Example 4]
In Example 2, a color filter was produced in the same manner as in Example 2 except that the ink formulation was changed to the same formulation as in Reference Example 3, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Examples 5 to 7]
In Examples 1 to 3, color filters were prepared in the same manner except that the water repellent treatment was not performed, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

As is apparent from Table 1, the color filter of the present invention in the examples has no color mixture between pixels and is preferable for display device applications. In the method for producing a color filter of the present invention, since a mask is not used, the shape of the dark color separation wall can be easily and freely changed according to the physical properties of the ink, and the darkness suitable for preventing mixed colors and white spots is prevented. Color separation walls can be formed. The color filters of Examples 1 to 3 subjected to the water repellent treatment were excellent in terms of no color mixing.
On the other hand, according to Reference Examples 2 and 3, it was found that when the physical properties of the ink were changed, a problem occurred due to the shape of the dark color separation wall.

[Example 8]
Using the color filters obtained in Examples 1 to 7, liquid crystal display devices 1 to 7 were produced as follows.

(Overcoat layer formation)
The obtained color filter is cleaned with a low-pressure mercury lamp (effective wavelength 254 nm) UV cleaning device to remove residues and foreign matters, and then the following transparent overcoat agent is applied and baked. After coating the front surface so that the thickness of the film was 1.5 μm, it was baked at 230 ° C. for 40 minutes. At this time, the coating liquid for forming the transparent overcoat layer was prepared by mixing a polyamic acid of the following chemical formula 6 and an epoxy compound of the chemical formula 7 in a weight ratio of 3: 1.

(Formation of ITO)
ITO (indium tin oxide) was formed on the color filter on which the overcoat layer was formed by sputtering to obtain an ITO transparent electrode substrate.

(Spacer formation)
In the same manner as the spacer forming method described in [Example 1] of JP-A-2004-240335, a spacer was formed at a location corresponding to the upper part of the dark color separation wall on the ITO transparent electrode produced above.

(Formation of liquid crystal alignment control protrusions)
Using the following positive photosensitive resin layer coating solution, a liquid crystal alignment control protrusion was formed at a location corresponding to the upper portion of the colored pixel on the ITO transparent electrode on which the spacer was formed.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. Display device substrates 1 to 3 were obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.

<Positive photosensitive resin layer coating solution formulation>
・ Positive resist solution (FH-2413F manufactured by Fujifilm Electronics Materials Co., Ltd.) 53.3 parts ・ Methyl ethyl ketone 46.7 parts ・ Surfactant 1 0.04 parts

(Creation of liquid crystal display device)
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant.
A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained.
Next, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as a green (G) LED, and DB1112H (Stanley (as a blue LED)) A side light type backlight is constructed using a chip type LED manufactured by Co., Ltd. and placed on the back side of the liquid crystal cell provided with the polarizing plate, thereby producing the liquid crystal display devices 1 to 7 of the present invention. did.

[Evaluation]
When the obtained liquid crystal display devices 1 to 7 were displayed in white and displayed black, the display quality was visually observed. A case where a pure color of white or black is displayed is considered good, and a case where it appears reddish is regarded as bad.

  The screens of the liquid crystal display devices provided with the color filters prepared in the examples were all good colors with no color mixing. Further, in both the white display and black display states, there was no deterioration in display quality that was slightly reddish, and the display quality was excellent.

It is a perspective view which shows the external appearance of the exposure unit which concerns on this invention. It is a perspective view which shows the structure of the scanner of the exposure unit which concerns on this invention. (A) is a top view which shows the exposed area | region formed in a photosensitive material, (B) is a figure which shows the arrangement | sequence of the exposure area by each exposure head. 1 is a perspective view showing a schematic configuration of an exposure head according to the present invention. (A) is sectional drawing of the subscanning direction along the optical axis which shows the structure of the exposure head shown in FIG. 4, (B) is a side view of (A). It is the elements on larger scale which show the structure of a digital micromirror device (DMD). (A) And (B) is explanatory drawing for demonstrating operation | movement of DMD. (A) And (B) is a top view which compares and shows the arrangement | positioning of an exposure beam, and a scanning line by the case where it does not arrange | position inclined DMD and the case where it arranges inclined. (A) is a perspective view showing a configuration of a fiber array light source, (B) is a partially enlarged view of (A), (C) and (D) are plan views showing an arrangement of light emitting points in a laser emitting portion. is there. It is a figure which shows the structure of a multimode optical fiber. It is a top view which shows the structure of a combined laser light source. It is a top view which shows the structure of a laser module. It is a side view which shows the structure of the laser module shown in FIG. It is a partial side view which shows the structure of the laser module shown in FIG. (A) And (B) is sectional drawing along the optical axis which shows the difference of the focal depth in the conventional exposure apparatus, and the focal depth in the exposure unit which concerns on this invention. (A) And (B) is a figure which shows the example of the use area | region of DMD. (A) is a side view when the use area of DMD is appropriate, (B) is a sectional view in the sub-scanning direction along the optical axis of (A). (A) is a top view which shows an example of the deep color separation wall in this invention. (B) is a plan view showing another example of the dark color separation wall in the present invention.

Explanation of symbols

10A: Light transmissive substrate 14: Pixel (R, G, B), Color filter 14A: Pixel part (transmission display part)
14B ... Pixel part (reflection display part)
50 ... Digital micromirror device (DMD)
54 ... Lens system 66 ... Fiber array light source 166 ... Exposure head (exposure unit according to the present invention)
171 ... Pixel unit 172 ... Dark color separation image wall

Claims (7)

A method of manufacturing a color filter having a pixel group consisting of a plurality of pixels having two or more colors on a substrate, wherein the pixels are isolated from each other by a dark color separation wall. A photosensitive resin composition for forming a dark color separation wall formed on a substrate while the wall satisfies the following condition (A) and light is modulated on the dark color separation wall based on the separation wall image data A method for producing a color filter, wherein a physical layer is subjected to relative scanning exposure, followed by development to form a separation wall, and then the pixels are formed by applying droplets of a colored liquid composition.
(A) The ratio A ₆₀₀ / A ₅₀₀ of the absorbance A _{600 at 600} nm and the absorbance A ₅₀₀ at ₅₀₀ nm is 0.7 to 1.4. 2. The method for producing a color filter according to claim 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. . The method for producing a color filter according to claim 1 or 2, wherein the dark color separation wall has an absorbance at 555 nm of 2.5 or more. 4. The color filter according to claim 1, wherein the photosensitive resin composition layer for dark color separation walls is formed by the following (1) or (2). Production method.
(1) A photosensitive resin composition containing a colorant is applied to a substrate and dried.
(2) A photosensitive transfer layer containing a colorant is formed by transferring the photosensitive transfer layer to a substrate using a transfer material formed on a temporary support. The method for producing a color filter according to claim 1, wherein the droplet application is an inkjet method. A color filter manufactured by the manufacturing method according to claim 1. A display device comprising the color filter according to claim 6.

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