JPH08201616A - Method for producing color filter and color filter obtained by the method - Google Patents

Abstract

PURPOSE: To produce an RGB or YMC color filter without need for an intricate process and capable of being easily produced and to improve the spectral transmittance and hue by conducting specified pattern exposure. CONSTITUTION: When pattern exposure is conducted in the production of an RGB or YMC color filter, a liq. crystal display panel with a white light source provided on the rear and a photosensitive materials set on the front is used, three color filters corresponding to the color sensitivity of the photosensitive material are successively inserted between the panel and the light source or the photosensitive material, a light of the desired color element of the panel is correspondingly transmitted according to an optional arrangement, and the exposure is successively conducted three times. Otherwise, three light sources of different wavelengths are provided on the rear in accordance with the color sensitivity of the photosensitive material, a liq. crystal display panel with a photosensitive material set on the front is used, the light sources are successively lit, a light of the desired color element of the panel is correspondingly transmitted according to an optional arrangement, and exposure is successively conducted three times.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a color filter in which pixels having red, green and blue portions having excellent spectral transmission characteristics, or pixels having yellow, magenta and cyan portions are arbitrarily arranged in a mosaic shape or a stripe shape. The present invention relates to a simple manufacturing method. In particular, the present invention relates to a method for producing a color filter having a pixel array and a shape corresponding to a liquid crystal display to be incorporated in a short time.

[0002]

2. Description of the Related Art Color filters are used in color face plates for CRT display, photoelectric conversion element plates for copying, filters for single-tube color television cameras, flat panel displays using liquid crystals, color solid-state image pickup elements and the like. . A commonly used color filter is formed by regularly arranging the three primary colors of blue, green and red, but there are some filters having four or more hues as necessary. For example, a color filter for an image pickup tube or a color filter for a liquid crystal display device requires a black pattern for various purposes.

Conventionally known methods for producing a color filter include a vapor deposition method, a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method and a resist electrodeposition transfer method. However, the color filters obtained by these methods have drawbacks such as requiring complicated manufacturing steps, being prone to pinholes and scratches, having a low yield, and being inaccurate.

In order to solve these drawbacks, an external development method (for example, JP-A-55-6342) and an internal development method (for example, JP-A-62-148952) using a silver halide color photographic light-sensitive material are used. No. 62-71950), a method for producing a color filter was investigated. But,
The former method requires color development at least 3 times,
It is hard to say that the treatment process is simple. The latter method has blue, green and red parts having excellent spectral transmission characteristics, as compared to the case where one type of conventional yellow, magenta and cyan couplers are used for each silver halide emulsion layer, and has a color filter part. There is an advantage that a micro color filter having a black portion having a higher optical density can be easily obtained. However, even with this method, it has been found that it is difficult to obtain red (R), green (G), and blue (B) portions having high spectral transmittance and excellent hue. The present inventors proposed in Japanese Patent Application No. 6-274649 a method for producing a color filter in which the hues of RGB are optimized by using a plurality of couplers of yellow, magenta or cyan.

These methods require a mask or mask color filter having a desired shape and arrangement when exposing a silver halide light-sensitive material. The arrangement and form of BGR or YMC of the color filter are various depending on the use, the manufacturer, each product, and the like. Therefore, the mask and mask color filter are frequently changed according to the arrangement and form of various color filters. In particular, when a mask color filter having a pattern of RGB or YMC is used, the mask color filter is manufactured by the conventional vapor deposition method,
The dyeing method or the pigment dispersion method has problems that the manufacturing process is complicated and the cost is high.

On the other hand, even if a coupler and a developer having excellent color reproducibility are combined, if the color separation exposure to the light-sensitive material does not match the spectral sensitivity of the light-sensitive material, the color of the color filter obtained. Reproducibility does not improve. It is considered that a color separation mask is created for each color of RGB or YMC and is exposed three times by overlapping, or one exposure is performed using the mask color filter in which RGB or YMC is arranged in a mosaic pattern, a stripe pattern, or the like. However,
It was easy to cause color misregistration. Further, recently, the size of liquid crystal display has been actively increased, and accordingly, the color filter has also been increased in size, further complicating the manufacturing process and increasing the manufacturing cost. Therefore, there is a demand for a method for easily and inexpensively manufacturing color filters having various types of BGR or YMC arrangements and forms.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned various drawbacks of the prior art, to require no complicated steps, to be suitable for mass production, and to have excellent spectral transmission characteristics and hue. Another object of the present invention is to provide a method of manufacturing a color filter having RGB or YMC. Furthermore, the present invention provides a method for easily manufacturing a color filter having a pixel arrangement and shape suitable for various types of liquid crystal displays to be incorporated in a short time, and an RGB color filter having excellent spectral transmission characteristics and hue obtained thereby.
Another object is to provide a color filter having YMC.

[0008]

As a result of careful consideration of the above-mentioned various characteristics, the present inventors have found that the above-mentioned object can be achieved by the following constitution. (1) In the method for producing an RGB or YMC color filter, which comprises pattern-exposing a light-sensitive material having at least three silver halide emulsion layers having different color sensitivities on a light-transmissive substrate, and performing color development and decolorization. A method for producing an RGB or YMC color filter, characterized in that the pattern exposure is performed by any of the following methods (a) and (b). (A) A liquid crystal display panel in which a white light source is provided on the back surface and the photosensitive material is provided on the front surface, and the color sensitivity of the photosensitive material is provided between the liquid crystal display panel and the light source or the photosensitive material. Three color filters are sequentially inserted, and correspondingly, light of a desired pixel of the liquid crystal display panel is transmitted according to an arbitrary arrangement, and exposure is sequentially performed three times. (B) A liquid crystal display panel in which three light sources having different wavelengths are provided on the back surface in correspondence with the color sensitivity of the light-sensitive material and the light-sensitive material is installed on the front surface, and the light sources are sequentially turned on. Light of a desired pixel of the liquid crystal display panel is transmitted according to an arbitrary arrangement, and exposure is sequentially performed three times. (2) Of the at least three couplers, the silver halide emulsion layer of the light-sensitive material is substantially coupled among the at least three couplers which form a dye of any one of yellow, magenta and cyan by coupling reaction with an oxidant of a developing agent. The above-mentioned (1), wherein each of the silver halide emulsion layers having different color sensitivity contains at least two kinds of couplers forming different dyes, and each layer emits blue, green and red. Manufacturing method of color filter. (3) The silver halide emulsion layer of the light-sensitive material is composed of at least two unit layers, and each of these at least two unit layers undergoes a coupling reaction with an oxidant of a developing agent to form yellow, Among at least three couplers forming dyes of magenta and cyan, couplers having different dyes formed from each other are contained respectively, and blue and green are respectively contained in silver halide emulsion layers having different color sensitivities. The method for producing a color filter according to (1) above, wherein the layer exhibits a red color. (4) At least three silver halide emulsion layers having different color sensitivities are provided on a release layer coated on an arbitrary support, and the emulsion surface is brought into close contact with a light-transmitting substrate, After peeling and removing the support, the emulsion surface is subjected to the pattern exposure,
The method for producing a color filter according to (1) above, which comprises color development and desilvering. (5) A color filter produced by the method described in any one of (1) to (4) above.

