KR20060109351A - Method of manufacturing color filter, color filter and display device having the same - Google Patents

Abstract

A color filter, a manufacturing method thereof, and a display device having the same are provided to change configuration of a color separation wall by performing an exposure process without using an exposure mask. A photosensitive material(150) is absorbed on the surface of a planar stage(152). An installation mount(156), which has a thick plate shape, is supported by four leg portions(154). Two guides are elongated along the moving direction of the stage. The stage is supported to reciprocate by the guide and oriented in the stage moving direction. A gate(160) is formed at the center of the installation mount. A scanner(162) and plural detection sensors(164) are formed at both ends of the installation mount about the gate. The scanner and the detection sensors are attached to the gate and fixed above the stage moving direction.

Description

A manufacturing method of a color filter, a color filter, and a display apparatus having the same {METHOD OF MANUFACTURING COLOR FILTER, COLOR FILTER AND DISPLAY DEVICE HAVING THE SAME}

1 is a perspective view showing the appearance of an exposure unit according to the present invention.

2 is a perspective view showing the configuration of a scanner of the exposure unit according to the present invention.

Fig. 3A is a plan view showing the exposed area formed in the photosensitive material, and (B) is a diagram showing the arrangement of the exposed areas by the respective exposure heads.

4 is a perspective view showing a schematic configuration of an exposure head according to the present invention.

5: (A) is sectional drawing of the sub scanning direction along the optical axis which shows the structure of the exposure head shown in FIG. 4, (B) is a side view of (A).

6 is a partially enlarged view showing the configuration of a digital micromirror device (DMD).

7A and 7B are explanatory diagrams for explaining the operation of the DMD.

8A and 8B are plan views showing the arrangement of the exposure beam and the scanning line in comparison with the case where the DMD is not inclined and in which the DMD is inclined.

Fig. 9 (A) is a perspective view showing the structure of a fiber array light source, (B) is a partially enlarged view of (A), and (C) and (D) are plan views showing the arrangement of light emitting points in the laser output unit. to be.

10 is a diagram illustrating a configuration of a multimode optical fiber.

11 is a plan view showing the configuration of a combined laser light source.

12 is a plan view showing the configuration of a laser module.

It is a side view which shows the structure of the laser module shown in FIG.

FIG. 14 is a partial side view illustrating the configuration of the laser module shown in FIG. 12.

15A and 15B are sectional views along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus in the exposure unit according to the present invention.

16A and 16B are diagrams showing an example of a use area of the DMD.

Fig. 17 (A) is a side view when the use area of the DMD is appropriate, and (B) is a sectional view of the sub scanning direction along the optical axis of (A).

Fig. 18A is a plan view showing an example of the deep color separation wall in the present invention, and (B) is a plan view showing another example of the deep color separation wall in the present invention.

(Explanation of the sign)

10A... Light transmissive substrate

14... Pixel (R, G, B), Color Filter

14A... Pixel section (transmission display section)

14B. Pixel section (reflection display section)

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 part

172... Deep wall

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

The color filter for display device is a structure which arrange | positioned the red, green, blue dot image on matrix, such as glass, respectively, and divided the boundary into the deep color isolation wall, such as a black matrix. Conventionally, as a manufacturing method of such a color filter, using the board | substrate, such as glass, as a support body, the coloring photosensitive resin liquid method by 1) a dyeing method, 2) printing method, 3) application | coating of the colored photosensitive resin liquid, and exposure and image development are repeated. (Coloring resist method) (for example, Japanese Patent Application Laid-Open No. Hei 1-5244949), 4) a method of transferring an image formed on a support sequentially, on a final or branched body, and 5) pre-colored photosensitive resin liquid A method of forming a multicolored image by forming a colored layer by coating on a support, and then directly transferring the photosensitive colored layer on a substrate, repeating exposure and developing by the number of colors, or the like (transfer method). This is known (for example, Japanese Patent Laid-Open No. 61-99102). Moreover, the method of using the inkjet method (Japanese Patent Laid-Open No. 8-227012) is also known.

Among these methods, the colored resist method has high positional accuracy and can produce a color filter. However, the colored resist method is not advantageous in terms of cost due to high loss in coating of the photosensitive layer resin solution. On the other hand, the inkjet method is advantageous in terms of cost because there is little loss of the resin liquid.

In the case of forming the color filter by the inkjet method, a dark separation wall (black matrix) is formed by collectively exposing a mercury lamp or the like on a glass substrate using an exposure mask, and then spraying coloring ink therein to form pixels. The method is usually used (for example, Japanese Patent Laid-Open No. 2003-337426).

In the case of forming the pixel of the color filter in the inkjet method, the sprayed coloring ink may be mixed with the adjacent pixels beyond the deep color separation wall and cause so-called mixed color, which is a big problem when this method is used. In order to prevent color mixing, there is a problem that deterioration of the display quality is caused unless measures such as adjusting the height of the deep isolation wall to some extent or adjusting the cross-sectional shape of the deep isolation wall are taken.

It is necessary to study the shape (for example, the radius of curvature of the inner part of the deep isolation wall) according to the physical properties of the ink (viscosity or surface tension). That is, when the ink used changes and physical properties change, it is necessary to change an expensive exposure mask.

The present invention provides a method of manufacturing a color filter for producing a pixel free of mixed color at low cost. The present invention also provides a color filter having a pixel that does not have mixed colors. In addition, the present invention provides a display device using a color filter having the pixel without the mixed color.

In view of the above circumstances, the present inventors have made intensive studies, and as a result, by using laser pattern exposure without using an exposure mask, the shape of the deep color separation wall can be freely changed, and as a result, the occurrence of mixed color can be prevented, We also found a valid method in terms of cost. In addition, the light is modulated on the basis of the isolation wall image data, while the photosensitive resin composition layer for formation of the deep color separation wall formed on the substrate is subjected to relative scanning exposure, and then developed to form the isolation wall. The shape can be changed, and as a result, the generation | occurrence | production of the mixed color can be prevented, and also the effective method was found from a viewpoint of cost, and the present invention was completed.

In other words, the present invention is (1) a method of manufacturing a color filter,

Forming a deep color separation wall having a height of 1.0 mu m or more by maskless exposure and development; And

After the deep color separation wall forming step, forming a pixel group by applying a droplet containing a colored liquid composition;

The color filter

Board; And

Comprising a plurality of said pixel groups having at least two colors formed on said substrate: and

The pixel is separated from each other by the deep color separation wall.

Moreover, this invention is (2) the manufacturing method of a color filter,

Forming a separation wall by subjecting the deep color separation wall to light by modulating light based on the separation wall image data, subjecting the deep color separation wall-forming photosensitive resin composition layer to be subjected to relative scan exposure and development; And

After the said relative scanning exposure process, the process of forming a pixel group by provision of the droplet containing a colored liquid composition is provided:

The color filter

Board; And

Comprising a plurality of said pixel groups having at least two colors formed on said substrate:

The pixels are isolated from each other by the deep color separation wall: and

The manufacturing method characterized by the above-mentioned ratio (A ₆₀₀ / A ₅₀₀ ) of the absorbance (A ₆₀₀ ) at ₆₀₀ nm and the absorbance (A ₅₀₀ ) at ₅₀₀ nm of the deep color separation wall is 0.7 to 1.4. .

Moreover, this invention provides the color filter manufactured by the manufacturing method as described in said (1) or (2).

In addition, the present invention provides a display device having the color filter.

The manufacturing method of the color filter of this invention has the pixel group which consists of a some pixel which has two or more colors of colors on a board | substrate, and is a manufacturing method of the color filter in which the said pixel is isolate | separated from each other by the deep color separation wall. The deep color separation wall is developed after maskless exposure, and formed to a height of 1.0 mu m or more, and then the pixel is formed by dropping a colored liquid composition.

The deep color separation wall is produced by forming a photosensitive resin composition layer (a deep photosensitive resin composition layer) containing a colorant on the substrate and then exposing and developing a maskless laser pattern under a lean oxygen atmosphere. The photosensitive resin composition layer is formed by a method of applying a deep photosensitive resin composition (coating method) and a method of transferring a photosensitive transfer material (transcription method).

In a preferred embodiment, the method for producing a color filter according to the present invention comprises the steps of performing a relative scan exposure on a deep color separation wall-forming photosensitive resin composition layer formed on a substrate while modulating light on the deep color separation wall based on the separation wall image data. Characterized in that it comprises a.

It is preferable that the value of the "absorbance at 600 nm / absorbance in 500 nm" of the deep color isolation wall in this invention is a range of 0.7-1.4. The 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 outside the above range, it is not preferable because the deep color separation wall is colored.

In order to obtain a color filter of good image quality, the color tone of the deep color isolation wall is important in addition to preventing the mixing of the pixels. Since the side of the deep isolation wall is not normally vertical, the color of the pixel such as red, blue, green and the color of the deep isolation wall is displayed at the peripheral portion of the pixel. In other words, no matter how pure the color of the pixels such as red, blue, green, etc., the color of the rich isolation wall is not achromatic, it does not become a good color tone when viewed from the whole screen.

As the color separation wall color tone, it is preferable to be blackish black. As the colorant of the color separation wall, for example, black colorants such as carbon black, titanium black, graphite, metal compounds (for example, iron oxide and titanium oxide) are used. It is desirable to.

However, what is generally called a black colorant (black pigment or black dye) is not strictly black (the absorbance of visible light is the same over the entire wavelength range). For example, even in the case of carbon black, which is a typical black pigment, the color tone changes depending on the manufacturing method, particle size, structure, and the like, but the particle size greatly contributes to this color tone.

From the viewpoint of dispersion stability, the colorant (pigment) used in the present invention preferably has a number average particle size of 0.001 to 0.1 µm, and more preferably 0.01 to 0.08 µm. Moreover, when the pigment number average particle diameter exceeds 0.1 micrometer, cancellation of the polarization by a pigment arises and contrast falls and it is unpreferable.

It is preferable that the particle diameter of the coloring agent in the manufacturing method of the color filter of this invention especially exists in the range containing 10-75 nm, and more preferably in the range which is 12-50 nm in the aspect containing the said relative scanning exposure process. And it is more preferable to exist in the range of 15-40 nm. If the particle size of the colorant is less than 10 nm or exceeds 75 nm, the value of A ₆₀₀ / A ₅₀₀ deviates from the range of 0.7 to 1.4, which is not preferable.

In addition, the "particle diameter" here means the diameter when the electron microscope photograph image of particle | grains is made into the circle of the same area. In addition, a "number average particle diameter" calculates said particle diameter about many particle | grains, and means these 100 average values.

The deep color separation wall forms a photosensitive resin composition layer containing a colorant on the substrate ("photosensitive resin composition layer for deep color separation walls" or "dark photosensitive resin composition layer") on the substrate, thereby separating the deep color separation wall from the wall. It is preferable to manufacture by carrying out the relative scan exposure of the photosensitive resin composition layer for formation of the deep-color isolation wall formed on the board | substrate, modulating light based on image data, and developing after that. The photosensitive resin composition layer may be formed by a method of applying a deep photosensitive resin composition (coating method) or a method of transferring a photosensitive transfer material (transcription method).

Hereinafter, the deep color photosensitive resin composition and the photosensitive transfer material will be described.

(Dark Photosensitive Resin Composition)

The deep isolation wall on the substrate is formed of a photosensitive resin composition (also referred to as a "dark photosensitive resin composition" or a "dark composition") containing a colorant. Here, a deep color composition is a composition which has high optical density, ie, high absorbance in 555 nm. It is preferable that the said optical density (the said absorbance) at the time of forming the coating film of the thickness corresponded to the height of a deep color isolation wall is 2.5 or more, It is more preferable to exist in the range of 2.5-10.0, and to exist in the range of 2.5-6.0. More preferably, it is especially preferable to exist in the range of 3.0-5.0.

In addition, since the deep color composition is preferably cured with a photo-opening clock as described later, the absorbance with respect to an exposure wavelength (generally an ultraviolet region) is also important. That is, it is preferable that the said optical density (the said absorbance) at the time of forming the coating film of the thickness corresponded to the height of a deep color isolation wall exists in the range of 2.0-10.0, More preferably, it exists in the range of 2.5-6.0 It is preferable and it is most preferable to exist in the range of 3.0-5.0. If it is less than 2.0, the shape of the isolation wall may not be desired. If it exceeds 10.0, the polymerization cannot be started and it becomes difficult to produce the isolation wall itself.

Hereinafter, the component in the said composition is demonstrated.

(coloring agent)

Specific examples of the colorant used in the present invention include those having a color index (C.I.) number described in the following dyes and pigments.

Organic pigments, inorganic pigments, dyes and the like can be preferably used for the deep color composition of the present invention. When light shielding properties are required for the photosensitive resin layer, metal oxide powders such as carbon black, titanium oxide, iron tetraoxide, and metal sulfide powders In addition to the light-shielding agent called metal powder, mixtures of pigments, such as red, blue, and green, can be used. Known coloring agents (dyes, pigments) can be used. When using a pigment in the said known coloring agent, it is preferable to disperse | distribute uniformly in a deep color composition.

As said well-known dye or pigment, the pigment and dye of Unexamined-Japanese-Patent No. 2005-17716 [0038]-[0053] specifically, are described in Unexamined-Japanese-Patent No. 2004-361447 [0068]-[0072] A pigment and the coloring agent of Unexamined-Japanese-Patent No. 2005-17521-[0088] can be used preferably.

In this invention, it is preferable to use a black coloring agent among the said coloring agents. Examples of the black colorant further include carbon black, titanium carbon, iron oxide, titanium oxide, graphite, and the like, and among them, carbon black is preferable.

It is preferable that the ratio of the coloring agent in solid content of the said rich color composition exists in the range of 30-70 mass% from a viewpoint of shortening image development time fully, It is more preferable to exist in the range of 40-60 mass%, 50-55 It is more preferable to exist in the range of mass%.

It is preferable to use the said pigment as a dispersion liquid. This dispersion liquid can be prepared by adding and dispersing the composition obtained by mixing the said pigment and a pigment dispersant beforehand to the organic solvent (or vehicle) mentioned later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state, and is liquid, and contains a portion (binder) that binds to the pigment to harden the coating film and a component (organic solvent) that dissolves and dilutes the coating film. . There is no restriction | limiting in particular as a disperser used when disperse | distributing the said pigment. Examples of the disperser include the kneader, roll mill, art rider, super mill, dissolver, homomixer, and sand described in Asakura Kunizo, Dictionary of Pigments, First Edition, Asakura Bookstore, 2000, Section 438. Known dispersers such as mills are included. Moreover, you may finely grind using frictional force by the mechanical grinding described in 310 of the said Asakura literature.