[0009]

Operation: To manufacture a color filter, a liquid crystal display panel is used, and pixels of each of the three colors are sequentially exposed to a silver halide light-sensitive material through a color filter corresponding to the color sensitivity of the light-sensitive material and developed. This makes it possible to easily manufacture a color filter having a desired pixel arrangement and shape and having RGB or YMC having excellent spectral transmission characteristics and hue. That is, the present invention uses the liquid crystal display panel which is planned to incorporate the color filter, and
Controlling the light transmittance of pixels corresponding to each color of B or YMC (that is, using a liquid crystal display panel as an optical shutter), and sequentially exposing the photosensitive material with light having a wavelength matching the color sensitivity of the photosensitive material. This makes it possible to easily and accurately manufacture color filters having various types of arrangements and shapes, and obtain color filters having excellent spectral transmission characteristics. Further, each emulsion layer having different color sensitivity of the light-sensitive material to be used contains a plurality of yellow, magenta and cyan couplers, respectively, and forms at least blue, green and red layers by color development processing. The spectral transmission characteristics and hue of the obtained color filter become more excellent.

One aspect of the method of the present invention will be specifically described with reference to the drawings. However, the content of the present invention is not limited to this. FIG. 1 is a schematic sectional view of an example of an exposure apparatus using a liquid crystal display panel that can be used in the method of the present invention. The apparatus comprises a light source 1, a liquid crystal display panel 3, a color filter 2 between them, and a color filter 2 on the side opposite to the color filter 2 and in close contact with the liquid crystal display panel 3, and an emulsion layer 4 is provided on a light transmissive substrate 5. It consists of a photosensitive material 15. In the present invention, the liquid crystal display panel 3 can be used in any type of transmissive liquid crystal display device, but in the present invention, one having a desired type of pixel arrangement and shape, that is, a completed color filter is incorporated. It is preferable to use a planned liquid crystal display panel. For details on color LCDs and their manufacturing methods, refer to “Fundamentals and Applications of Liquid Crystals” by Shoichi Matsumoto and Ryo Kakuda (published by the Industrial Research Committee in 1991), “Flat Panel Display 1994” edited by Nikkei Microdevices (1993). (Published by Nikkei BP Co., Ltd.), Japanese Patent Laid-Open No. 1-114820, and the like.

The liquid crystal display panel 3 shown in FIG. 1 has a liquid crystal layer 6 in the center thereof, an alignment film 7 on both upper and lower sides thereof, and an alignment film 7 thereof.
Transparent electrodes 10 and 11 which are respectively in contact with the upper and lower light-transmissive substrates 8 and 9 are disposed on the upper and lower sides of the substrate. The light transmissive substrates 8 and 9 are in contact with each other via the seal material 12 and spacers (not shown) on both side surfaces thereof. Here, in the active matrix driving LCD using a three-terminal switching array such as a TFT, the transparent electrode 10 is formed as an entire surface integral electrode, and is a simple matrix driving LC.
In an active matrix driving LCD using a two-terminal switching array such as D or MIM, it is usually formed as a stripe electrode. In addition, the transparent electrode 11 is TF
In an active matrix drive LCD using a three-terminal switching array such as T, it is a pixel electrode connected by a TFT element, and in a simple matrix drive LCD such as STN, it is a stripe electrode, and is arranged perpendicular to the transparent electrode 10. To be done. In addition, the polarizing plates 13 and 14 are disposed on the upper and lower sides of the light transmissive substrates 8 and 9, respectively. Furthermore,
If necessary, a retardation plate may be provided between the polarizing plate and the light transmissive substrate, and an electrode protective coat may be further provided between the transparent electrode and the alignment film, and the light transmissive substrate is soda lime glass. In such cases, the surface of the transparent electrode may be coated with an alkali sealant.

In the method of the present invention, exposure is performed for each pixel of each color that constitutes a desired color filter. First, for one color pixel, the voltage applied to the liquid crystal display panel 3 is changed to change the orientation of the liquid crystal so that the light of the pixel of that color is transmitted. At this time, the liquid crystals of the pixels of other colors do not change their orientation. Then, the photosensitive material 15 is exposed through the liquid crystal display panel 3 with light having a wavelength corresponding to the color sensitivity of the first silver halide emulsion layer. After that, the pixels of other colors are similarly changed so that the light of the pixels of the corresponding color is transmitted, and the wavelength is adjusted to the color sensitivity of other silver halide emulsion layers to correspond to the pixels of each color. Then, the photosensitive material 15 is exposed. Here, as the light source 1, as shown in FIG. 1, a white light source (for example, an incandescent lamp, a fluorescent lamp, an EL
The wavelength of light can be adjusted by disposing the color filter 2 between the light source 1 and the light transmissive substrate 9 using a lamp, an LED, or the like). Here, the arrangement of the color filter 2 is not limited to the above, and the arrangement between the light source 1 and the liquid crystal display panel 3,
Or if it is between the liquid crystal display panel 3 and the photosensitive material 4,
Any place is acceptable.

As the light source, an exposure device (for example, LED or laser) having its respective wavelength is prepared,
The wavelength may be changed for each exposure. As the exposure method, a surface exposure method or a scanning exposure method can be used. As the scanning exposure method, line (slit) scanning or point scanning exposure such as LED laser exposure can be applied. In the present invention, a backlight normally used for a liquid crystal display as a light source (in this case, a direct type or an edge light type may be used)
And a method of using the above-mentioned color filter is preferable because the apparatus configuration is simple. As the color filter 2 that can be used in the present invention, a commercially available color separation filter, interference filter or the like can be used according to the color sensitivity of the light-sensitive material. The color sensitivity of the light-sensitive material can be made not only red-sensitive, green-sensitive and blue-sensitive but also yellow-sensitive and infrared-sensitive by appropriately selecting a spectral sensitizer to be combined. In particular, when a light emitting diode, a laser or the like is used as a light source, it is preferable to have infrared sensitivity. More specifically, the exposure method using the above liquid crystal display panel is described in, for example, JP-A-60-
The liquid crystal driving method of 32679 can be applied.

A black matrix is usually formed between each pixel of RGB or YMC to improve the contrast and color purity. The Black Matrix is
It may be formed at the same time as each pixel, or a Cr film, a carbon film, or the like may be formed separately.