It is preferable that the deep color composition in this invention contains a binder (resin, a polymer), an initiator, and a monomer at least other than the said coloring agent. If necessary, further known additives such as plasticizers, fillers, stabilizers, polymerization inhibitors, surfactants, solvents, adhesion promoters and the like can be added. In addition, the deep color composition is preferably softened or tacky at a temperature of at least 150 ° C. or lower, and preferably thermoplastic. From this point of view, it can be modified by adding a compatible plasticizer.

(Binder (resin, polymer))

As a binder used for a deep color composition, the polymer which has polar groups, such as a carboxylic acid group and a carboxylate group, in a side chain is preferable. Examples include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like described in Japanese Patent Application Laid-Open No. 59-71048; Can be. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned. In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further preferred examples thereof include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Patent No. 4139391 and polyunsaturated copolymers of benzyl (meth) acrylate and (meth) acrylic acid and other monomers. Can be. The binder polymers having these polar groups may be used alone or in a state of a composition used in combination with an ordinary film-forming polymer.

(Initiator)

As a method of hardening a deep color composition, although the thermal clock which uses a thermal initiator and the optical clock which uses a photoinitiator are common, in this invention, it is preferable to use a photoinitiator. The photopolymerization initiator used herein can generate active species for initiating polymerization of the polyfunctional monomer described later by irradiation (also referred to as exposure) of radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, and X-ray. It is a compound and can be suitably selected from a well-known photoinitiator or photoinitiator system.

For example, trihalomethyl group-containing compound, acridine compound, acetophenone compound, biimidazole compound, triazine compound, benzoin compound, benzophenone compound, α-diketone compound, polynuclear quinone compound, A xanthone compound, a diazo compound, etc. are mentioned.

Specifically, the trihalomethyl oxazole derivative substituted with the trihalomethyl group or the s-triazine derivative described in Japanese Patent Laid-Open No. 2001-117230, the trihalomethyl-s described in the specification of US Pat. Trihalomethyl group-containing compounds such as triazine compounds and trihalomethyloxadiazole compounds described in the specification of US Patent No. 4212976;

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, Acridine-based compounds such as bis (9-acridinyl) alkanes such as 11-bis (9-acridinyl) undecane and 1,12-bis (9-acridinyl) dodecane;

6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2 Triazine-based compounds such as, 4-bis (trichloromethyl) -s-triazine; In addition, 9,10- dimethyl benzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaaryl biimidazole / mercapto benzimidazole, benzyl dimethyl ketal, thioxanthone / amine, 2,2 '-Bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Among these, at least 1 sort (s) chosen from a trihalomethyl group containing compound, an acridine type compound, an acetophenone type compound, a biimidazole type compound, and a triazine type compound is preferable, and a trihalomethyl group containing compound and an acridine type are especially preferable. It is preferable to contain at least 1 sort (s) chosen from a compound. Trihalomethyl group-containing compounds and acridine-based compounds are useful in terms of versatility and low cost.

As a trihalomethyl group containing compound, 2-trichloromethyl-5- (p-styryl styryl) -1,3,4-oxadiazole is especially preferable, and 9-phenylacrylic as an acridine type compound is preferable. Dine, and also 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxy Trihalomethyl group-containing compounds such as styryl) -5-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. It is preferable that the total amount in the deep color composition of the said initiator exists in the range of 0.1-20 mass% of the total solid (mass) of a deep color composition, and it is especially preferable to exist in the range of 0.5-10 mass%. When the total amount is less than 0.1% by mass, the efficiency of photocuring of the composition may be low, which may require a long time for exposure. When the total amount exceeds 20% by mass, the image pattern formed may be broken or rough on the pattern surface when developing. This may become easy to see.

The initiator may be configured by using a hydrogen donor together. As said hydrogen donor, since a sensitivity can be improved more, a mercaptan type compound, an amine compound, etc. which are defined below are preferable. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the said photoinitiator by exposure.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus and having one or more, preferably 1 to 3, and more preferably 1 to 2 mercapto groups directly bonded to the mother nucleus (hereinafter, , "Mercaptan-based hydrogen donor"). In addition, the amine compound is a compound having a benzene ring or a heterocycle as a parent nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, " Amine-based hydrogen donor "). Moreover, these hydrogen donors may have a mercapto group and an amino group simultaneously.

Specific examples of the mercaptan-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadia Sol, 2-mercapto-2,5-dimethylaminopyridine, and the like. Among these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is especially preferable.

Specific examples of the amine-based hydrogen donor include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiope Non-ethyl, dimethyl-4- benzoate, 4-dimethylamino benzoic 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 may be used alone or in combination of two or more kinds thereof, and at least one mercaptan-based compound is used because the formed image is hardly eliminated from the permanent supporter upon development, and the strength and sensitivity can be improved. Preference is given to using a combination of a hydrogen donor and at least one amine hydrogen donor.

Specific examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4 '. -Bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) Benzophenone etc. are mentioned. More preferred combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, Particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

In the case where the mercaptan-based hydrogen donor and the amine-based hydrogen donor are combined, the mass ratio (M: A) of the mercaptan-based hydrogen donor (M) and the amine-based hydrogen donor (A) is usually 1: 1 to 1: 4. Preferably, 1: 1-1: 3 are more preferable. It is preferable that the total amount in the deep color composition of the said hydrogen donor exists in the range of 0.1-20 mass% of the total solid (mass) of a deep color composition, and it is especially preferable to exist in the range of 0.5-10 mass%.

(Monomer)

As a polyfunctional monomer used for a deep color composition, the following compound can be used individually or in combination with another monomer. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, and trimetholpropane tree (meth) ) Acrylate, 2-ethyl-2-butyl-propanedioldi (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, polyoxyethylated trimetholpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenyl Benzene, 1,4-dihydroxybenzenedi (meth) acrylate, decamethylene glycoldi (meth) acrylate, styrene, diallyl fumarate, trimellitic acid triallyl, lauryl (meth) acrylate, (meth Acrylamide, Xyl Lenbis (meth) acrylamide etc. are mentioned.

Furthermore, the compound which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethyleneglycol mono (meth) acrylate, hexamethylene diisocyanate, toluene diisocyanate, xylene The reactant with diisocyanate, such as diisocyanate, can also be used.

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

It is preferable that content in the deep color composition of a polyfunctional monomer exists in the range of 5-80 mass% with respect to the total solid (mass) of a deep color composition, and it is especially preferable to exist in the range of 10-70 mass%. When the said content is less than 5 mass%, the tolerance to the alkaline developing solution in the exposure part of a composition may be inferior, and when it exceeds 80 mass%, the adhesiveness at the time of setting it as a deep color composition will increase, and handleability will fall behind. There is a fall.

(solvent)

In the deep color composition of this invention, in addition to the said component, you may use an organic solvent further. 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.

(Surfactants)

In the deep color separation wall or the photosensitive transfer material in the present invention, the deep color composition can be applied to the substrate or the support by using a slit nozzle or the like described later. The film thickness can be controlled to effectively prevent coating variations.

As said surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a preferable thing.

Moreover, it is common that content of surfactant with respect to the total solid of a deep color composition exists in the range of 0.001-1 mass%, It is preferable to exist in the range of 0.01-0.5 mass%, It exists in the range of 0.03-0.3 mass%. Is particularly preferred.

(UV absorber)

The deep color composition of this invention can contain a ultraviolet absorber as needed. As a ultraviolet absorber, in addition to the compound of Unexamined-Japanese-Patent No. 5-72724, a salicylate type, a benzophenone type, a benzotriazole type, a cyanoacrylate type, a nickel chelate type, a hindered amine type, etc. are mentioned. .

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-phenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -ceva Kate, 4-t-butylphenylsalicylate, 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-triazin-2-yl] amino} -3-phenylcoumarin, etc. The can.

Moreover, it is common that content of the ultraviolet absorber with respect to the total solid of a deep color composition exists in the range of 0.5-15 mass%, It is preferable to exist in the range of 1-12 mass%, and it exists in the range of 1.2-10 mass%. Is particularly preferred.

(Etc)

(Thermal polymerization inhibitor)

Moreover, it is preferable that the deep 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, pyrogarol, t-butylcatechol, benzoquinone, 4,4'- Thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine, etc. are mentioned. have.

Moreover, it is common that content of the thermal-polymerization inhibitor with respect to the total solid of a deep color composition exists in the range of 0.01-1 mass%, It is preferable to exist in the range of 0.02-0.7 mass%, and it exists in the range of 0.05-0.5 mass%. Is particularly preferred.

In addition, in the deepening composition in this invention, in addition to the said additive, the "adhesion adjuvant" of Unexamined-Japanese-Patent No. 11-133600, other additives, etc. can be contained.

The thickness of the deep color photosensitive resin composition layer according to the present invention depends on the solid content of the deep color photosensitive resin composition and the thickness of the color separation wall to be formed, and is not particularly limited, but is generally 1 µm or more and 1.0 to 12. It is preferable to exist in the range of micrometers, It is more preferable to exist in the range of 1.5-10 micrometers, It is still more preferable to exist in the range of 1.8-8 micrometers, It is especially preferable to exist in the range of 2-6 micrometers.

(Photosensitive transfer material)

In order to easily and inexpensively realize the shape of the isolation wall in the present invention, a deep photosensitive transfer material comprising a layer of at least a dark photosensitive resin composition on a support and an oxygen barrier layer if necessary (hereinafter, And the following methods (3) and (4) characterized by the use of a "photosensitive transfer material"). In the case where a material having an oxygen barrier layer is used, the layer made of the deep color photosensitive resin composition is protected by the oxygen barrier layer, and thus automatically becomes a lean oxygen atmosphere. Therefore, since the exposure process does not have to be performed under inert gas or reduced pressure, there is an advantage that the development process can be used as it is.

(Support)

Since the branch in the photosensitive transfer material is chemically and thermally stable and is made of a flexible material, it can be appropriately selected. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. Especially, a biaxially stretched polyethylene terephthalate film is especially preferable. It is preferable that the thickness of the said support body exists in the range of 5-300 micrometers, and it is preferable that it exists in the range of 20-150 micrometers.

(Dark Photosensitive Resin Composition Layer)

The deep color photosensitive resin composition layer in the said photosensitive transfer material is formed from the said deep color composition, and the characteristics, formation methods, etc. of the shape etc. are the same as the layer formed by the said apply | coating method, and its preferable form is also the same.

(Oxygen barrier)

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

(Thermoplastic layer)

The said photosensitive transfer material may have a thermoplastic resin layer as needed. It is preferable that such a thermoplastic resin layer is alkali-soluble, it is comprised by containing at least a resin component, and it is preferable that a substantial softening point is 80 degrees C or less as said resin component. By forming such a thermoplastic resin layer, in the deep color separation wall formation method mentioned later, favorable adhesiveness with a permanent support body can be exhibited.

Examples of the alkali-soluble thermoplastic resin having a softening point of 80 ° C. or lower include a saponified product of ethylene and an acrylic acid ester copolymer, a saponified product of a styrene and a (meth) acrylic acid ester copolymer, a saponified product of a vinyltoluene and a (meth) acrylic acid ester copolymer, and a poly And saponified products such as (meth) acrylic acid ester copolymers such as (meth) acrylic acid ester, butyl (meth) acrylate and vinyl acetate.

At least one kind of said thermoplastic resin can be suitably selected and used for a thermoplastic resin layer, and "Plastic performance manual" (Japan Plastic Industry Federation, All-Japan Plastic Molding Industry Association, Published by Industrial Association, October 1968) Soluble in alkaline aqueous solution among organic polymers having a softening point of about 80 ° C. or less.

Also in the case of an organic polymer material having a softening point of 80 ° C or higher, the actual softening point can be lowered to 80 ° C or lower by adding various plasticizers compatible with the polymer material in the organic polymer material. In addition, to these organic polymer materials, various polymers, supercooling substances, adhesion modifiers or surfactants, mold release agents, and the like may be added to the organic polymer material in order to control the adhesion to the supporting member in a range in which the actual softening point does not exceed 80 ° C.

Specific examples of the preferred plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate and cresyl diphenyl phosphate biphenyl diphenyl phosphate.

(Protective film)

On the photosensitive resin layer, it is preferable to form a thin protective film in order to protect it from contamination and damage at the time of storage. The protective film may be made of the same or similar material as the supporting member, but must be easily separated from the photosensitive resin layer. As the protective film material, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable. Moreover, it is common that the thickness of a protective film exists in the range of 4-40 micrometers, It is preferable to exist in the range of 5-30 micrometers, It is especially preferable to exist in the range of 10-25 micrometers.

(Method of Manufacturing Photosensitive Transfer Material)

The photosensitive transfer material of the present invention forms a thermoplastic resin layer by applying and drying a coating liquid (coating liquid for thermoplastic resin layer) in which an additive of a thermoplastic resin layer is dissolved on a base member, and then on a thermoplastic resin layer. A solution of an oxygen barrier layer material composed of a solvent which does not dissolve the thermoplastic resin layer is applied and dried, and then the coating liquid for the deep-colored photosensitive resin composition layer is formed by applying and drying the solvent that does not dissolve the oxygen barrier layer (intermediate layer). This can be produced. In the case where the thermoplastic resin layer is not formed, the solvent of the oxygen barrier layer becomes unnecessary.

In addition, a sheet having a thermoplastic resin layer and an oxygen barrier layer formed on the supporting member and a sheet having a dark photosensitive resin composition layer formed on the protective film are prepared, and the oxygen barrier layer and the deep photosensitive resin composition layer are in contact with each other. Also by bonding, a sheet in which a thermoplastic resin layer is formed on the support and a sheet in which a dark photosensitive resin composition layer and an oxygen barrier layer are formed on a protective film are prepared, and the thermoplastic resin layer and the oxygen barrier layer are It can also manufacture by joining each other so that it may contact.

Moreover, although application | coating in the said manufacturing method can be performed by a well-known coating apparatus etc., in this invention, it is preferable to carry out by the coating apparatus (slit coater) using a slit-shaped nozzle.

(Board)

As the substrate (permanent support), a metallic support, a metal foil support, glass, ceramic, a synthetic resin film, or the like can be used. Especially preferably, glass and a transparent synthetic resin film which are transparent and are excellent in dimensional stability are mentioned.