The photosensitive material 15 thus exposed for each color is color-developed and decolorized by the method described below to obtain a color filter. The color filter on the light transmissive substrate manufactured by the method of the present invention can be directly used for a liquid crystal display device. Also,
In the manufactured color filter, a resin having heat resistance, water resistance, organic solvent resistance, and high specific electric resistivity can be applied as an outermost layer as a protective film (overcoat layer). Examples of such resins are US Pat. No. 4,698,295,
No. 4,668,601, European patent application EP-179,
No. 636A, No. 556,810A, JP-A-3-163.
No. 416, No. 3-188153, No. 5-78443.
No. 1-276101, JP-A-60-216307.
No. 63-218771 and the like. The obtained color filter preferably has as few irregularities on the surface as possible, particularly preferably ± 0.5 μm or less.

The color filter produced by the method of the present invention may be further provided with a transparent electrode (ITO) by vapor deposition coating, for example, vacuum vapor deposition or sputtering. Furthermore, an alignment film of polyimide resin or the like can be provided thereon. Further, a polarizing film or a retardation film may be provided on the surface of the color filter opposite to the emulsion surface of the light transmissive substrate.

Photosensitive material 15 that can be used in the present invention
The emulsion layer may be produced by directly providing an emulsion layer on a light-transmissive substrate such as a glass substrate, or a release layer coated on another support as described in Japanese Patent Application No. 6-303977. You may manufacture it by providing an emulsion layer on top and making the emulsion surface adhere to a light-transmissive substrate. When the photosensitive material is provided directly on a light-transmitting substrate such as a glass substrate, it can be provided by using a coating method such as spin coating. However,
It is not easy to manufacture a photosensitive material having a multi-layered structure on a hard light-transmitting substrate such as a glass substrate by spin coating. Therefore, the method of providing it on another support (the above-mentioned peeling method) is preferable.

The method for producing the color filter of the present invention will be described in more detail with reference to specific examples. (I) As an example of a silver halide light-sensitive material which can be used in the present invention, a material having a characteristic curve shown in FIG. 2 is used, and a blue-sensitive emulsion layer contains a cyan coupler and a magenta coupler to obtain a green-sensitive material. The emulsion layer contains a yellow coupler and a cyan coupler, and the red-sensitive emulsion layer contains a yellow coupler and a magenta coupler. And
The liquid crystal display panel is driven to sequentially expose it with blue, green and red light so that the exposure can be performed at the points A and B in FIG. After that, color development, bleaching / fixing, and washing with water are performed to obtain blue (B) as shown in FIG.
A color filter that develops green (G) and red (R) is obtained.

(II) FIG. 4 shows another example of the layer structure of the silver halide photosensitive material which can be used in the present invention. FIG.
As a result, since the same type of coupler can be added to the layer adjacent to each silver halide emulsion layer, the color mixture of the dyes between the emulsion layers can be reduced and the thickness of the color filter can be reduced without the intermediate layer. . In order to produce a color filter using the silver halide light-sensitive material which can be used in the present invention, after exposure as in the case of the above (I), color development, bleaching / fixing and washing treatment are carried out. A color filter that develops blue, green, and red as shown in FIG. Here, three of the silver halide emulsion layers having different color sensitivities are each composed of at least two unit layers, and the unit layers having the same color sensitivities are layers having different sensitivities. Or a layer having the same sensitivity may be used. The two unit layers each contain one type of coupler that forms different hues.

(III) As another example of the silver halide light-sensitive material which can be used in the present invention, a blue-sensitive emulsion layer contains a yellow coupler, a green-sensitive emulsion layer contains a magenta coupler, and a red-sensitive emulsion. The emulsion layer contains a cyan coupler. After exposure as in the case of the above (I), color development, bleaching / fixing, and washing with water are carried out to obtain a color filter that develops yellow, magenta, and cyan as shown in FIG. Further, by using an internal latent image type auto positive emulsion for the silver halide emulsion in this constitution and performing the fog treatment described later, a color filter that develops blue, green and red as shown in FIG. 3 can be obtained.

In the above (I), (II) and (III), 3
The two color sensitivities are not limited to a combination of blue sensitivity, green sensitivity and red sensitivity, and may be combined with infrared sensitivity or yellow sensitivity, or plural infrared sensitivities having different photosensitive wavelength regions may be adopted. The preparations for coating three silver halide emulsion layers having different color sensitivities are not limited to the above order but can be arbitrarily set. Further, in addition to the above-mentioned layer constitution, an undercoat layer, an intermediate layer, a bleachable yellow filter layer, a protective layer, an ultraviolet absorbing layer or the like may be provided if necessary. As the binder or protective colloid that can be used in the silver halide emulsion layer, intermediate layer and protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic polymers can also be used. . Examples of hydrophilic polymers include polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl butyral, and poly-N.
-Vinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, carrageenan, gum arabic, hydroxyalkyl cellulose, carboxymethyl cellulose, cellulose sulfate, cellulose acetate hydrogen phthalate, and cellulose derivatives such as sodium alginate. A copolymer may be used.

Further, a graft polymer of gelatin and another polymer may be used. As the gelatin-graft polymer, gelatin is added to acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and vinyl-based polymers such as acrylonitrile and styrene. It is possible to use grafted monomers or copolymers of monomers. Particularly preferred is a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate. Examples of these are described in US Pat. Nos. 2,763,625, 2,831,767, 2,956,884, and JP-A-56-65133.

As typical synthetic hydrophilic polymer substances, for example, West German patent application (OLS) 2,312,708, US Pat. Nos. 3,620,751 and 3,879,205.
And those described in JP-B-43-7561 can also be used. The above hydrophilic polymers may be used alone,
You may use 2 or more types together.

As gelatin, alkali treatment, acid treatment,
What was subjected to any of the enzyme treatments, or a mixture thereof may be used. It can also be obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultonic acid, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds. Gelatin derivatives are also used. Specific examples of the gelatin derivative are U.S. Pat. Nos. 2,614,928, 3,132,945, 3,186,846, 3,312,553, British Patents 861,414 and 1,033. No. 189, No. 1,005,784, and Japanese Examined Patent Publication No. 42-26845.

In the above peeling method, preferably, the layers other than the peeling layer of the light-sensitive material are composed of a binder mainly containing gelatin (including its derivative), and the peeling layer contains a polymer other than gelatin (including its derivative). It is composed of the main layers. What is a gelatin-based binder?
It means that about 80% or more of the binder is gelatin or a gelatin derivative. Similarly, the release layer contains about 80% or more of the hydrophilic polymer other than gelatin. The hydrophilic polymers may be used alone or in combination of two or more. When the content of the hydrophilic polymer is about 80% or more, the rest may contain gelatin or a gelatin derivative, and may further contain a dispersion of a hydrophobic compound.

The hydrophilic polymer of the release layer is preferably a cellulose derivative, and particularly preferably hydroxyalkyl cellulose. Examples of the compound include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and the like. Also, a mixture thereof is effective. The release layer is suitably 0.02 to 2.0 g / m ² , preferably 0.05.
~ 1.0 g / m ² .

In the present invention, at least one layer adjacent to the release layer contains about 8 parts of gelatin or gelatin derivative.
It is preferable to provide a gelatin-based layer containing 0% or more.
The remaining about 20% or less may include dispersions of the hydrophilic polymers or hydrophobic compounds described above. This layer is 0.01 ~
2.0 g / m ² is suitable, and preferably 0.05-1.
It is 0 g / m ² . In the present invention, the total coating amount of the binder (hydrophilic polymer) other than the release layer of the light-sensitive material is 20 g /
m ² or less, preferably 10 g / m ² or less, particularly 2 to 8
It is preferably g / m ² .

In the peeling method in the present invention, it is preferable that the emulsion surface of the silver halide light-sensitive material is brought into close contact with the light-transmissive substrate, the emulsion surface is subjected to pattern exposure, and a color image is obtained by development. Thereby, a highly accurate color filter can be manufactured. On the contrary, when the emulsion surface is brought into close contact with the light transmissive substrate after the color image is formed on the light-sensitive material, the emulsion surface is thin and soft, so that the pattern image is likely to be distorted at the time of the close contact. Further, it is preferable that the support is peeled off and removed after the emulsion surface is brought into close contact with the light transmissive substrate. The support may be peeled and removed before or after the exposure. It is preferable to peel and remove before exposure because it does not cause distortion in the pattern image.

To bring the emulsion surface of the silver halide light-sensitive material into close contact with the light-transmissive substrate, it is possible to use a commercially available adhesive capable of bonding the substrate and the emulsion layer, particularly the protective layer of the light-sensitive material. it can. Thermosetting resin type as adhesive
There are various types such as a thermoplastic resin type, an elastomer type, and a polymer alloy type, which can be used according to the material to be adhered. For example, when the substrate is glass and the binder of the emulsion layer or the protective layer is mainly gelatin, an epoxy-based polymer alloy type adhesive is preferable.

In the present invention, when the binder of the layers other than the release layer is mainly composed of gelatin, a preferable adhesion method is to apply a liquid containing gelatin and colloidal silica to the adhesion surface of the substrate (especially glass substrate) in advance using a spin coater or the like. It is a method in which the emulsion surface (especially protective layer) of the light-sensitive material is overlaid and heated and adhered by a laminator, iron, hot press or the like. In this case, the mixing ratio of gelatin and colloidal silica is 10: 1 to 1:10. The average particle size of colloidal silica is preferably 0.5 μm or less, and particularly preferably 0.1 μm or less. The heating temperature is 60 ° C. to 180 ° C., and the heating time can be arbitrarily set, but 0.1 second to 60 seconds is preferable. Further, the heating contact may be performed in the presence of a trace amount of water.

In the above case, after heat-adhesion, the support of the light-sensitive material is peeled off and removed (at this time, it is preferable to adjust the relative humidity to 50% or more in order to suppress the generation of static electricity) before color development. It is preferable to carry out a hardening treatment. As the hardener, those known in the photographic industry can be used. For example, aldehyde-based, ethyleneimine-based, isoxazole-based, epoxy-based, vinylsulfone-based, acryloyl-based, carbodiimide-based, cyanuric chloride-based, maleimide-based, acetylene-based, methanesulfonic acid ester-based, chrome myoban, potassium myoban And these are used alone or in combination. Also,
In the case of so-called multi-layering, in which a plurality of color filters are produced on one substrate, the photosensitive layer and the like in unnecessary portions can be decomposed and removed by using, for example, an enzyme solution or a sodium hypochlorite solution. This operation, whether before or after dura treatment,
It can be carried out anywhere in the process steps described below.

In the present invention, the material constituting the light transmissive substrate is preferably transparent, optically isotropic and has sufficient heat resistance, for example polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, Examples thereof include polycarbonate, polyether sulfone, cellulose acetate, polyarylate, soda glass, borosilicate glass, and quartz. The surface of the substrate made of these materials may be subjected to undercoating treatment, if necessary. Furthermore, treatments such as glow discharge, corona discharge, and ultraviolet (UV) irradiation may be performed.

The light transmissive substrate can be used in the form of a plate, a sheet or a film. The thickness of the substrate can be set appropriately according to the application and material,
Generally, it is 0.01 to 10 mm. For example, in the case of a glass substrate, the thickness is in the range of 0.3 to 3 mm.

The light-sensitive material that can be used in the present invention is
It is possible to use an external color reversal film, an internal color reversal film, a color negative film by a color negative process, a display color film, an auto positive color film and the like which can obtain a positive image by color reversal processing. These are described in the Science Photo Handbook (above) (Maruzen), pages 559-564, page 569, The.
The Theory of the Photographic Process 4th Edition,
It is described in the THJames edition. In addition, JP-A-6
No. 3-261361, and an inner type color light-sensitive material containing two or more kinds of couplers having different hues obtained by color development in the same light-sensitive silver halide emulsion layer, and the same as described in No. 64-79701. It is also possible to use an external color light-sensitive material which is developed with a developer containing two or more kinds of couplers showing different colors for the same light-sensitive silver halide and a developing agent.

In the light-sensitive material used in the present invention, the silver halide emulsion layer undergoes a coupling reaction with an oxidant of a developing agent, as described in JP-A-63-261361.
Each of the silver halide emulsion layers having different color sensitivity contains at least two couplers which form substantially different dyes among at least three couplers which form yellow, magenta and cyan dyes. It is preferable that the layers are layers emitting blue, green and red, respectively. On the other hand, as described in JP-A-62-71950, the silver halide emulsion layers of the light-sensitive material are each composed of at least two unit layers, and at least two of these unit layers are used.
In each of the three unit layers, among at least three types of couplers that form a dye of any one of yellow, magenta and cyan by a coupling reaction with an oxidized product of a developing agent, a coupler having a different dye is formed. It is preferable that the silver halide emulsion layers having different color sensitivities are blue, green and red, respectively.
As described above, a color obtained by forming layers respectively exhibiting blue, green, and red by using a plurality of couplers of at least three types of couplers forming a dye of any one of yellow, magenta, and cyan The spectral transmission characteristics and hue of the filter can be improved.

The light-sensitive material and the processing method which can be preferably used in the present invention will be outlined below. Preferred silver halides contained in the emulsion layer of the light-sensitive material used in the present invention are silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide, and the average iodide content is Is preferably 3% or less and 0%. Particularly preferably, it is substantially pure silver bromide or pure silver chloride.