(Dark isolation wall)

The deep color separation wall of each pixel may be formed by a coating method using the deep color photosensitive resin composition (deep color composition) or a transfer method using a photosensitive transfer material described later. Formation may be performed in a lean oxygen atmosphere.

Here, under the lean oxygen atmosphere, the partial pressure of oxygen at the time of photocuring the deep color composition or the deep color composition layer in the present invention indicates that the oxygen partial pressure is 0.15 atm or lower, or under an oxygen barrier layer capable of blocking oxygen. In detail, it is as follows.

In general, since the partial pressure of oxygen is 0.21 atm under atmospheric pressure (1 atm), in order to lower the partial pressure of oxygen to 0.15 atm or less, (a) the atmosphere at the time of exposure is reduced to 0.71 atm or less, or (b) other than air and oxygen. Can be achieved by mixing 40 vol% or more of a gas (eg an inert gas such as nitrogen or argon) with respect to air.

The lean oxygen atmosphere in the present invention is not particularly limited and any of the above methods can be used.

When using the method of the said oxygen partial pressure below 0.15 atmosphere, 0.10 atmosphere or less is preferable, 0.08 atmosphere or less is more preferable, 0.05 atmosphere or less is especially preferable. If the oxygen partial pressure is higher than 0.15 atm, the surface of the deep isolation wall may not be sufficiently cured, and the height of the deep isolation wall may be lower than the target.

There is no restriction | limiting in particular in the minimum of oxygen partial pressure. Although the partial pressure of oxygen can be substantially zero by replacing the vacuum or atmosphere with a gas (for example, nitrogen) other than air, this is also a preferred method. Oxygen partial pressure can be measured using an oxygen meter.

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

The said reduced pressure refers to the state of 500 hPa or less, Preferably it is 100 hPa or less.

As mentioned above, although the deep color separation wall of this invention is formed using the said deep color composition, it is preferable to manufacture by the coating method of following (1) and (2), and the transcription method of following (3) and (4). .

That is, (1) the deep color separation wall is formed by applying the deep color photosensitive resin composition containing a colorant to a substrate and then exposing and developing under a lean oxygen atmosphere (oxygen partial pressure is 0.15 atm or less).

(2) The deep color separation wall is developed by applying a deep color photosensitive resin composition containing a colorant to a substrate and then exposing it under a lean oxygen atmosphere (in which an oxygen barrier layer is formed on the deep color photosensitive resin composition layer). To form.

(3) After transferring the photosensitive transfer material having a deep photosensitive transfer layer (dark photosensitive resin composition layer) formed on the branch body by the deep photosensitive resin composition on the substrate, under a lean oxygen atmosphere (oxygen partial pressure is 0.15). Exposure and development under atmospheric pressure).

(4) After transferring a photosensitive transfer material having a deep photosensitive transfer layer (a deep photosensitive resin composition layer) formed on a branch member by the deep photosensitive resin composition on the substrate, under a lean oxygen atmosphere (the deep photosensitive resin) It is formed by exposing and developing in the state which formed the oxygen barrier layer on the composition layer.

The deep color separation wall separates two or more pixel groups and is generally black, but is not limited to black.

(Oxygen barrier)

The oxygen barrier layer referred to in the present invention is a layer having an oxygen transmittance of 500 cm 3 / (m 2 · day · atm) or less, but the oxygen transmission rate is preferably 100 cm 3 / (m 2 · day · atm) or less, and 50 cm 3 / ( M 2 · day · atm) or less.

When the oxygen transmittance is higher than 500 cm 3 / (m 2 · day · atm), oxygen cannot be blocked efficiently, and it is difficult to make the isolation wall the desired shape.

Specifically, a layer containing polyethylene, polyvinylidene chloride, polyvinyl alcohol, and the like as the main component is preferable, but among these, polyvinyl alcohol as the main component is preferable.

As polyvinyl alcohol, it is preferable that saponification degree is 80% or more. It is preferable that content of the said polyvinyl alcohol in the oxygen barrier layer of this invention exists in the range of 25 mass%-99 mass%, It is more preferable that it exists in the range of 50 mass%-90 mass%, 50 mass% It is especially preferable to exist in the range of -80 mass%.

Moreover, although you may add polymers, such as a polyvinylpyrrolidone and a polyacrylamide, as needed, polyvinylpyrrolidone is preferable among these. It is preferable to exist in the range of 1-40 mass% of the whole layer, and, as for the addition amount of these polymers, it is more preferable to exist in the range of 10-35 mass%. When the addition amount of polyvinylpyrrolidone is too large, oxygen barrier property may become inadequate.

On the substrate, when the high absorbance deep color composition as described above is photopolymerized under the lean oxygen atmosphere as described above, the amount of exposure from the surface of the composition to the substrate is attenuated by absorption of the composition itself, resulting in surface Hardening progresses more. Further, due to the lean oxygen atmosphere high group, polymerization inhibition at the surface of the composition is suppressed, and this also results in more hardening of the surface.

These values are actually measured by cutting the deep color separation wall formed on the substrate vertically for each substrate, exposing the cross section, and directly observing with a microscope or the like.

By going through the step of fixing the separation wall shape thus obtained, for example, when used in a color filter, the ink once dispersed in the voids becomes difficult to cross the deep color separation wall. As a result, a good color filter can be obtained by preventing mixed color with adjacent pixels.

In the present invention, the height h of the deep color separation wall (the distance between the point H of the height of the deep color separation wall and the base G of the waterline lowered from the H to the substrate) is 1.0 μm or more. It is preferable to exist in the range of 1.5 micrometers or more and 10 micrometers or less, It is more preferable to exist in the range of 1.8 micrometers or more and 7.0 micrometers or less, It is especially preferable to exist in the range of 2.0 micrometers or more and 5.0 micrometers or less. By setting the height h in the range of 1.0 µm or more and 10 µm or less, mixed color can be prevented more effectively. If the height is less than 1.5 mu m, mixed color may occur. If the height exceeds 10 mu m, the formation of the deep color separation wall becomes difficult.

The absorbance at 555 nm of the deep color separation wall of the present invention is preferably 2.5 or more, more preferably in the range of 2.5 to 10.0, still more preferably in the range of 2.5 to 6.0, and in the range of 3.0 to 5.0 It is particularly preferred to be at.

By setting it as the said absorbance range, the display apparatus with high contrast is obtained and it is preferable. In addition, in terms of the display quality of the display device, the color of the deep color separation wall is preferably black.

The absorbance at 555 nm of the deep color separation wall of the present invention is preferably 2.5 or more, more preferably in the range of 2.5 to 10.0, still more preferably in the range of 2.5 to 6.0, and in the range of 3.0 to 5.0 It is particularly desirable to have.

The absorbance of the deep color separation wall and the absorbance at 555 nm can be measured by a known spectrophotometer. In this invention, it measured using UV-2100 (brand name, the Shimadzu Corporation).

(Formation of deep isolation wall)

(Formation of deep color separation walls using deep color composition)

Although an example of the method of apply | coating on a board | substrate using a deep color composition on a board | substrate and forming a deep color isolation wall is demonstrated below, this invention is not limited to this.

First, after cleaning the substrate, the substrate is heat treated to stabilize the surface state. After the temperature control of the substrate, the deep color composition is applied. Subsequently, one part of the solvent is dried to remove the fluidity of the coating layer. If necessary, an unnecessary coating liquid around the substrate is removed using an edge bead remover (EBR) or the like, and then prebaked to obtain a deep photosensitive resin composition layer.

The method of the said application is not specifically limited, It can carry out using the coater for glass substrates (for example, brand name: MH-1600, FSA Asia company) etc. which have a well-known slit-shaped nozzle.

The drying can be performed using a known drying apparatus (for example, a vacuum drying apparatus (VCD; manufactured by Tokyo Takagyo Co., Ltd.), etc.).

Although the prebaking method is not specifically limited, For example, it can achieve by performing at 120 degreeC for 3 minutes. The film thickness of the obtained deep color photosensitive resin composition layer is as described above.

Subsequently, the sample obtained above is maskless-exposed and the deep isolation wall pattern is obtained. Preferably, the deep color photosensitive resin composition layer is subjected to relative scanning exposure while modulating light based on the separation wall image data, and then developed to form a separation wall.

It is preferable to set it as said lean oxygen atmosphere at the time of exposure. The atmosphere can be realized by setting the oxygen partial pressure to 0.15 atmosphere or less, or by forming an oxygen barrier layer. The oxygen partial pressure at this time can be measured using an oxygen meter (G-102 type, Iijimaden High School, etc.).

Hereinafter, maskless exposure (relative scanning exposure) will be described in detail.

(Maskless exposure (relative scanning exposure))

As the exposure method of the present invention, there is a method of using an ultra-high pressure mercury lamp and a method of using a laser, but the latter is preferable.

As the laser used in the present invention, known lasers such as argon laser, He-Ne laser, semiconductor laser, carbon dioxide laser, and YAG laser can be used.

Although the wavelength of a laser is not specifically limited, Among them, although it is preferable to select from the wavelength range of 300-500 nm from a viewpoint of the resolution of a deep color isolation wall, the cost of a laser apparatus, and the availability, it is preferable that it is 340-450 nm. It is more preferable to select from the wavelength range, particularly preferably 405 nm.

The beam diameter of laser is not particularly limited, but among them, from the viewpoint of resolution of the deep color isolation wall, the 1 / e ² of a Gaussian beam and 5~30㎛ is preferable, more preferably 7~20㎛.

Although it does not specifically limit as an energy amount of a laser beam, Especially, 1-100 mJ / cm <2> is preferable and 5-20 mJ / cm <2> is more preferable from a viewpoint of an exposure time and a resolution.

In the present invention, it is necessary to spatially modulate the laser light in accordance with the image data. For this purpose it is desirable to use a digital micromirror device which is a spatial light modulation element.

As said exposure apparatus, it can expose using the following apparatus, for example.

Although an example of the three-dimensional exposure apparatus using a laser beam is shown below, the exposure apparatus in this invention is not limited to this.

As shown in FIG. 1, the exposure unit includes a flat stage stage 152 that adsorbs and holds the photosensitive material 150 on its surface. On the upper surface of the thick plate-shaped mounting table 156 supported by the four leg portions 154, two guides 158 extending along the stage moving direction are provided. The stage 152 is arranged such that its longitudinal direction is directed toward the stage moving direction, and is supported by the guide 158 so as to be reciprocated. This exposure apparatus is also provided with a driving device (not shown) for driving the stage 152 along the guide 158.

In the center portion of the mounting table 156, a c-shaped gate 160 is provided so as to span the movement path of the stage 152. Each end of the c-shaped gate 160 is fixed to both sides of the mounting table 156. A scanner 162 is provided on one side with the gate 160 interposed therebetween, 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. It is. The scanner 162 and the detection sensor 164 are attached to the gate 160, respectively, and are fixedly arranged above the movement path of the stage 152. In addition, the scanner 162 and the detection sensor 164 are connected to the controller which abbreviate | omits illustration which controls these.

As shown in Figs. 2 and 3 (B), the scanner 162 includes a plurality of (for example, 14) exposure heads arranged in a substantially matrix of m rows n columns (e.g., 3 rows and 5 columns). 166). In this example, four exposure heads 166 are arranged in the third row in relation to the width of the photosensitive material 150. Incidentally, in the case where the respective exposure heads arranged in the nth column of the mth row are shown, the exposure head _166mn is represented.

The exposure area 168 by the exposure head 166 has a rectangular shape in which the sub scanning direction is a short side. Accordingly, as the stage 152 moves, a band-shaped exposure completion area 170 is formed in each photosensitive material 150 for each of the exposure heads 166. In addition, when showing the exposure area | region by each exposure head arrange | positioned at the nth column of the mth line, it describes as exposure area | region _168mn .

In addition, as shown in Figs. 3A and 3B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposure completed area 170 is arranged without a gap in the direction orthogonal to the sub-scanning direction, Arranged at predetermined intervals (natural multiplication of the long side of the exposure area, here twice) in the arrangement direction. For this reason, the portion which cannot be exposed between the exposure area 168 ₁₁ and the exposure area 168 ₁₂ of the first row is exposed by the exposure area 168 ₂₁ of the second row and the exposure area 168 ₃₁ of the third row. can do.

Each of the exposure heads 166 _{11 to} 166 _mn is a spatial light modulator that modulates the incident light beam for each pixel according to image data, as shown in Figs. 4, 5A and (B). A 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 control signals for driving control of each micromirror in the area 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. In addition, 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. In addition, control of the angle of a reflection surface is mentioned later.

On the light incidence side of the DMD 50, a fiber array light source 66, a fiber array, having a laser exit section arranged in one row along the direction in which the exit end (light emission point) of the optical fiber corresponds to the long deflection of the exposure area 168. A lens system 67 for correcting the laser light emitted from the light source 66 and condensing 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. have.

The lens system 67 includes a pair of combined lenses 71 for parallelizing the laser light emitted from the fiber array light source 66 and a pair of combined lenses 73 for correcting the light quantity distribution of the parallel lighted laser light to be uniform. And a condenser lens 75 for condensing the laser light with the corrected light amount distribution on the DMD. The combined lens 73 extends the luminous flux in the portion close to the optical axis of the lens with respect to the arrangement direction of the laser output stage, and narrows the luminous flux in the portion away from the optical axis, and passes the light as it is in the direction orthogonal to this arrangement direction. The laser beam is corrected so that the light quantity distribution is uniform.

On the light reflection side of the DMD 50, lens systems 54 and 58 are formed to form laser light reflected by the DMD 50 on the scanning surface (exposed surface) 56 of the photosensitive material 150. The lens systems 54 and 58 are arranged such that the DMD 50 and the exposed surface 56 are in an airspace relationship.

In the DMD 50, as shown in FIG. 6, a micromirror (micromirror) 62 is disposed on the SRAM cell (memory cell) 60 by being supported by a support, and constitutes a pixel. It is a mirror device comprised by arranging many (for example, 600 * 800) micromirrors in grid form. Each pixel is provided with a micromirror 62 supported at the top by a support, and a material having a high reflectance such as aluminum is deposited on the surface of the micromirror 62. Moreover, the reflectance of the micromirror 62 is 90% or more. Further, just below the micromirror 62, a SRAM cell 60 of a CMOS of a silicon gate manufactured by a manufacturing line of a conventional semiconductor memory through a post including a hinge and a yoke is disposed, and a monolithic ( Integrated).