The silver halide grains in the emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, and twins. It may have a crystal defect such as a plane or a composite form thereof. A cube or an octahedron is particularly preferable.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion, but it is 0.15. Preference is given to using monodisperse emulsions with a grain size of microns to 1.5 microns and a coefficient of variation of 15% or less.

The silver halide emulsion which can be used in the present invention is
For example, Research Disclosure (RD), 17
Volume 6 No. 17643 (December 1978), 22-23
Page, "I. Emulsion preparation and type
s) ”, and ibid. No. 18716 (1979, 11)
Mon), pp. 648, "The Physics and Chemistry of Photography" by Graphide,
Published by Paul Montel (P.Glafkides, Chemic et Phisiqu
e Photographique (Paul Montel, 1967)), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuff
in, Photographic Emulsion Chemistry (Focal Press, １
966)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al, Mak.
ing and Coating Photographic Emulsion (Focal Press,
1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are written by Gatov, Gutoff, Photographic Science and Eng.
ineering, Vol. 14, pp. 248-257 (1970)
Year): U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are listed in Research Disclosure No. 17643, No. 18716, and No. 18716.
It is described in No. 307105, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosure magazines, and the relevant portions are shown in the following table.

Additive type RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24 page 648 right column-866-868 page Supersensitization Agent page 649 right column 4 whitening agent page 24 648 page right column 868 page 5 antifoggant page 24 to 25 page 649 right column 868 to 870 and stabilizer 6 light absorber, page 25 to 26 page 649 right column 〜873 Luther dye, purple 650 page left column Outer line absorbent 7 Stain inhibitor 25 page right column 650 page left to right column 8 Dye image stabilizer 25 page 650 page left column 872 page 9 Hardener 26 page 651 page left Column 874-875 page 10 Binder 26 page ibid 873-874 page 11 plasticizer, lubricant page 27 650 page right column 876 page 12 Coating aid, surface 26-27 page ibid 875-876 activator 13 antistatic agent 27 Page ibid 876-877 pages

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. .

As the coupler used in the present invention, a two-equivalent color coupler in which an active position is substituted with a leaving group is more preferable than a four-equivalent color coupler in which an active position is a hydrogen atom, because the coated silver amount can be reduced. A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is
US Pat. Nos. 2,407,210 and 2,875,0
57 and 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,408,194 are preferable.
Nos. 447,928, 3,935,501, 4,022,620 and the like, or oxygen atom-releasing yellow couplers or JP-B-58-10739.
U.S. Pat. Nos. 4,401,752 and 4,32
6,024, RD18053 (April 1979), British Patent No. 1,425,020, West German Application Publication No. 2,2.
No. 19,917, No. 2,261,361, No. 2,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A Nos. 329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of magenta couplers usable in the present invention include oil-protected couplers, preferably 5-pyrazolone couplers and pyrazoloazole couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is US Pat.
No. 1,082, No. 2,343,703, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
No. 062,653, No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. European Patent No. 73,63
The 5-pyrazolone-based coupler having a ballast group described in No. 6 provides high color density.

As the pyrazoloazole coupler, pyrazolobenzimidazoles described in US Pat. No. 3,369,879, preferably US Pat. No. 3,725,06.
No. 7, pyrazolo [5,1-c] [1,2,
4] Triazoles, Research Disclosure 2
4220 (June 1984) and pyrazolotetrazoles and Research Disclosure 24230.
(June 1984), pyrazolopyrazoles. The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable in view of the small yellow sub-absorption of the color forming dye and the light fastness, and the pyrazolo compounds described in European Patent No. 119,860 are preferable. [1,5-b]
[1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil protect type naphthol type and phenol type couplers. US Pat. No. 2,474,293
-Type couplers described in U.S. Pat. No. 4,054
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and U.S. Pat.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,002, a phenolic cyan coupler having an alkyl group of ethyl group or more at the meta position of the phenol nucleus, US Pat. Nos. 2,772,162, and 3,
No. 758,308, No. 4,126,396, No. 4,334,011, No. 4,327,173, No. 4,500,635, West German Patent Publication No. 3,329,
2,5-diacylamino-substituted phenol couplers described in U.S. Pat. No. 729, and U.S. Pat. No. 3,446,6.
No. 22, No. 4,333, 999, No. 4,451,
Nos. 559 and 4,427,767, and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. In the present invention, 2,5-diacylamino-substituted phenol couplers are preferable from the viewpoints of fastness to temperature and humidity desired as a color filter, coloring hue and the like. Further, the carbostyryl-based coupler described in Japanese Patent Application No. 6-84315 is preferable in terms of high fastness to heat and light.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282 and British Patent No. 2,102,173.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
Patents described in D17643, VII to F, JP-A-5
Nos. 7-151944, 57-154234, 60
Those described in US Pat. No. 4,184,248 and US Pat. No. 4,248,962 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent 2,093
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
Competitive couplers described in US Pat.
No. 472, No. 4,338, 393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
Examples thereof include DIR redox compound releasing couplers described in 5950 and the like, and couplers releasing a dye that restores color after separation described in EP 173,302A.

In the light-sensitive material according to the present invention, a layer containing a coupler has a layered structure of EP 0,277,589A2.
It is preferred to use color image-storing improving compounds as described in US Pat. In particular, it is preferably used in combination with a pyrazoloazole-based magenta coupler.

That is, the compound (F) which reacts with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or remains after the color development processing. The use of a compound (G) which reacts with an oxidized product of an aromatic amine-based developing agent to form a chemically inactive and substantially colorless compound, simultaneously or alone, is effective in, for example, storage after processing. It is preferable in order to prevent the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

The light-sensitive material according to the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color fog inhibitor.

In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to the cyan coloring layer. As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794), a 4-thiazolidone compound (for example, US Pat. No. 3,314,794 and No. 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat. No. 3,705,805 and the same). No. 3,707,395), a budadiene compound (for example, US Pat.
No. 045,229) or a benzoxazole compound (for example, US Pat. No. 3,406,070).
No. 4,271,307). Ultraviolet absorbing couplers (for example, α-naphthol type cyan dye forming couplers) and ultraviolet absorbing polymers may be used. These ultraviolet absorbers may be mordanted to a specific layer. Among them, the benzotriazole compound substituted with the above aryl group is preferable.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material of the present invention has antibacterial properties as described in JP-A-63-271247. It is preferable to add a fungicide.

Hydrophobic additives such as couplers used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.
Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,2.
No. 541, 230 and the like.

For the outer type light-sensitive material, a coupler soluble in a developing solution is used instead of a hydrophobic coupler, and it is added not in the light-sensitive material but in the color developing solution. Specific examples of this coupler are described in JP-A No. 64-79701.

Further, regarding the internal latent image type emulsion and silver halide grains which can be used for the direct positive light-sensitive material such as the auto positive color film and the auto positive color paper of the present invention, JP-A-63-81337, JP- Kaihei 1-
No. 282545 and the like. The internal latent image type emulsion may be a conversion type emulsion or a core / shell type emulsion, but a core / shell type emulsion is preferred.

Details of the color couplers which can be used in the direct positive light-sensitive material are described in JP-A-63-81337, pages 19 to 27, and various compounds which can be contained in the light-sensitive material (prevention of color fog). Agents, anti-fading agents, dyes, etc.) are respectively described on pages 28 to 30 of the same specification.

Suitable supports usable for the light-sensitive material in the present invention are, for example, the above-mentioned RD. No. 17643-2
64 from the right column on page 8 and page 647 of the same No. 18716
It is described in the left column on page 8. The surface of these supports may be subbed. In addition, glow discharge, corona discharge,
UV irradiation or the like may be performed. The back surface of the support may be coated with carbon black or the like to increase heat and electric conductivity.

The light-sensitive material used in the present invention is RD.
No. 17643, pages 28-29, and No. 1871.
The development process can be carried out by a usual method described in the left column to the right column of 651 of No. 6.

For example, a color development processing step, a desilvering processing step, and a water washing processing step are carried out. In the desilvering step, instead of the bleaching step using a bleaching solution and the fixing step using a fixing solution, a bleach-fixing processing step using a bleach-fixing solution can be performed, a bleaching processing step, a fixing processing step, The bleach-fix processing steps may be combined in any order. The stabilizing process may be performed instead of the washing process, or the stabilizing process may be performed after the washing process. It is also possible to perform a monobath processing step using a one-bath development bleach-fix processing solution in which color development, bleaching and fixing are carried out in one bath. In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step, an adjusting step, an intensifying step and the like may be performed. In these processes, a so-called activator processing step may be performed instead of the color development processing step.

As the dye image-forming compound used in the light-sensitive material for color filter in the present invention, in addition to the above-mentioned color coupler, a diffusible dye corresponding to the reaction of reducing silver halide to silver or vice versa. Diffusion-resistant dye-donor compounds that release are mentioned. Specific examples of such dye-donating compounds are disclosed in JP-A-59-185333 and JP-A-63-185333.
-201653, European Patent EP 220,746B,
U.S. Pat. Nos. 4,500,626 and 4,639,40
No. 8, No. 4,783,396, No. 4,232,107
No. 4,619,884, 4,450,223
Nos. 4,503,137 and 4,559,290. A light-sensitive material containing such a dye-donating compound in the present invention is disclosed in US Pat.
No. 510, West German Patent OLS-2,916,582, JP-A No. 54-143230, Japanese Patent Application No. 5-205554, and the like. A filter can be formed.

The film thickness of the light-sensitive material for color filters of the present invention is preferably 20 μm or less in the case of the inner type, and especially 5 to 15
μ is more preferred. In the case of external photosensitive material, it is 15μ
The following is preferable, and 3 to 10 μ is particularly preferable.

When a direct positive type color light-sensitive material is used in the present invention, an aromatic primary amine type color developing agent is used after imagewise exposure and after or while being fogged with light or a nucleating agent. Including, preferably pH 12 or less,
It is preferable to directly form a positive color image by color development, bleaching and fixing treatment with a surface developer. The pH of this developer is more preferably in the range of 11.0 to 10.0.

The fogging treatment that can be used in the present invention is carried out in the presence of a so-called "light fogging method" for giving a second exposure to the entire surface of the photosensitive layer and a "chemical fogging method" in the presence of a nucleating agent. Either of the processing methods may be used. Development processing may be performed in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

Regarding the optical fogging method, the above-mentioned Japanese Patent Laid-Open No. 63-63
No. 81313, page 33, line 17 to page 35, last line, and the nucleating agent that can be used in the present invention is described on pages 50 to 53 of the specification, particularly the same specification. It is preferable to use the compounds represented by the general formulas [N-1] and [N-2].

With respect to the nucleation accelerator that can be used in the present invention,
It is described on pages 54 to 57 of the same specification, and a specific example thereof is (A-1) described on pages 55 to 57 of the same.
The use of (A-13) is preferred.

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EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these. Example 1 A color photographic material A was prepared by simultaneously coating multiple layers 1 to 9 having the following constitution on a polyethylene terephthalate film having a thickness of 100 μm and subjected to gelatin subbing.
The components and the coating amount (g / m ² unit) are shown below. For silver halide and colloidal silver emulsions, the coating amounts in terms of silver are shown. The emulsion used for each layer was prepared according to the method for producing emulsion EM-1 described below.

First Layer (Release Layer) Hydroxyethyl Cellulose. . . . 0.50 Polyvinylpyrrolidone (K-30). . . . 0.15

Second layer (adjacent layer to gelatin) Gelatin. . . . 0.50

Third Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.45 μ, size distribution 8%, octahedron). . . . 0.54 gelatin. . . . 1.40 Yellow coupler (ExY-1). . . . 1.02 Anti-fading agent (Cpd-12). . . . 0.13 Antistaining agent (Cpd-7). . . . 0.06 polymer (Cpd-13). . . . 0.12 High boiling point solvent (Solv-4). . . . 0.36

Fourth Layer (Intermediate Layer) Gelatin. . . . 1.13 Color mixing inhibitor (Cpd-3). . . . 0.08 High boiling point solvent (Solv-1). . . . 0.05 high boiling solvent (Solv-2). . . . 0.12 UV absorber (Cpd-1). . . . 0.01 UV absorber (Cpd-8). . . . 0.02 UV absorber (Cpd-9). . . . 0.06 UV absorber (Cpd-10). . . . 0.04 Polymer (Cpd-11). . . . 0.05 yellow dye (YF-1). . . . 0.15

Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.32 μ, size distribution 8%, octahedron). . . . 0.42 gelatin. . . . 1.26 Magenta Coupler (ExM-1). . . . 0.41 Anti-fading agent (Cpd-4). . . . 0.28 Anti-staining agent (Cpd-5). . . . 0.02 Anti-staining agent (Cpd-6). . . . 0.04 Anti-fading agent (Cpd-7). . . . 0.06 High boiling point solvent (Solv-2). . . . 0.95 high boiling point solvent (Solv-3). . . . 0.29

Sixth Layer (Intermediate Layer) Gelatin. . . . 1.13 Color mixing inhibitor (Cpd-3). . . . 0.08 High boiling point solvent (Solv-1). . . . 0.05 high boiling solvent (Solv-2). . . . 0.13

Seventh Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.3 μ, size distribution [variation coefficient] 8%, 8 Face piece). . . . 0.48 gelatin. . . . 0.80 cyan coupler (ExC-1). . . . 0.40 cyan coupler (ExC-2). . . . 0.34 Anti-fading agent (Cpd-1). . . . 0.05 anti-fading agent (Cpd-2). . . . 0.12 High boiling point solvent (Solv-1). . . . 0.35