When a digital signal is recorded in the SRAM cell 60 of the DMD 50, the micromirror 62 supported on the support has ± α degrees with respect to the substrate side on which the DMD 50 is arranged with respect to the diagonal. For example, ± 10 degrees). Fig. 7A shows a state in which the micromirror 62 is inclined at + α degrees, and Fig. 7B shows a state in which the micromirror 62 is inclined at -α degrees. Therefore, in accordance with the image signal, the inclination of the micromirror 62 in each pixel of the DMD 50 is controlled as shown in FIG. 6, so that the light incident on the DMD 50 is in each micromirror 62. ) Is reflected in the inclined direction.

6 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled at + α degrees or -α degrees. On-off control of each micromirror 62 is performed by the controller not shown connected to DMD50. Further, a light absorber (not shown) is arranged in the direction in which the light beam is reflected by the off-state micromirror 62.

In addition, the DMD 50 is preferably disposed slightly inclined such that the short side forms a predetermined angle θ (for example, 1 ° to 5 °) with the sub scanning direction. FIG. 8 (A) shows the scanning trajectory of the reflected image (exposure beam) 53 by each micromirror in the case where the DMD 50 is not inclined. FIG. 8 (B) shows the scanning trajectory of the DMD 50 inclined. The scanning trajectory of the exposure beam 53 is shown.

In the DMD 50, micromirror rows in which a plurality of micromirrors are arranged in the longitudinal direction (for example, 800) are arranged in a plurality of sets (for example, 600 sets) in the width direction. as shown, the pitch (P in the scanning line in the case where the pitch (P ₁₎ of the scanning loci (the scanning lines) of, by inclining the DMD (50), the exposure beam (53) by each micro-mirror, which does not incline the DMD (50) _It becomes narrower than ₂ ), and the resolution can be improved significantly. On the other hand, since the inclination angle of the DMD 50 is minute, the scan width W ₂ when the DMD 50 is inclined and the scan width W ₁ when the DMD 50 is not inclined are substantially the same.

In addition, the same scanning line image is superimposed by different micromirror rows and exposed (multi-exposure). In this way, by the multiple exposure, the minute amount of the exposure position can be controlled and high-precision exposure can be realized. In addition, the joints between the plurality of exposure heads arranged in the main scanning direction can be connected without step by minute exposure position control.

In addition, instead of tilting the DMD 50, the same effect can be obtained by arranging the micromirror rows in a zigzag form at a predetermined interval shifted in the direction orthogonal to the sub-scanning direction.

As shown in Fig. 9A, the fiber array light source 66 includes a plurality (for example, six) laser modules 64, and each laser module 64 includes a multimode optical fiber 30. One end of is combined. At the other end of the multimode optical fiber 30, an optical fiber 31 whose core diameter is the same as the multimode optical fiber 30 and whose clad diameter is smaller than the multimode optical fiber 30 is combined, as shown in Fig. 9C. The output end portions (light emitting points) of the optical fiber 31 are arranged in one row along the main scanning direction orthogonal to the sub-scanning direction, so that the laser emitting portion 68 is formed. As shown in Fig. 9D, the light emitting points may be arranged in two rows along the main scanning direction.

As shown in FIG. 9 (B), the exit end of the optical fiber 31 is fitted and fixed to two support plates 65 having a flat surface. Moreover, in order to protect the end surface of the optical fiber 31, the transparent protective plate 63, such as glass, is arrange | positioned at the light output side of the optical fiber 31. As shown in FIG. The protective plate 63 may be arranged in close contact with the end face of the optical fiber 31, or may be arranged so that the end face of the optical fiber 31 is sealed. The exit end of the optical fiber 31 is easy to be collected and deteriorated due to high optical density, but by arranging the protective plate 63, adhesion of dust to the end surface can be prevented and the deterioration can be delayed.

Here, in order to arrange the exit ends of the optical fiber 31 having a small clad diameter in one row without a gap, the multi-mode optical fiber 30 is stacked between two multi-mode optical fibers 30 adjacent to each other with a large clad diameter. The exit end of the optical fiber 31 coupled to the overlapped multimode optical fiber 30 is interposed between the two exit ends of the optical fiber 31 coupled to the two multimode optical fibers 30 adjacent in a large clad diameter portion. It is arranged to fit in.

For example, as shown in FIG. 10, the optical fiber 31 having a clad diameter of 1 to 30 cm in length is coaxially coaxially with the distal end portion of the multi-mode optical fiber 30 having a large clad diameter on the laser light output side. Can be obtained by combining. The two optical fibers are fused and joined to the exit end surface of the multimode optical fiber 30 so that the center axes of both optical fibers are coincident with each other. As described above, the diameter of the core 31a of the optical fiber 31 is the same size as the diameter of the core 30a of the multimode optical fiber 30.

Further, a short optical fiber in which an optical fiber having a short length and a large clad diameter is fused to an optical fiber having a small clad diameter may be coupled to an exit end of the multimode optical fiber 30 through a ferrule or an optical connector. By detachably attaching using a connector or the like, the tip portion can be easily replaced, for example, when an optical fiber having a small clad diameter is broken, thereby reducing the cost of maintenance of the exposure head. In addition, below, the optical fiber 31 may be called the exit end part of the multi-mode optical fiber 30.

As the multimode optical fiber 30 and the optical fiber 31, any of a step index optical fiber, a graded index optical fiber, and a composite optical fiber may be sufficient. For example, a step index optical fiber manufactured by Mitsubishi Densen Kogyo Co., Ltd. can be used. Here, the multimode optical fiber 30 and the optical fiber 31 are step index type optical fibers, and the multimode optical fiber 30 has a cladding diameter of 125 µm, a core diameter of 25 µm, NA of 0.2, and an incident cross section coat. The transmittance is 99.5% or more, and the optical fiber 31 has a cladding diameter of 60 µm, a core diameter of 25 µm, and NA of 0.2.

In general, in the laser light in the infrared region, when the cladding diameter of the optical fiber is reduced, the propagation loss increases. For this reason, the preferable cladding diameter is determined according to the wavelength band of a laser beam. However, the shorter the wavelength, the smaller the propagation loss, and in the laser light having a wavelength of 405 nm emitted from the GaN semiconductor laser, the thickness of the clad {(clad diameter-core diameter) / 2} is infrared light in the wavelength band of 800 nm. The propagation loss is hardly increased even when it is about one half of propagating infrared rays and about one quarter of propagating infrared light in the 1.5 탆 wavelength band for communication. Therefore, the cladding diameter can be made small to 60 micrometers.

However, the cladding diameter of the optical fiber 31 is not limited to 60 µm. Although the cladding diameter of the optical fiber used in the conventional fiber light source is 125 µm, the smaller the clad diameter, the deeper the depth of focus. Therefore, the clad diameter of the multimode optical fiber is preferably 80 µm or less, more preferably 60 µm or less. 40 micrometers or less are more preferable. On the other hand, since the core diameter is required at least 3 to 4 µm, the clad diameter of the optical fiber 31 is preferably 10 µm or more.

The laser module 64 is comprised by the harmonic laser light source (fiber light source) shown in FIG. The multiplexing laser light source is a lateral multimode or single mode GaN semiconductor laser (LD1, LD2, LD3, LD4, LD5, LD6) on a plurality of chips (for example, seven) arranged 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 semiconductor lasers LD1 to LD7, one condenser lens 20, It consists of one multimode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, all 20 laser beams can be incident on a multimode optical fiber having a cladding diameter of 60 µm, a core diameter of 50 µm, and NA of 0.2, thereby realizing the required amount of light of the exposure head and further reducing the number of optical fibers. Can be reduced.

The GaN semiconductor lasers LD1 to LD7 have a common oscillation wavelength (for example, 405 nm), and a maximum output power is 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, a laser having an oscillation wavelength other than 405 nm in the wavelength range of 350 nm to 450 nm may be used.

As shown in Figs. 12 and 13, the combined wave laser light source is housed in a box-shaped package 40 which is open upward along with other optical elements. The package 40 is provided with the package cover 41 manufactured so that the opening may be closed, and after a degassing process, a sealing gas is introduced and the opening of the package 40 is closed with the package cover 41, so that the package ( The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the 40 and the package cover 41.

The base plate 42 is fixed to the bottom surface of the package 40. On the upper surface of the base plate 42, the heat block 10, the condenser lens holder 45 holding the condenser lens 20, And a fiber holder 46 for holding the incidence end of the multimode optical fiber 30. The exit end of the multimode optical fiber 30 is drawn out of the package from the opening formed in the wall surface of the package 40.

The collimator lens holder 44 is attached to the side of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the cross section of the package 40, and the wiring 47 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is led out of the package through the opening.

In addition, in FIG. 13, in order to avoid the complexity of drawing, only the GaN type semiconductor laser LD7 of several GaN type semiconductor lasers was numbered, and only the collimator lens 17 of the some collimator lenses was numbered.

Fig. 14 shows the front shape of the attachment portion of the collimator lenses 11 to 17. Figs. Each of the collimator lenses 11-17 is formed in the shape which cut | disconnected the area | region containing the optical axis of the circular lens with an aspherical surface in the parallel plane elongated. This elongate collimator lens can be formed by, for example, molding a resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the array direction of the light emitting points so that the longitudinal direction is orthogonal to the array direction of the light emitting points of the GaN semiconductor lasers LD1 to LD7 (left and right directions in FIG. 14).

On the other hand, GaN-based semiconductor lasers LD1 to LD7 are each provided with an active layer having a light emission width of 2 μm, and have spread angles in a direction parallel to the active layer and in a direction perpendicular to each other, for example, in a state of 10 ° and 30 °, respectively. Lasers for emitting laser beams B1 to B7 are used. These GaN semiconductor lasers LD1 to LD7 are provided so that the light emitting points are arranged in one column in a direction parallel to the active layer.

Therefore, as for the laser beams B1 to B7 emitted from each light emitting point, the direction of spreading angle coincides with the longitudinal direction with respect to the collimator lenses 11 to 17 having a long and thin shape as described above. The smaller direction enters in a state coinciding 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 beam diameters in the horizontal and vertical directions of the laser beams B1 to B7 incident thereon are 0.9 mm and 2.6 mm, respectively. . In addition, each of the collimator lens (11-17) is a focal length _{(f 1) = 3mm, NA} = 0.6, a lens arrangement pitch = 1.25mm.

The condenser lens 20 cuts the region including the optical axis of the circular lens having an aspherical surface in a parallel plane, elongated in a parallel plane, elongated in the array direction of the collimator lenses 11 to 17, that is, perpendicular to it. It is formed in a short shape in the direction. This condenser lens 20 has a focal length f _{2 of} 23 mm and NA of 0.2. This condensing lens 20 is also formed by, for example, molding a resin or optical glass.

Next, the operation of the exposure apparatus will be described.

In each exposure head 166 of the scanner 162, the laser beams B1, which are emitted in a divergent light state from each of the GaN semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66, Each of B2, B3, B4, B5, B6, and B7 is parallelized by the corresponding collimator lenses 11-17. The parallel beam laser beams B1 to B7 are collected by the condensing lens 20 and converge on the incident end surface of the core 30a of the multimode optical fiber 30.

Here, the condensing optical system is constituted by the collimator lenses 11 to 17 and the condensing lens 20, and the condensing optical system is constituted 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 enter the core 30a of the multi-mode optical fiber 30 to propagate in the optical fiber, and one laser beam B ) Is emitted from the optical fiber 31 coupled to the output end of the multi-mode 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 semiconductor lasers LD1 to LD7 is 30 mW, the laser beams B1 to B7 are arranged in an array. For each of the optical fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW x 0.85 x 7) can be obtained. Therefore, the output from the laser output unit 68 in which six optical fibers 31 are arranged in an array is about 1 W (= 180 mW x 6).

In the laser emission section 68 of the fiber array light source 66, the light emitting points of high brightness are arranged in a line along the main scanning direction. Since the conventional fiber light source that combines laser light from a single semiconductor laser into one optical fiber has a low output power, a desired output cannot be obtained without multi-column arrangement. You can get the output you want with just one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are combined one-to-one, a laser having an output of about 30 mW is usually used as a semiconductor laser, and a fiber diameter of 50 µm, a clad diameter of 125 µm, and NA (number of openings) are used as optical fibers. Since 0.2 multimode optical fiber is used, if you want to obtain an output of about 1 W, 48 multimode optical fibers must be bundled (8 x 6), and the area of the light emitting area is 0.62 mm2 (0.675 mm x 0.925 mm). The luminance in the laser exit section 68 is 1.6 × 10 6 (W / m 2), and the luminance per optical fiber is 3.2 × 10 6 (W / m 2).

As described above, the output of about 1 W can be obtained with six multi-mode optical fibers, and the area of the light emitting area in the laser emission unit 68 is 0.0081 mm 2 (0.325 mm x 0.025 mm). The luminance at the section 68 is 123 × 10 ⁶ (W / m 2), which is about 80 times higher than in the prior art. In addition, the luminance per optical fiber is 90 × 10 ⁶ (W / m 2), which is about 28 times higher than in the prior art.

Here, with reference to Figs. 15A and 15B, the difference between the depth of focus of the conventional exposure head and the exposure head according to the present invention will be described. The diameter of the sub scanning direction of the light emitting area of the bundle-shaped fiber light source of the conventional exposure head is 0.675 mm, and the diameter of the sub scanning direction of the light emitting area 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 becomes large, and as a result, the scanning surface ( The angle of the light beam incident on 5) becomes large. For this reason, a beam diameter tends to become large with respect to a condensing direction (deviation of a focus direction).

On the other hand, as shown in Fig. 15B, in the exposure head according to the present invention, since the diameter of the sub-scan direction of the light emitting region of the fiber array light source 66 is small, it passes through the lens system 67 to the DMD 50. The angle of the incident light beam becomes small, and as a result, the angle of the light beam incident on the scanning surface 56 becomes small. That is, the depth of focus is deepened. In this example, the diameter of the sub scanning direction of the light emitting area is about 30 times that of the conventional one, and a depth of focus corresponding to approximately the diffraction limit can be obtained. Therefore, it is suitable for exposure of a micro spot. The effect on the depth of focus is more pronounced and effective as the required light amount of the exposure head is larger. In this example, one pixel size projected on the exposure surface is 10 µm x 10 µm. The DMD is a reflective spatial modulator, but FIGS. 15A and 15B are exploded views for explaining the optical relationship.

The image data according to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and once stored in the frame memory in the controller. This image data is data which shows the density | concentration of each pixel which comprises an image by two values (with or without dot recording).

The stage 152 which adsorbs 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 stage 152 passes under the gate 160, if the tip of the photosensitive material 150 is detected by the detection sensor 164 attached to the gate 160, the image data stored in the frame memory is plural lines. It is sequentially read out minute by minute, and a control signal is generated for each exposure head 166 based on the image data read by the data processing unit. Then, by the mirror driving control unit, each of the micromirrors of the DMD 50 is turned on and off for each exposure head 166 based on the generated control signal.

When the laser light is irradiated to the DMD 50 from the fiber array light source 66, the laser light reflected when the micromirror of the DMD 50 is turned on is transferred to the photosensitive material 150 by the lens systems 54 and 58. An image is formed on the exposed surface 56. In this way, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, so that the photosensitive material 150 is exposed in pixel units (exposure region 168) approximately equal to the number of pixels used in the DMD 50. do. In addition, since the photosensitive material 150 is moved together with the stage 152 at a constant speed, the photosensitive material 150 is sub-injected by the scanner 162 in the opposite direction to the stage moving direction, so that each of the exposure heads 166 is stripped. The exposed area 170 of the image 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 subscanning direction. Only micromirror rows (e.g. 800 x 100 rows) are controlled to be driven.

As shown in Fig. 16A, the micromirror rows arranged at the center of the DMD 50 may be used, and as shown in Fig. 16B, the micromirror rows arranged at the ends of the DMD 50 may be used. good. In addition, when some micromirror generate | occur | produces a defect, you may change suitably the micromirror train used according to a situation, such as using the micromirror train which a defect did not generate | occur | produce.

The data processing speed of the DMD 50 is limited, and since the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line becomes faster by using only a part of the micromirror columns. On the other hand, in the case of the exposure system which continuously moves the exposure head relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

For example, when using only 300 sets of 600 sets of micromirror trains, the modulation can be performed twice as fast as one line compared with the case where all 600 sets are used. Of the 600 sets of micromirror trains, only 200 sets are used, which can be modulated three times faster per line than in the case where all 600 sets are used. That is, an area of 500 mm in the sub-scanning direction can be exposed for 17 seconds. In addition, 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 for 9 seconds.

The number of micromirror rows used, that is, the number of micromirrors arranged in the sub-scanning direction, is preferably 10 or more and 200 or less, more preferably 10 or more and 100 or less. Since the area per micromirror equivalent to one pixel is 15 µm x 15 µm, an area of 12 mm × 150 µm or more and 12 mm × 3 mm or less is preferable in terms of the DMD 50 used area. The area of 150 µm or more and 12 mm x 1.5 mm or less is more preferable.

When the number of micromirror rows to be used is in the above range, as shown in Figs. 17A and 17B, the laser light emitted from the fiber array light source 66 is roughly parallelized by the lens system 67 to be applied to the DMD 50. You can investigate. It is preferable that the irradiation area irradiated with the laser light by the DMD 50 coincides with the use area of the DMD 50. If the irradiation area is wider than the use area, the utilization efficiency of the laser light is reduced.

On the other hand, although the diameter of the sub-scan direction of the light beam focused on the DMD 50 needs to be made small according to the number of micromirrors arranged in the sub-scan direction by the lens system 67, the number of micromirror rows to be used is 10. If less, the angle of the light beam incident on the DMD 50 becomes large and the depth of focus of the light beam on the scanning surface 56 becomes shallow, which is not preferable. It is also preferable from the viewpoint of the modulation rate that the number of micromirror rows to be used is 200 or less. In addition, although the DMD is a reflective spatial modulator, Figs. 17A and 17B are exploded views for explaining the optical relationship.

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

As described above, the exposure unit (exposure device) according to the present invention includes a micromirror train in which 800 micromirrors are arranged in the main scanning direction and has a DMD in which 600 sets are arranged in the subscanning direction. Since only a part of the micromirror rows is controlled to be driven, the modulation rate per line becomes faster than when driving all the micromirror rows. This makes it possible to expose at high speed.

As exposure by the said ultra-high pressure mercury lamp, it is performed by a proximity exposure machine (for example, Hitachi High-Tech Engineering Co., Ltd.) etc., and it can select suitably (for example, 300mJ / cm <2>) as an exposure amount. In addition, the oxygen partial pressure at this time can be measured using the said oxygen meter.

Next, it is developed with a developing solution to obtain a patterned image, which is subsequently washed with water to obtain a deep color separation wall if necessary.

It is preferable to spray pure water with a shower nozzle etc. before the said image development, and to wet the surface of the said deep photosensitive resin composition layer uniformly. As the developing solution to be used in the developing treatment, a lean aqueous solution of an alkaline substance is used, but a small amount of an organic solvent miscible with water may be added.

As an alkaline substance in the method by application | coating of the said deep color composition and the method of using the photosensitive transfer material mentioned later, alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate) , Potassium carbonate), alkali metal bicarbonates (e.g. sodium bicarbonate, potassium hydrogen carbonate), alkali metal silicates (e.g. sodium silicate, potassium silicate), alkali metal metasilicates (e.g. sodium metasilicate, Potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example tetramethylammonium hydroxide), trisodium phosphate, etc. are mentioned. As for the density | concentration of an alkaline substance, 0.01-30 mass% is preferable, and pH is preferable 8-14.

As said "an organic solvent miscible with water", for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monon- Butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-capro Lactam, N-methylpyrrolidone, etc. are mentioned preferably. As for the density | concentration of the water and miscible organic solvent, 0.1-30 mass% is preferable. Moreover, a well-known surfactant can also be added and 0.01-10 mass% is preferable as a density | concentration of the said surfactant.

The developer can be used either as a solution or as a spray solution. When the uncured portion of the photosensitive resin composition layer is removed, a method such as rubbing with a rotary brush or a wet sponge in the developer can be combined. As for the liquid temperature of a developing solution, 40 degrees is preferable normally from room temperature vicinity. The developing time depends on the composition of the photosensitive resin composition layer, the alkalinity and temperature of the developing solution, and the type and concentration of the organic solvent, but is usually about 10 seconds to 2 minutes. When too short, the phenomenon of a non-exposed part may become inadequate and the absorbance of an ultraviolet-ray may also become inadequate, and when too long, an exposed part may also be etched. In either case, it is difficult to make the separation wall shape desirable. In this developing step, the separating wall shape is formed as described above.

In the developing tank, a roller conveyor or the like is provided, and the substrate moves horizontally. In the sense of preventing damage to 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 remains 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 preferable that the substrate is inclined at an angle. The inclination angle is preferably 5 ° to 30 °.

In addition, it is preferable to spray pure water before developing and to wet the photosensitive resin layer, resulting in a uniform developing result.

In addition, after the development, air is lightly sprayed onto the substrate to remove excess liquid substantially, followed by shower washing, which results in a more uniform development. Further, before washing with water, by spraying ultrapure water at a pressure of 3 to 10 MPa with an ultra-high pressure cleaning nozzle to remove residue, a high-quality phase free of residue is obtained. If the substrate is returned to the substrate with water droplets attached thereto, the process may be contaminated or stains remain on the substrate. Therefore, it is preferable to remove water with an air knife to remove excess water or droplets.

In addition to the above exposure and development steps, steps such as post exposure, heat treatment, and the like may be performed as the manufacturing steps of the deep color separation wall of the present invention. As said process, the process of Paragraph No. [0067]-[0074] of Unexamined-Japanese-Patent No. 2005-3861 can be used as a preferable thing.

In addition, in order to prevent the mixed color at the time of imparting a droplet, at least a part of the upper surface of the deep color isolation wall is ink repellent, and the pixel is separated from each other between the deep color isolation walls. It is preferable to form. Here, a part of the upper surface of the deep color separation wall means at least a part of the surface on the deep color separation wall on the side opposite to the surface on the side contacting the substrate of the deep color separation wall.

Regarding the ink repellent treatment, for example, (1) a method of mixing ink repellent material into a deep color separation wall (see Japanese Patent Laid-Open No. 2005-36160), and (2) forming a new ink repellent layer. Method (see, for example, Japanese Patent Application Laid-Open No. 5-241011), (3) Method of imparting ink repellency by plasma treatment (see, for example, Japanese Patent Application Laid-Open No. 2002-62420), (4) deep color A method of coating ink repellent material on the wall surface of the separating wall (for example, see Japanese Patent Application Laid-open No. Hei 10-123500), and the like. Preference is given to a method of carrying out ink treatment.

Below, the water repellent treatment will be described in detail.

(1) Method of mixing water-repellent material into the separating wall

As a means of preventing "mixing color", there is a method of producing a separation wall using a photoresist obtained from the deep color composition of the present invention containing a fluorine-containing resin (A).

A fluorine-containing resin is a copolymer containing the monomeric unit based on the monomer which has an ethylenic double bond and an Rf group (a), and the monomeric unit based on the monomer which has an ethylenic double bond and an acidic group (b), and is an acid value It is preferable that it is 1-300 mgKOH / g.

As an ethylenic double bond, a (meth) acryloyl group, a vinyl group, and an allyl group are mentioned.

As the monomer 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 Etc. can be mentioned. However, R ¹ represents a hydrogen atom or a methyl group, Q ¹ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and Q ² represents a divalent organic group having 1 to 6 carbon atoms, respectively. Q ¹ and Q ² may have a cyclic structure.

Specific examples of Q ¹ and Q ² include —CH ₂ —, —CH ₂ CH ₂ —, —CH (CH ₃ ) —, —CH ₂ CH ₂ CH ₂ —, —C (CH ₃ ) ₂ —, and —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. Among them, from the viewpoint of ease of synthesis, -CH _2- , -CH ₂ CH _2- , -CH ₂ CH (OH) CH ₂ -is preferred.

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

CH ₂ = CHCOOCH ₂ CF ₂ O (CF ₂ CF ₂ O) _n-1 CF ₃ (n is 3 to 9), CH ₂ = CHCOOCH ₂ CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _{n -1} C ₆ F ₁₃ (n is 2 to 6), CH ₂ = CHCOOCH ₂ CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₃ F ₇ (n is 2 to 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 to 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 to 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 to 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 to 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 to 6).

As for content of the monomeric unit based on the ethylenic double bond in a fluorine-containing resin, and the monomer which has Rf group (a), 1-95% etc. are preferable, 5-80% is more preferable, 20-60% More preferred. If it is the said range, a fluorine-containing resin will have favorable ink repellency and the developability of the photosensitive composition of this invention will become favorable.

As a monomer which has an acidic group (b), the monomer which has a carboxyl group, the monomer which has a phenolic hydroxyl group, the sulfonic acid group, and the monomer which has a hydroxyl group are mentioned. 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, or salts thereof. These may be used independently and may use 2 or more types together.

As a monomer which has a phenolic hydroxyl group, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, etc. are mentioned. At least one hydrogen atom of these benzene rings is an alkyl group such as methyl group, ethyl group, n-butyl group, alkoxy group such as methoxy group, ethoxy group, n-butoxy group, at least one hydrogen atom of halogen group, alkyl group is halogen atom Substituted haloalkyl group, nitro group, cyano group, compound substituted with amide group, etc. are mentioned. These may be used independently and may use 2 or more types together.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl and (meth) acrylic acid-2- Sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, or salts thereof. These may be used independently and may use 2 or more types together.

As a specific example of the monomer which has a hydroxyl group, vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Meta) 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-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.

Moreover, as a monomer which has a hydroxyl group, the monomer which has a polyoxyalkylene chain whose terminal is a hydroxyl group may be sufficient. 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 from 1 to 100, hereinafter identical), 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 1 to 100. The same applies below), 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 independently and may use 2 or more types together.

0.1-40% etc. are preferable, as for content of the monomeric unit based on the monomer which has an acidic group (b) in a fluorine-containing resin, 0.5-30% is more preferable, and its 1-20% is still more preferable. If it is the said range, a fluorine-containing resin will show favorable ink repellency and the developability of a photosensitive composition will become favorable.

When the fluorine-containing resin is a copolymer having a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a) and a monomer unit based on a monomer having an ethylenic double bond and an acid group (b), the Rf group (a ) And a monomer unit that does not have an acidic group (b) (hereinafter referred to as "other monomer").

As other monomers, hydrocarbon type olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, (meth) acrylamides, aromatic vinyl compounds, Chloroolefins, pulluloolefins, and conjugated dienes are mentioned. A functional group may contain in these compounds, for example, a hydroxyl group, a carbonyl group, an alkoxy group, an amide group, etc. are mentioned. Moreover, you may have group which has a polysiloxane structure. However, the monomer unit based on these other monomers does not have Rf group (a) and acidic group (b). These may be used independently and may use 2 or more types together. Since (meth) acrylic acid ester and (meth) acrylamide are especially excellent in the heat resistance of the coating film formed from the photosensitive resin composition of this invention, it is preferable.

In the fluorine-containing resin, the proportion of monomer units based on other monomers is preferably 80% or less, more preferably 70% or less. The developability of the photosensitive composition of this invention becomes it favorable that it is the said range.

The fluorine-containing resin in the present invention contains a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a), and a monomer unit based on a monomer having an ethylenic double bond and an acid group (b). In addition to being obtained by synthesizing a copolymer, it is also obtained by various modification methods for reacting a polymer having a reaction site with a compound having an Rf group (a) and / or a compound having an acidic group (b).

As various modification methods for reacting a compound having an Rf group (a) with a polymer having a reaction site, for example, a method of reacting a compound having an Rf group (a) with a carboxyl group after copolymerizing a monomer having an epoxy group in advance, an epoxy group The method of making the Rf group (a) and the compound which has a hydroxyl group react after copolymerizing the monomer which has a before is mentioned. Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

As a compound which has Rf group (a) and a carboxyl group, the compound represented by following formula (3) is mentioned.

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 1-20, n shows the integer of 2-50.

As a compound which has Rf group (a) and a hydroxyl group, the compound represented by following formula 4 is mentioned.

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 1-20, n shows the integer of 2-50.

As various modification methods for making the compound which has an acidic group (b) react with the polymer which has a reaction site, the method of making an acid anhydride react after copolymerizing the monomer which has a hydroxyl group previously, for example is mentioned. Furthermore, the method of making the compound which has a hydroxyl group react after copolymerizing the acid anhydride which has ethylenic double bond in advance is mentioned.

As a specific example of the monomer which has a hydroxyl group, vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Meta) 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-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl), etc. are mentioned.