Eighth layer (anti-irradiation dye layer) Gelatin. . . . 0.50 anti-irradiation dye (Dye-1, 2, 3, 4 in a 10: 10: 13: 15 molar ratio). . . . 0.04

Ninth Layer (Protective Layer) Gelatin. . . . 0.70 Colloidal silver emulsion (average grain size 0.02μ). . . . 0.20 surfactant (Cpd-14). . . . 0.06 Hardener (H-1). . . . 0.12

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous solution of gelatin at 60 ° C. for 8 minutes with vigorous stirring, and octahedral silver bromide having an average particle size of 0.15 μm. The particles were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione was added per mol of silver. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were successively added per mol of silver, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. Using the grains thus obtained as a core, the grains were further grown in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.32 μ was obtained. The coefficient of variation of particle size was about 8%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was mixed at 60 ° C for 6
The mixture was heated for 0 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 for silver halide,
^10-2 wt%, Cpd-15 ^10-2 as nucleation accelerator
% By weight. Also, as a stabilizer of silver halide, Cpd
-16 was added. Further, in each layer, sodium dodecylbenzene sulfonate as an emulsification dispersion aid, ethyl acetate as an auxiliary solvent, Cpd-17 as a coating aid, and potassium polystyrene sulfonate as a thickening agent were used.

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A transparent non-alkali glass (30 cm × 30 cm) having a thickness of 1.1 mm was used as a light transmissive substrate, and a black matrix was formed by Cr vapor deposition. Gelatin and colloidal silica (average particle size 7-9n on the surface)
m) was mixed at a weight ratio of 1: 3, and saponin was added as a surfactant for coating. The coating thickness of the dry film was 0.2 μm.

The protective layer of the color light-sensitive material described above was brought into close contact with the coating surface of the light transmissive substrate. At this time, some moisture was applied to the emulsion surface of the light-sensitive material. After that, the temperature of the contact surface is about 1
Using a laminator whose temperature is set to 30 ° C,
It was passed at a linear velocity of 0.45 m / min. After cooling to about room temperature, the support of the light-sensitive material was peeled off from the emulsion surface. The emulsion surface was evenly adhered to the substrate, and no white spots were observed. The photosensitive material obtained above was exposed using the apparatus shown in FIG. That is, a color separation filter SP-1 manufactured by Fuji Photo Film Co., Ltd. is inserted as a color filter 2, and the liquid crystal driving method described in JP-A-60-32679 is used.
Only the B pixel is allowed to transmit light, the white light source is scanned as the backlight to perform the first exposure (B exposure), the color separation filter is similarly switched to SP-2, and the G pixel is allowed to transmit light. Second exposure (G exposure) was performed, the color separation filter was further switched to SP-3, the R pixel was made to transmit light, and the third exposure (R exposure) was performed.

The above exposed substrate was developed according to the following steps, and a color filter having B, G and R colors was prepared by a single operation. (Processing step) (Temperature) (Time) Hardening treatment 38 ° C 3 minutes Water washing-1 35 ° C 1 minute Color development 38 ° C 5 minutes Bleach fixing 38 ° C 2 minutes Water washing-2 35 ° C 1 minute Water washing-3 35 ° C 1 minute Dry 60 ℃ 2 minutes

The composition of each processing solution is as follows. Hardening solution Sodium sulfate (anhydrous) 160.0 g Sodium carbonate (anhydrous) 4.6 g Formalin (37%) 20.0 ml Water is added to 1 liter pH (25 ° C) = 10.0

Color developer D-Sorbit 0.15 g Sodium naphthalenesulfonate / formalin condensate 0.15 g Nitrilotris (methylenephosphonic acid) 5 sodium salt 1.80 g Diethylenetriamine 5 acetic acid 0.50 g 1-Hydroxyethylidene-1,1 -Diphosphonic acid 0.15 g diethylene glycol 12.0 ml benzyl alcohol 13.5 ml potassium bromide 0.70 g, benzotriazole 0.003 g sodium sulfite 2.40 g disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.0 g Triethanolamine 6.00 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoalline.3 / 2 sulfuric acid monohydrate 6.00 g Potassium carbonate 30.0 g Water was added 1 Li Le pH (25 ℃) = 11.0

Bleach-fixing solution Ethylenediaminetetraacetic acid 5.0 g Ethylenediaminetetraacetic acid / ferric ammonium 55.0 g Ammonium thiosulfate (750 g / liter) 160 ml Ammonium sulfite 40.0 g Ammonium nitrate 10.0 g Water is added to 1 liter pH (25 ° C. ) = 6.0

Rinsing water Deionized water with conductivity of 5 μS or less

The obtained color filter has B, G, and R patterns in which the absorbance of each component of cyan, magenta, and yellow is 1.0 to 1.7, and white spots and color blurring are not seen. It had excellent spectral transmission characteristics and had a desired pixel arrangement and shape.

Example 2 As described in the example of JP-A-63-293348, gelatin subbing was carried out on a polyethylene terephthalate support having a thickness of 100 .mu.m and coated with carbon black dispersed in polyvinyl chloride as a back layer. Then, the first to tenth layers having the structure shown below were simultaneously coated in multiple layers to prepare a color light-sensitive material B. The components and the coating amount (g / m ² unit) are shown below. For silver halide and colloidal silver emulsions, the coating amounts in terms of silver are shown. As for the compounds, the same compounds as in Example 1 were used except for those specifically mentioned. Each layer of the silver halide emulsion is negative type silver chlorobromide.

First Layer (Release Layer) Hydroxyethyl Cellulose. . . . 0.72 Terminal-alkyl modified polyvinyl alcohol (saponification degree 98 mol%, degree of polymerization 300). . . . 0.15

Second Layer (Adjacent Layer to Gelatin) Gelatin. . . . 0.45

Third Layer (UV Absorbing Layer) Gelatin. . . . 0.45 UV absorber (Cpd-1). . . . 0.01 UV absorber (Cpd-8). . . . 0.02 UV absorber (Cpd-9). . . . 0.06 UV absorber (Cpd-10). . . . 0.03 polymer (Cpd-11). . . . 0.05

Fourth Layer (Red Sensitive Layer) Silver chlorobromide emulsion spectrally sensitized with a red sensitizing dye (ExS-11) (Br: 25%, 0.2 μ). . . . 0.50 gelatin. . . . 1.50 Yellow coupler (ExY-1). . . . 0.52 Magenta Coupler (ExM-2). . . . 0.25 color image stabilizer (Cpd-21). . . . 0.09 Color image stabilizer (Cpd-4). . . . 0.12 Color image stabilizer (Cpd-22). . . . 0.01 high boiling solvent (Solv-1). . . . 0.25 high boiling solvent (Solv-2). . . . 0.07 High boiling point solvent (Solv-3). . . . 0.14 Compound (Cpd-23). . . . 0.04