Moreover, as a monomer which has a hydroxyl group, the monomer which has a polyoxyalkylene chain whose terminal is a hydroxyl group may be sufficient. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (wherein g is an integer from 1 to 100, hereinafter equals), 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 1 to 100. The same applies to the following.), and CH ₂ = C (CH ₃ ) COOC ₂ H ₄ O (C ₂ H ₄ O) _h (C ₃ H ₆ O) _k H. These may be used independently and may use 2 or more types together.

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 acid, and 3,4,5,6-anhydride. Tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic acid, 2-buten-1-ylscenic anhydride, and the like.

As a compound which has a hydroxyl group, the compound which has one or more hydroxyl groups may be sufficient, and the specific example of the monomer which has a hydroxyl group shown above, alcohols, such as ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, 2 -Cellulsolves such as methoxy ethanol, 2-ethoxy ethanol, 2-butoxy ethanol, 2- (2-methoxy ethoxy) ethanol, 2- (2- ethoxy ethoxy) ethanol, 2- (2 Carbitols, such as -butoxyethoxy) ethanol, etc. are mentioned. Preferred are compounds having one hydroxyl group in the molecule. These may be used independently and may use 2 or more types together.

The polymer having the reaction site that becomes the precursor of the fluorine-containing resin or the fluorine-containing resin can be synthesized by dissolving the monomer in a solvent with a chain transfer agent, if necessary, by heating, adding a polymerization initiator and reacting the same. .

The acid value of the fluorine-containing resin is preferably in the range of 1 to 300 mgKOH / g, more preferably in the range of 5 to 200 mgKOH / g, and particularly preferably in the range of 10 to 150 mgKOH / g. If it is this range, developability of the photosensitive composition of this invention will become favorable. In addition, an acid value is the mass (unit mg) of potassium hydroxide required for neutralizing 1 g of resin, and in this specification, a unit is described as mgKOH / g.

The number average molecular weight of the fluorine-containing resin is preferably 500 or more and less than 20000, more preferably 2000 or more and less than 15,000. The developability of the photosensitive composition of this invention is favorable in it being the said range. The number average molecular weight is measured using polystyrene as a reference material by gel permeation chromatography.

It is preferable that the compounding quantity of a fluorine-containing resin (A) exists in the range of 0.01-50 mass% with respect to solid content in the photosensitive composition, It is more preferable that it exists in the range of 0.1-30% mass%, 0.2-10 mass It is particularly preferable to be in the range of%. If it is the said range, a photosensitive composition will show favorable ink repellency and ink deterioration property, and developability will become favorable.

(2) How to form a water repellent layer

As a means of preventing "mixing color", there is a method of producing a partition wall having ink repellency at a position coinciding with the separating wall on the substrate on which the separating wall is formed.

As the partition wall having ink repellency, it is preferable to use a silicone rubber layer. It is essential for the silicone rubber layer to be applied to the surface layer to have a repulsive effect on the solution and ink used for coloring, but it is not limited to this, but it is composed mainly of linear organic polysiloxanes having molecular weights of several thousand to several hundred thousand having the following repeating units. will be.

N is an integer of 2 or more, and R is an independent C1-C10 alkyl group, alkenyl group, or phenyl group, respectively. Silicone rubber is obtained by sparse crosslinking of such linear organic polysiloxane. The crosslinking agent is so-called acetoxysilane, ketooxime silane, alkoxysilane, aminosilane, amide silane, alkenioxy silane and the like used in the room temperature (low temperature) -curable silicone rubber. In combination, it becomes silicone rubber of a deacetic acid type, a oxime type, a dealcohol type, a deamine type, a deamide type, and a deketone type, respectively. In addition, a small amount of organic tin compound or the like is added to the silicone rubber as a catalyst. In order to adhere | attach a photosensitive resin layer and a silicone rubber layer, various things may be used as an adhesive layer between layers, and an aminosilane compound and an organic titanate compound are especially preferable. Instead of forming 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 the additive adhesive component, an aminosilane compound or an organic titanate compound can be used.

The exposure for fabricating the partition wall is performed by using the isolation wall as a mask, on the back side of the substrate, and by scattering irradiated UV light, expanding the incident light above the size of the transmission site, acting on the photosensitive resin, and reacting and solubilizing the resin. Make the part larger on the silicone rubber surface side. After exposing in this way, it can develop with n-heptane / ethanol liquid mixture, and can produce the partition wall which has a silicone rubber surface layer.

(3) Method of imparting water repellency by plasma treatment

As a means of preventing "mixing color", there is a method of performing a water repellent treatment by plasma on a substrate on which a separation wall is formed.

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 is used as the gas containing at least a fluorine atom introduced in this step. desirable. In particular, C ₅ F ₈ (octafluorocyclopentene) has an ozone depletion capacity of 0, and an atmospheric life of 0.98 years compared to the conventional gas (CF ₄ : 50,000 years, C ₄ F ₈ : 3200 years). short. Therefore, the global warming coefficient is 90 (100-year integrated value at CO ₂ = 2), which is very small compared to the conventional gas (CF ₄ : 6500, C ₄ F ₈ : 8700), and is very effective for protecting the ozone layer and the global environment. It is preferable to use in this invention.

In addition, as introduction gas, you may use together gases, such as oxygen, argon, helium, as needed. In this step, when the halogen gas selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ is used, a mixed gas of at least one kind and O ₂ is used. It is possible to control the degree of ink repellency of the surface of the separating wall to be treated. However, in the mixed gas, the mixing ratio of O ₂ is the oxidation by the O ₂ is the dominant more than 30%, it may interfere with the ink-repellent effect to improve, and O ₂ mixing ratio exceeds 30% When the mixed gas is used, it is necessary to use the mixing ratio of O ₂ in the range of 30% or less since the damage to the lower surface resin is remarkable.

As the plasma generating method, low frequency discharge, high frequency discharge, microwave discharge, or the like can be used, and conditions such as pressure, gas flow rate, discharge frequency, and processing time during the plasma treatment can be arbitrarily set.

(4) How to apply water-repellent material on the upper surface of the isolation wall

As a means of preventing "mixing color", there is a method of applying a water repellent material to the entire surface of the substrate on which the isolation wall is formed.

As a material having water repellency, it is generally considered to be a water repellent material such as fluororesins such as polytetrafluoroethylene, silicone rubber, perfluoroalkyl acrylate, hydrocarbon acrylate, methylsiloxane, and the contact angle with respect to the colorant is 60 °. The above is not particularly limited.

As a method of applying the water repellent material, it is possible to select an optimal method for each material such as slit coat, spin coat, dip coat, roll coat as long as it does not affect the substrate, the isolation wall, or the like.

Next, UVO ₃ treatment is performed from the back side of the substrate through the isolation wall, and the water-repellent film in portions other than the isolation wall is selectively removed or hydrophilized (the contact angle to the colorant differs by 30 ° or more from before and after the treatment).

If the water repellent material can be removed or hydrophilized, the patterning method can be selected according to the material such as dry ablation such as laser ablation, plasma ashing, corona discharge treatment, and wet treatment using alkali. . The lift-off method and the like are also effective as long as it is possible to pattern a water repellent material on the isolation wall.

Among the water-repellent treatment methods of (1) to (4) above, a water-repellent treatment method using plasma (3) is particularly preferable from the viewpoint of "simple process".

(Formation of deep color separation wall using photosensitive transfer material)

First, after the above-mentioned protective film of the photosensitive transfer material is peeled off, the surface of the exposed deep color photosensitive resin composition layer is bonded on a permanent support (substrate), and then laminated by heating and pressing through a laminator or the like (laminated body). . As a laminator, what was suitably selected from the conventionally well-known laminator, a vacuum laminator, etc. can be used, In order to raise productivity more, an auto cut laminator can also be used.

Subsequently, the branched body was removed, the maskless exposure was irradiated to the upper side of the removal surface after removing the branched body, and subjected to development treatment using a predetermined processing liquid after the irradiation to obtain a patterned image. Water washing is performed to obtain a deep color separation wall.

About the detail of the developing solution and maskless exposure used for a developing process, the developing solution and maskless exposure in formation using the said coating method are used similarly.

(Pixel)

The pixel and the colored liquid composition in the present invention will be described in the section "Method of Manufacturing Color Filter" described later.

(Overcoat layer)

After forming the colored area (colored pixel) and the deep color separation wall as described above, and manufacturing the color filter, the overcoat layer can be formed by covering the entire surface of the color area and the deep color separation wall for the purpose of improving resistance. have.

The overcoat layer can protect colored areas such as R, G, and B and the deep color separation wall, and make the surface flat. However, it is preferable not to form in the point which process water increases.

An overcoat layer can be comprised using resin (made by OC), and acrylic resin composition, an epoxy resin composition, a polyimide resin composition etc. are mentioned as resin (made by OC). Especially, since the resin component of the photocurable composition for color filters is excellent in transparency in a visible light region normally has acrylic resin as a main component, and is excellent in adhesiveness, an acrylic resin composition is preferable. As an example of an overcoat layer, Paragraph Nos. [0018]-[0028] of Unexamined-Japanese-Patent No. 2003-287618, As a commercial item of an overcoat, Optomer SS6699G by JSR Corporation is mentioned.

(Production method of color filter)

(Formation of each pixel)

The manufacturing method of the color filter of this invention has a pixel group which consists of several pixel which has two or more colors on a board | substrate, these pixels are isolate | separated from each other by the said deep color isolation wall, and the said some pixel is colored liquid. It is characterized by forming by dropping the composition.

In other words, the liquid crystal composition for forming two or more colors of pixels (for example, each pixel of RGB) is applied to the voids between the deep isolation walls formed on the substrate in the developing step to infiltrate the pores of the deep isolation walls by adding droplets. A plurality of pixels having colors of more than the color are formed.

As a method of injecting the colored liquid composition into droplets and infiltrating into the isolation wall voids, a known one such as an inkjet method or a stripe-based coating method can be used, and an inkjet method is preferable in terms of cost. The stripe base coating method is a method of forming a stripe pixel by applying a droplet onto a substrate using a base having a narrow droplet discharge hole.

In addition, before forming each pixel in this way, the shape of the deep color isolation wall may be fixed, and the means is not specifically limited, The following are mentioned.

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 herein refers to heating a substrate having a deep color separation wall with an electric furnace, a dryer, or irradiating an infrared lamp.

As for the inkjet method used for forming each pixel, a known method such as a method of thermosetting ink, a photocuring method, a method of forming a transparent aqueous phase layer on a substrate in advance, and then spraying the same can be used.

Preferably, after forming each pixel, the heating process of heat processing (so-called baking process) is provided. That is, the board | substrate which has a layer photopolymerized by light irradiation is heated with an electric furnace, a dryer, etc., or an infrared lamp is irradiated. The temperature and time of heating depend on the composition of the deep color composition and the thickness of the formed layer, but generally from about 10 minutes to about 120 ° C to about 250 ° C in terms of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. It is preferred to heat for about 120 minutes.

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

(Inkjet method)

As the inkjet method used in the present invention, a method of spraying charged ink continuously and controlling by electric field, intermittently spraying ink using a piezoelectric element, heating ink and using the foaming thereof Various methods, such as the method of spraying intermittently, can be employ | adopted.

The ink to be used may be oil or water. In addition, both the dye and the pigment can be used for the coloring material contained in the ink, and in terms of durability, the use of the pigment is more preferable. In addition, a coloring ink of a coating method (a colored resin composition, for example, Japanese Patent Laid-Open Publication Nos. 2005-3861 and [0076] and [0078]) and Japan, which are used for producing a known color filter. The composition for inkjets of Unexamined-Japanese-Patent No. 10-195358 [0009]-[0026], Unexamined-Japanese-Patent No. 2004-339332, and Unexamined-Japanese-Patent No. 2002-372615 can also be used.

To the ink in the present invention, in consideration of the step after coloring, a component which is cured by heating or cured by energy rays such as ultraviolet rays may be added. Various components of thermosetting resins are widely used as components cured by heating, and examples of components cured by energy rays include those in which a photoreaction initiator is added to an acrylate derivative or a methacrylate derivative. It is more preferable to have acryloyl group and a methacryloyl group in a molecule especially in consideration of heat resistance. These acrylate derivatives and methacrylate derivatives can preferably be used water-soluble ones, and can be used by emulsifying even water-soluble ones.

In this case, the photosensitive resin composition containing the coloring agent, such as a pigment, mentioned in the term of the said "darkening composition" can be used as a preferable thing.

Moreover, as ink which can be used in this invention, the thermosetting ink for color filters containing at least a binder and the bifunctional to trifunctional epoxy group containing monomer can also be used as a preferable thing.

It is preferable that the color filter in this invention is a color filter pixel-formed by the inkjet system, and it is preferable to form the color filter of three colors by spraying RGB tricolor ink.

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, a PLZT, or the like. It can also be used to use color cameras or 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, and a CRT display device. For the definition of the display device and the explanation of each display device, for example, "Electronic display device (Aki Sasaki, published by Industrial Society of Japan, 1990)", "Display device (Ibuki Sunsho, Industrial Books Co., Ltd., 1989) Issuance) ”.

Among the display devices of the present invention, liquid crystal display devices are particularly preferable. The liquid crystal display device is described in, for example, "next-generation liquid crystal display technology" (Tatsuo Uchida editorial, 1994). There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology." Among these, the present invention is particularly effective for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, a "color TFT liquid crystal display (public publication Co., Ltd. 1996)". In addition, the present invention can be applied to a liquid crystal display device having an enlarged viewing angle such as a transverse 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 and LCD Display Technology and the Latest Trends in the Market (Issue 2001, published by Toray Research Center Research and Research).

In addition to the color filter, the liquid crystal display is composed of 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 these members, for example, the market for '94 liquid crystal display peripheral materials and chemicals (Kenta Shima Kentaro Co., Ltd. C 1994), and the current status and future prospects of the 2003 liquid crystal display market (the lower volume) (Homoyoshi Omote) Fuji Chimera Research Institute, 2003).

(Target use)

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

(Example)

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail using an Example. The present invention is not limited to these. In addition, "%" and "part" represent "mass%" and "mass part" unless there is particular notice, and a "molecular weight" shows a "mass average molecular weight."

(Preparation of a deep photosensitive composition)

The deep color photosensitive composition first weighs the carbon black dispersion and propylene glycol monomethyl ether acetate in the amount described in the following color photosensitive composition formulation, mixes at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 RPM for 10 minutes, and then, Methyl ethyl ketone, binder P-1, hydroquinone monomethyl ether, DPHA liquid, 7- [2- [4- (3-hydroxymethylpiperidino) -6-diethylamino] triazylamino] -3- Phenylcoumarin, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.) It is obtained by stirring for 30 minutes at 150 RPM at a temperature of 40 ℃ (± 2 degrees).

(Dark photosensitive composition prescription)

Carbon black dispersion: 25 parts

Propylene glycol monomethyl ether acetate: 8 parts

Methyl ethyl ketone: 53 parts

Binder P-1: 9.1

Hydroquinone monomethyl ether: 0.002 parts

DPHA liquid: 4.2 parts

7- [2- [4- (3-hydroxymethylpiperidino) -6-diethylamino] triazylamino] -3-phenylcoumarin: 0.75 parts

2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole: 0.16 parts

Surfactant 1: 0.045 parts

(Carbon Black Dispersion)

Carbon black (Nipex35 from Dexter): 13.1%

Dispersant: 0.65%

Polymer (benzyl methacrylate / methacrylic acid = random copolymer of 72/28 molar ratio, molecular weight 37000): 6.72%

Propylene glycol monomethyl ether acetate: 79.53%

(Binder P-1)

Polymer (benzyl methacrylate / methacrylic acid = random copolymer of 78/22 molar ratio, molecular weight 38000): 27%

Propylene glycol monomethyl ether acetate: 73%

(DPHA liquid)

Dipentaerythritol hexaacrylate

(Polymer banned MEHQ 500ppm, Nihon Kayaku Co., Ltd., brand name: KAYARAD DPHA): 76%

Propylene glycol monomethyl ether acetate: 24%

(Surfactant 1)

Structure 1: 30%

Methyl ethyl ketone: 70%

Structure 1

(Example 1-1)

(Formation of deep isolation wall)

The alkali-free glass substrate was washed with a UV cleaner, then brush-washed with a detergent, and then ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.

After cooling the said board | substrate and adjusting the temperature to 23 degreeC, the said deep photosensitive resin composition was apply | coated with the glass substrate coater (ASF Asia make, brand name: MH-1600) which has a slit-shaped nozzle. Subsequently, one part of the solvent was dried for 30 seconds with a VCD (Vacuum Dryer; manufactured by Tokyo-Kago Kogyo Co., Ltd.) to remove the fluidity of the coating layer, and then the unnecessary coating liquid around the substrate was removed with EBR and prebaked at 120 ° C for 3 minutes. To give a thick photosensitive resin composition layer having a thickness of 2.4 μm.

Subsequently, this sample was exposed by the following method using the following apparatus.

(Exposure device)

1 to 17, a space for modulating the fiber array light source 66 capable of emitting 405 nm laser light and the incident laser beam (output 10 mJ / cm 2, 1 / e ² diameter 10 μm) in accordance with image data Lens system 54 having a digital micromirror device (DMD) 50 that is an optical modulation element, a data processing unit, and a mirror driving control unit, and an image of a controller (not shown) connected to the DMD and laser light reflected by the DMD to form an image on an exposed surface. Is provided with an exposure head (exposure unit according to the present invention) 166 which is configured by installing a controller and which is controlled by a controller (not shown) and relatively moved in a direction intersecting a predetermined direction with respect to the exposed surface. Ready device.

(Exposure)

Next, the exposure apparatus configured as described above was exposed with an energy amount of 40 mJ / cm 2 with a laser beam having a wavelength of 405 nm to obtain a deep color separation wall pattern. Moreover, exposure was performed in nitrogen atmosphere by nitrogen purge. The oxygen partial pressure was measured using an oxygen meter (trade name: G-102 type, manufactured by Iijima Denshi Kogyo Co., Ltd.).

Next, pure water was sprayed with a shower nozzle to uniformly wet the surface of the deep photosensitive resin composition layer, and then KOH-based developer (KOH, nonionic surfactant-containing product, trade name: CDK-1, FUJIFILM Electronics, Inc.) Was diluted 100-fold with pure water) and shower-developed at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterned image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, followed by heat treatment at 220 ° C. for 30 minutes to obtain a deeply isolated wall having the shape shown in FIG. 18 (A).

(Plasma water repellent treatment)

Plasma water repellent treatment was performed on the substrate on which the deep separation wall was formed using the cathode coupling type parallel plate type plasma processing apparatus under the following conditions.

Gas Used: CF ₄

Gas flow rate: 80sccm

Pressure: 40 Pa

RF power: 50W

Processing time: 30sec

(Pixel formation)

Subsequently, the ink of each of R, G, and B was applied to the gap between the black matrix patterned isolation walls and colored using an ink jet apparatus.

Among these components, the ink is first mixed with a pigment, a polymer dispersant and a solvent, to obtain a pigment dispersion using three rolls and a bead mill, while the pigment dispersion is sufficiently stirred with a dissolver or the like, and other materials Was added in small portions to prepare R (red) ink 1. At this time, the viscosity of the R (red) ink 1 was 7.5 cPs. In addition, the viscosity of the red ink was measured at the temperature of 20 degreeC using the viscosity measuring device (brand name VIBROVISCOMETER CJV5000, A & D company).

(The composition of R ink 1)

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

Polymeric dispersant (SALPERS 24000 by Avecia): 1 part

Binder (glycidyl methacrylate-styrene copolymer): 3 parts

1 epoxy resin (novolak-type epoxy resin, Yukacel company Epicoat 154): 2 parts

Second epoxy resin (neopentyl glycol diglycidyl ether): 5 parts

Curing agent (trimellitic acid): 4 parts

Solvent: Ethyl 3-ethoxypropionate: 80 parts

A G (green) ink 1 was prepared in the same manner as in the case of the R ink except that the same amount of C.I. Pigment Green 36 was used instead of the C.I. Pigment Red 254 in the above composition. A B (blue) ink 1 was prepared in the same manner as in the case of the R ink except that the same amount of C.I. Pigment Blue 15: 6 was used instead of the C.I.Pigment Red 254 in the following composition.

By baking the color filter after pixel coloring in a 230 degreeC oven for 30 minutes, the black matrix and each pixel were fully hardened | cured and the color filter was obtained.

(evaluation)

Evaluation of Absorbance (Optical Concentration) of 555 nm

Except for exposing to the whole sample surface without using an exposure mask, the layer of the sample thin film for a measurement whose OD becomes 3.0 or less was produced on the glass plate by the method similar to the method of manufacturing a deep color isolation wall. Measure the absorbance (optical density) at wavelength 555 nm of this sample using a spectrophotometer (UV-2100, manufactured by Shimadzu Seisakusho) (OD), and separately measure the absorbance (optical density) of the glass substrate in the same way. measuring and (OD _0), has a value obtained by subtracting the OD ₀ to OD at the absorbance (optical density) of the isolation wall of the hyperchromic 555㎚. Subsequently, using a contact surface roughness meter (trade name: P-10, manufactured by KLA Tencol Co., Ltd.), the film thickness of the sample for measurement was measured, and from the relationship between the optical concentration (absorbance) and the film thickness of the measurement result. The absorbance (optical density) of the deep color separation wall of the film thickness produced in the Example was calculated.

(Evaluation of height)

The height of the deep color isolation wall was measured using the contact surface roughness meter (brand name: P-10, KK Tencol Co., Ltd. product).

Mixed color evaluation between pixels (1)

The obtained color filter was visually observed with a 200-fold optical microscope to examine the presence or absence of color mixing between pixels. 1000 pixels were observed and divided into the following ranks. The results are shown in Table 1. Permitted are A rank and B rank.

A rank: There is not mixed color at all

B rank: 1 to 3 mixed colors

C rank: 4-10 places of mixed colors

D rank: Things more than 11 places of mixed colors

Mixed color evaluation between pixels (2)

The obtained color filter was visually observed with a 200-times optical microscope from the opposite side of the side where the pixel was formed on the board | substrate (surface used as an observer side when it is a panel), and the presence or absence of the mixed color between pixels was investigated. 2000 pixels were observed and divided into the following ranks. The results are shown in Table 1. Permitted are A rank and B rank.

A rank: There is not mixed color at all

B rank: 1 to 6 mixed colors

C rank: 7 to 20 mixed colors

D rank: There are more than 21 places of mixed colors

(White evaluation between pixels)

The obtained color filter was observed with an optical microscope of 200 times from the opposite side (the side which becomes an observer side when it is a panel) of the side in which the pixel was formed on the board | substrate, and it evaluated about white (the place where ink does not adhere to a pixel). did.

Observation of white was performed about arbitrary 100 points of the convex angle in the pixel isolation wall side in a pixel.

A rank: There is not white at all

B rank: There are less than five white

C rank: There are less than ten white more than five

D rank: There are ten or more white

(Example 1-2)

In Example 1-1, the deep color separation wall of the shape shown to FIG. 18 (B) was obtained by the same method as Example 1-1 except having changed the exposure pattern of a laser beam into FIG. 18 (B).

This sample was produced in the same manner as in Example 1-1 and evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

(Example 1-3)

(Production of Photosensitive Resin Transfer Material)

The following thermoplastic resin layer, an oxygen barrier layer (middle layer) and a deep color photosensitive resin composition layer are formed on a polyethylene terephthalate film base member having a thickness of 75 μm in order from the base body, and a protective film (polypropylene having a thickness of 12 μm) thereon. Film) was pressed to obtain a photosensitive resin transfer material.

(Formation of the thermoplastic resin layer)

The following coating liquid for thermoplastic resin layers was apply | coated using a slit-shaped nozzle so that a dry film thickness might be set to 14.5 micrometers, and it dried at 100 degreeC for 3 minutes, and obtained the thermoplastic resin layer.

(Coating liquid prescription 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 = 100000, Tg ≒ 70 ° C.): 5.83 parts

Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10000, Tg ≒ 100 ° C.): 13.6 parts

2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.): 9.1 parts

Surfactant 1: 0.54 parts

(Formation of oxygen barrier layer (intermediate layer))

On the above-mentioned thermoplastic resin layer, the coating liquid for oxygen blocking layer (intermediate layer) below was apply | coated so that a dry film thickness might be 1.6 micrometer using the slit-shaped nozzle, and it dried at 100 degreeC for 3 minutes, and formed the oxygen barrier layer (intermediate layer). .

(Coating liquid prescription for oxygen barrier layer (middle layer))

Polyvinyl alcohol: 2.1 parts

(PVA205 (soap ratio = 88%); Kuraray Co., Ltd.)

Polyvinylpyrrolidone: 0.95 parts

(PVP, K-30; product made by ISP Japan)

Methanol: 44 parts

Distilled water: 53 parts

(Formation of deep photosensitive resin composition layer)

The deep color photosensitive resin composition of Example 1 was apply | coated so that a dry film thickness might be 2.2 micrometer on the said intermediate | middle layer, and it dried at 100 degreeC for 3 minutes, and the deep photosensitive resin composition layer was formed.

(Formation of deep isolation wall)

The alkali-free glass substrate was washed with a rotary brush having nylon bristles while spraying the glass detergent liquid adjusted to 25 ° C. for 20 seconds with a shower, and after washing with pure water, the silane coupling liquid (N-β (aminoethyl) γ- 0.3 mass% of aminopropyl trimethoxysilane aqueous solution, brand name: KBM603, the Shin-Etsu Chemical Co., Ltd. product was sprayed for 20 second by shower, and the pure water shower wash | cleaned. This board | substrate was heated at 100 degreeC for 2 minutes with the board | substrate preheater.

After peeling off the protective film of the said photosensitive resin transfer material, the board | substrate heated at the said 100 degreeC for 2 minutes using the laminator (brand name: Lamic II type, the Hitachi Industries Co., Ltd.), the rubber roller temperature 130 degreeC, 100N of line pressures / cm and a conveyance speed of 2.2 m / min, were laminated to form a deep photosensitive resin composition layer.

Subsequently, the said sample was exposed by the method similar to Example 1-1.

30 ° C. with a triethanolamine developer (2.5% triethanolamine content, nonionic surfactant content, polypropylene antifoaming agent, trade name: T-PD1 (Fuji Shacin Film product) diluted 10-fold with pure water) Ultrasonically, the shower development was performed at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier layer.

Subsequently, Na-carbonate developer (0.06 mol / liter of sodium bicarbonate, the same concentration of sodium carbonate, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer containing, brand name: T-CD1 (Fuji Shacin Film product) ), Which was diluted 5 times with pure water, was shower-developed at a cone nozzle pressure of 0.15 MPa for 30 seconds at 29 ° C., and the deep photosensitive resin composition layer was developed.

Subsequently, the cone nozzle pressure was 33 ° C. for 20 seconds using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, and brand name “10-fold dilution of T-SD1 (Fuji Shacin Film product) with pure water”). The residue was removed by a rotating brush having a shower and nylon wool at 0.02 MPa, and a pattern image was obtained, and then post-exposure with light of 500 mJ / cm 2 with ultra-high pressure mercury lamp from the side of the resin layer with respect to the substrate. It heat-processed 15 degreeC and obtained the deep color isolation wall of the shape shown to FIG. 18A.

Subsequently, water repellent treatment was performed by the following method.

(Water repellent treatment by coating method)

Alkali-soluble photosensitive resin (hex to which the fluorine-type surfactant (made by Sumitomo 3M, Florade FC-430) is previously added to 0.5 mass% (for solid content of the photosensitive resin) on the board | substrate with which the rich isolation wall was formed. Japan Co., Ltd. and positive type photoresist AZP4210) were apply | coated using a slit-shaped nozzle so that it might become a film thickness of 2 micrometers, and 90 degreeC and 30-minute heat processing were performed in the warm air circulation dryer.

Subsequently, the substrate was formed with an exposure dose of 110 mJ / cm 2 (38 mW / cm 2 x 2.9 seconds) through the deep separation wall from the substrate back side, and then placed in an inorganic alkaline developer (Hex Japan, AZ400K developer, 1: 4). After immersion rotation for 80 seconds, a rinse treatment was performed for 30 to 60 seconds in pure water, and a surface energy difference was provided inside and outside the pixel by forming a water-repellent resin layer on the deep color separation wall. Surface energy inside and outside the pixel after the water repellent resin layer is formed is 10 to 15 dyn / cm (10 to 15 x 10 ^-3 N / m) outside the pixel (on the resin layer), and 55 dyn / cm (55 on the glass substrate). X10 ^-3 N / m) before and after.

This sample was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

(Reference Example 1-1)

In Example 1-1, the color filter was produced like Example 1-1 except having changed the deep color isolation wall formation into the following mask exposure, and it evaluated similarly to Example 1-1. The results are shown in Table 1.

(Mask exposure)

Proximity type exposure machine (product made by Hitachi Hi-Tech Denshi Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, between the exposure mask surface and the deep color photosensitive resin composition layer with the substrate and the mask (a quartz exposure mask having an image pattern) upright. The distance of was set to 200 micrometers, and pattern exposure was performed by exposure amount 300mJ / cm <2>. Exposure was carried out under nitrogen purge and under nitrogen atmosphere. However, the mask shape is the shape of FIG. 18A.

(Reference Example 1-2)

In Example 1-1, the color filter was formed in the same manner as in Example 1-1 except that the dark-separated wall was formed by the same mask exposure as in Reference Example 1-1, and the ink was changed to the following prescription. It produced and evaluated similarly to Example 1-1.

The results are shown in Table 1.

(The composition of R ink 2)

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

Polymer Dispersant (Salpers 24000, manufactured by AVECIA): 1 part

Binder (glycidyl methacrylate-styrene copolymer): 7 parts

1 epoxy resin (novolak-type epoxy resin, Yukacel company Epicoat 154): 3 parts

Curing agent (trimellitic acid): 4 parts

Solvent: 3-ethoxy ethyl propionate: 80 parts

In the ink, among the above components, first, a pigment, a polymer dispersant, and a solvent are mixed, a pigment dispersion is obtained by using three rolls and a bead mill, and the pigment dispersion is mixed with other materials while sufficiently stirring the dissolver. Small amounts were added and R (red) ink 2 was prepared. The viscosity of the R (red) ink 2 at this time was 11 cPs.

A G (green) ink 2 was prepared in the same manner as in the case of R ink except that the same amount of C. I. pigment green 36 was used instead of C.I. pigment red 254 in the above composition. A B (blue) ink 2 was prepared in the same manner as in the case of R ink except that the same amount of C.I. Pigment Blue 15: 6 was used instead of the C.I.Pigment Red 254 in the following composition.

(Reference Example 1-3)

In Example 1-1, the color filter was formed in the same manner as in Example 1-1, except that the deep color separation wall was formed by the same mask exposure as in Reference Example 1-1, and the ink was changed to the following prescription. It produced and evaluated similarly to Example 1-1. The results are shown in Table 1.

(The composition of R ink 3)

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

Polymer Dispersant (SALPERS 24000, manufactured by AVECIA): 1 part

Binder (glycidyl methacrylate-styrene copolymer): 8.5 parts

1 epoxy resin (novolak-type epoxy resin, Yukacel company Epicoat 154): 1.5 parts

Curing agent (trimellitic acid): 4 parts

Solvent: Ethyl 3-ethoxypropionate: 80 parts

Among the above components, the ink is first mixed with a pigment, a polymer dispersant, and a solvent, to obtain a pigment dispersion using three rolls and a bead mill, while the pigment dispersion is sufficiently stirred with a dissolver or the like and other materials. Was added little by little, and R (red) ink 3 was prepared. At this time, the viscosity of R (red) ink 3 was 14 cPs.

A G (green) ink 3 was prepared in the same manner as in the case of R ink except that the same amount of C. I. pigment Green 36 was used instead of C.I. Pigment Red 254 in the above composition. In addition, B (blue) ink 3 was prepared in the same manner as in the case of R ink except that the same amount of C.I. Pigment Blue 15: 6 was used instead of C.I. Pigment Red 254 in the following composition.

(Example 1-4)

In Example 1-2, the color filter was produced like Example 1-2 except having changed the prescription of ink into the prescription same as the reference example 1-3, and it carried out similarly to Example 1-1. Evaluated. The results are shown in Table 1.

(Examples 1-5 to 1-7)

In Examples 1-1 to 1-3, a color filter was produced in the same manner as in Example 1-1 except that no water repellent treatment was performed. The results are shown in Table 1.

In addition, the "curvature radius of a deep isolation wall" in Table 1 is the curvature radius of the inner part of the deep isolation wall shown in the top view of the color filter of FIG.

Table 1

(Examples 2-1 to 2-7 and Reference Examples 2-1 to 2-3)

In the thick photosensitive composition, the amount of the carbon black dispersion was changed to 23 parts, the amount of the DPHA solution was changed to 4.5 parts, and the amount of the surfactant 1 was changed to 0.055 parts, respectively, and the amount of the dispersant in the carbon black dispersion was 0.80% and propylene. Example 2-1 which was a color filter sample in the same procedure as Example 1-1 to 1-7 and Reference Examples 1-1 to 1-3, except that the amount of glycol monomethyl ether acetate was changed to 79.38%, respectively. 2-7 and Reference Examples 2-1 to 2-3 were produced.

The produced Examples 2-1 to 2-7 and Reference Examples 2-1 to 2-3 were evaluated in the same manner as in Examples 1-1 to 1-7 and Reference Examples 1-1 to 1-3. . Moreover, the blackness of the deep color isolation wall was evaluated by the following procedure. The results are shown in Table 2.

(Evaluation of Blackness of Deep Insulating Wall)

Except for exposing to the whole sample surface without using an exposure mask, it carried out similarly to the method of manufacturing a deep color isolation wall, and produced the layer of the sample thin film for a measurement whose OD becomes 3.0 or less on the glass plate. The absorbance of the 450 nm-650 nm wavelength range of this sample was measured using the spectrophotometer (The Shimadzu Corporation), UV-2100. The 500 nm and 600 nm values were calculated | required from this chart, and it calculated by the following formula. However, the absorbance of the glass substrate was measured in the same manner (OD ₀ ), and the values obtained by subtracting the respective OD ₀ values were taken as absorbances at 600 nm and absorbances at 500 nm, respectively. Subsequently, the film thickness of the sample for measurement was measured using a contact surface roughness meter (trade name: P-10, manufactured by K-Eighten Co., Ltd.), and from the relationship between the absorbance of the measurement result and the film thickness, The absorbance of the thick isolation wall of the produced film thickness was computed, and blackness was evaluated by the absorbance ratio shown by a following formula.

Absorbance (A ₆₀₀ ) at blackness = 600 nm Absorbance (A ₅₀₀ ) at ₅₀₀ nm

Table 2

As can be seen from Table 1 and Table 2, the color filter of the present invention in the embodiment is suitable for display devices because there is no color mixing between pixels. Since the mask is not used in the manufacturing method of the color filter of the present invention, the shape of the deep color separation wall can be changed easily and freely according to the properties of the ink, so that the deep color separation wall suitable for the prevention of mixed color and the white can be formed. Can be. The color filters of Examples 1-1 to 1-3 and Example 2-1 to 2-3 that were subjected to a water repellent treatment were of good quality in that there was no color mixing.

On the other hand, according to the reference examples 1-2, 1-3, 2-2, and 1-3, when the physical properties of ink changed, it turned out that a defect arises by the shape of a deep color isolation wall.

(Example 8)

(Example of liquid crystal display device)

Using the color filters obtained in Examples 1-1 to 1-7 and 2-1 to 2-7, liquid crystal display devices 1-1 to 1-7 and 2-1 to 2-7 were produced as follows. .

(Overcoat layer formation)

The obtained color filter is washed with a low pressure mercury lamp (effective wavelength 254 nm) UV cleaning device to remove residues and foreign substances, and then the following transparent overcoat agent is applied and baked. It baked for 40 minutes at 230 degreeC after apply | coating front surface so that the film thickness might be 1.5 micrometer. At this time, the coating liquid which forms a transparent overcoat layer mixed and used the polyamic acid of following formula (6) and the epoxy compound of the formula (7) by 3: 1 weight ratio.

Formula 6

Formula 7

(Formation of ITO)

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

(Formation of spacer)

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

(Formation of projection for liquid crystal alignment control)

Using the coating liquid for positive type photosensitive resin below, the liquid crystal aligning control processus | protrusion was formed in the location corresponded to the upper part of the colored pixel on the ITO transparent electrode in which the said spacer was formed.

However, the following method used the exposure, image development, and baking process.

Proximity exposure machine (Hitachi Hi-Tech Denshi Engineering Co., Ltd.) is arrange | positioned so that a predetermined photomask may be 100 micrometers distance from the surface of the photosensitive resin layer, and it proxies through the said photomask at 150mJ / cm <2> by the ultra-high pressure mercury lamp. Miti exposure.

Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying onto the substrate at 33 ° C. for 30 seconds with a shower developing device. In this way, by developing and removing the unnecessary part (exposure part) of the photosensitive resin layer, the board | substrates 1-3 for liquid crystal display devices in which the liquid crystal orientation control protrusion which consists of the photosensitive resin layer patterned in the desired shape on the color filter side board | substrate were formed. Got it.

Subsequently, baking the board | substrate for liquid crystal display devices in which the said liquid crystal orientation control protrusion was formed for 30 minutes under 230 illustration was formed, and the hardened liquid crystal orientation control protrusion was formed on the liquid crystal display device substrate.

(Coating liquid prescription for positive type photosensitive resin layer)

Positive resist liquid (FH-2413F manufactured by Fujifilm Electronics): 53.3 parts

Methyl ethyl ketone: 46.7 parts

Surfactant 1: 0.04 parts

(Production of LCD)

After that, a UV-curable resin sealant is applied by a dispenser method at a position corresponding to the black matrix outer frame formed around the pixel group of the color filter, and the liquid crystal for MVA mode is dropped and bonded to the counter substrate. After that, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealing agent.

The polarizing plate HLC2-2518 made from Sanritsu Co., Ltd. was stuck on both surfaces of the liquid crystal cell obtained in this way.

Subsequently, FR1112H (chip type LED by Stanley Co., Ltd.) as red (R) LED, DG1112H (chip type LED by Stanley Co., Ltd.) as green (G) LED, and DB1112H (Stanley Co., Ltd.) as blue (B) LED. And a side light type backlight, which are arranged on the side of the backside of the liquid crystal cell in which the polarizing plate is formed, and the liquid crystal display devices 1-1 to 1-7 and 2-1 of the present invention. -2-7 was produced.

(evaluation)

The display quality in the case where the obtained liquid crystal display devices 1-1 to 1-7 and 2-1 to 2-7 were displayed in white, and black display was observed visually. The case where white or black pure color is displayed is made good, and the case where it looks reddish is made defective.

The screen of the liquid crystal display device provided with the color filter produced in Example was a good screen without any color mixing. In addition, there was no deterioration of the display quality such that the white display and the black display state were slightly reddish.

(Example of liquid crystal display device)

Using the color filters obtained in Examples 2-1 to 2-3, liquid crystal display devices 2-1 to 2-3 were produced in the same procedure as liquid crystal display devices 1-1 to 1-3.

When the obtained liquid crystal display devices 2-1 to 2-3 displayed white and the display quality in the case where black displayed, were visually observed. The case where white or black pure color is displayed is made good and the case where it looks reddish is made defective.

The screen of the liquid crystal display device provided with the color filter produced in Example was a good screen without any color mixing. In addition, there was no deterioration of the display quality which was slightly reddish in both the white display and the black display state, and the display quality was also excellent. In particular, when the quality of black display was compared with respect to the liquid crystal display devices 1-5 to 1-7, black finish improved in order of 1-5, 1-6, 1-7.

According to the manufacturing method of the color filter provided by this invention, since exposure is performed without using an exposure mask, the shape of a deep color isolation wall can be changed freely and the pixel without a mixed color can be manufactured at low cost. In addition, the color filter provided by the present invention has a pixel having no color mixture by the manufacturing method. In addition, the display device provided by the present invention uses a color filter having the pixel without the mixed color.

Claims (14)

As a manufacturing method of a color filter, Forming a deep color separation wall having a height of 1.0 mu m or more by maskless exposure and development; And After the deep color separation wall forming step, forming a pixel group by applying a droplet containing a colored liquid composition: The color filter, Board; And Comprising a plurality of said pixel groups having at least two colors formed on said substrate: and And the pixels are separated from each other by the deep color separation wall. The method of manufacturing a color filter according to claim 1, wherein the pixel forming step is performed in a state where at least a part of the upper surface of the deep color separation wall has water repellency. The method of manufacturing a color filter according to claim 1 or 2, wherein an optical density of the deep color separation wall is 2.5 or more. The method for manufacturing a color filter according to any one of claims 1 to 3, wherein the deep color separation wall forming step includes the following steps (1) or (2): (1) a step of coating and drying a photosensitive resin composition containing a colorant on a substrate, exposing and developing with a laser; or (2) The process of transferring the said photosensitive transfer layer to a board | substrate, exposing with a laser, and developing using the transfer material in which the photosensitive transfer layer containing a coloring agent was formed on the branch body. The method of manufacturing a color filter according to any one of claims 1 to 4, wherein the droplet applying is performed by an inkjet method. The color filter manufactured by the manufacturing method in any one of Claims 1-5. A display device comprising the color filter according to claim 6. As a manufacturing method of a color filter, Forming a separation wall by subjecting the deep color separation wall to light by modulating light on the basis of the separation wall image data and subjecting the photosensitive resin composition layer for formation of the color separation wall formed on the substrate to be subjected to relative scanning exposure and developing; And After said relative scanning exposure process, forming a pixel group by applying a droplet containing a colored liquid composition: The color filter, Board; And Comprising a plurality of said pixel groups having at least two colors formed on said substrate: The pixels are isolated from each other by the deep color separation wall: and A ratio (A ₆₀₀ / A ₅₀₀ ) of absorbance (A ₆₀₀ ) at ₆₀₀ nm of the deep color separation wall to absorbance (A ₅₀₀ ) at ₅₀₀ nm is 0.7 to 1.4. The method of manufacturing a color filter according to claim 8, wherein the pixel forming step is performed in a state where at least a part of the upper surface of the deep color separation wall has water repellency. The method for manufacturing a color filter according to claim 8 or 9, wherein the absorbance at 555 nm of the deep color separation wall is 2.5 or more. The method for producing a color filter according to any one of claims 8 to 10, wherein the step of forming the photosensitive resin composition layer for the deep color separation wall comprises the following (1) or (2): (1) applying and drying the photosensitive resin composition containing a coloring agent to a board | substrate, and applying and drying the photosensitive resin composition containing a coloring agent to a board | substrate; or (2) The process of transferring the said photosensitive transfer layer to a board | substrate using the transfer material in which the photosensitive transfer layer containing a coloring agent was formed on the base body. 12. The method for manufacturing a color filter according to any one of claims 8 to 11, wherein the drop applying is performed by an inkjet method. The color filter manufactured by the manufacturing method in any one of Claims 8-12. A display apparatus comprising the color filter according to claim 13.

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