Fifth Layer (Intermediate Layer) Gelatin. . . . 0.90 Color mixing inhibitor (Cpd-3). . . . 0.04 UV absorber (Cpd-1). . . . 0.02 UV absorber (Cpd-8). . . . 0.04 UV absorber (Cpd-9). . . . 0.12 UV absorber (Cpd-10). . . . 0.06 polymer (Cpd-11). . . . 0.10

Sixth Layer (Green Sensitive Layer) Silver chlorobromide emulsion spectrally sensitized with a green sensitizing dye (ExS-12, 13) (Br: 30%, 0.2 μ). . . . 0.65 gelatin. . . . 1.20 Cyan coupler (ExC-1). . . . 0.35 Yellow coupler (ExY-2). . . . 0.67 color image stabilizer (Cpd-1). . . . 0.08 Color image stabilizer (Cpd-9). . . . 0.04 color image stabilizer (Cpd-10). . . . 0.07 Color image stabilizer (Cpd-21). . . . 0.12 Polymer (Cpd-13). . . . 0.17 High boiling point solvent (Solv-2). . . . 0.19 High boiling point solvent (Solv-1). . . . 0.23

Seventh Layer (Intermediate Layer) Gelatin. . . . 0.90 Color mixing inhibitor (Cpd-3). . . . 0.08 UV absorber (Cpd-1). . . . 0.01 UV absorber (Cpd-8). . . . 0.02 UV absorber (Cpd-9). . . . 0.06 UV absorber (Cpd-10). . . . 0.03 polymer (Cpd-11). . . . 0.05

Eighth Layer (Blue Sensitive Layer) Silver chlorobromide emulsion spectrally sensitized with a blue sensitizing dye (ExS-14) (Br: 80%, 0.5 μ). . . . 0.47 Antifoggant (Cpd-20). . . . 0.04 Gelatin. . . . 1.40 Cyan coupler (ExC-3). . . . 0.50 Magenta coupler (ExM-1). . . . 0.04 color image stabilizer (Cpd-1). . . . 0.04 color image stabilizer (Cpd-9). . . . 0.05 color image stabilizer (Cpd-10). . . . 0.07 Color image stabilizer (Cpd-4). . . . 0.04 color image stabilizer (Cpd-22). . . . 0.01 Polymer (Cpd-13). . . . 0.05 high boiling solvent (Solv-2). . . . 0.25 high boiling solvent (Solv-3). . . . 0.12 9th layer (anti-irradiation dye layer) Gelatin. . . . 0.50 anti-irradiation dye (Dye-1, 2, 3, 4 in a 10: 10: 13: 15 molar ratio). . . . 0.04

Tenth Layer (Protective Layer) Gelatin. . . . 0.70 Colloidal silver emulsion (0.02μ). . . . 0.20 polymer (Cpd-25). . . . 0.29 surfactant (Cpd-14). . . . 0.06 Hardener (H-1). . . . 0.25

In each silver halide emulsion layer, the blue-sensitive layer was 4.0 × 10 ^-6 mol, the green-sensitive layer was 3.0 × 10 ^-5 mol, and the red-sensitive layer was 1. 0 × 10 ^-5 mol of C
pd-24 was added. In addition, in the blue and green layers,
1.2 × 10 ^-2 mol per mol of silver halide blue-sensitive layer, a 1.1 × 10 ^-2 mol of Cpd-16 in the green-sensitive layer was added. Further, in each layer, sodium dodecylbenzene sulfonate as an emulsification dispersion aid, ethyl acetate as an auxiliary solvent,
Cpd-17 was used as a coating aid, and potassium polystyrene sulfonate was used as a thickening agent.

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[0111]

[Chemical 9]

The same light-transmitting substrate as in Example 1 was used and the emulsion layer was transferred onto the substrate by the same operation. The same exposure apparatus as in Example 1 was used for the same exposure. After that, development processing was performed according to the following steps, and a color filter that developed B, G, and R was prepared by one operation. (Treatment process) (Temperature) (Time) Hardening treatment 38 ° C 3 minutes Water washing-1 35 ° C 1 minute Color development 38 ° C 1 minute 30 seconds Bleach fixing 38 ° C 1 minute 30 seconds Water washing-2 35 ° C 1 minute Water washing-3 35 ° C 1 min. Washing with water-4 35 ° C 30 sec. Drying 80 ° C with 1 min.

The composition of the color developer is as follows:
A processing solution having the same composition as in Example 1 was used except for the color developing solution. Color developer 800 ml Ethylenediaminetetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triethanolamine 12.0 g Potassium chloride 6.5 g Potassium bromide 0.03 g Potassium carbonate 27.0 g Fluorescent brightening Agent (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5.0 g Sodium triisopropylnaphthalene (β) sulfonate 0.1 g N-ethyl-N- (β -Methanesulfonamidoethyl) -3-methyl-4-aminoanilino / 3/2 sulfuric acid monohydrate 5.0 g Water was added to 1 liter pH (25 ° C) = 10.0

A color filter having cyan, magenta and yellow components B, G and R having an absorbance of 0.9 to 1.6, no white spots and peeling defects and excellent spectral transmission characteristics can be obtained. It was Moreover, the obtained color filter had a desired pixel arrangement and shape.

Example 3 A color light-sensitive material C having the following constitution was prepared by using the same support, silver halide emulsion, coupler, additive and the like as the light-sensitive material B.

First Layer (Release Layer) Hydroxyethyl Cellulose ... 0.72 Terminal Alkyl Modified Polyvinyl Alcohol (Saponification Degree: 98%, Polymerization Degree: 300) ... 0.15

Second layer (adjacent layer to gelatin) Gelatin ... 0.50

Third Layer (First Red Sensitive Layer) Silver chlorobromide (Br: 25%, 0.2μ) spectrally sensitized with a red sensitizing dye (ExS-11) ... 0.20 gelatin ... -0.78 Magenta coupler (ExM-2) ... 0.25 Color image stabilizer (Cpd-4) ... 0.12 Anti-stain agent (Cpd-5) ... 0.01 Anti-stain agent (Cpd-6) ... 0.02 Anti-staining agent (Cpd-7) ... 0.03 Color image stabilizer (Cpd-22) ... 0.01 Compound (Cpd-23) ... 0.01 High boiling point solvent (Solv-2) ... 0.53 High boiling point solvent (Solv-3) ... 0.14

Fourth Layer (Second Red Sensitive Layer) Silver chlorobromide spectrally sensitized with a red sensitizing dye (ExS-11) (Br: 25%, 0.2 μ) ... 0.30 gelatin ... -0.84 Yellow coupler (ExY-1) ... 0.52 Anti-staining agent (Cpd-7) ... 0.03 Anti-fading agent (Cpd-12) ... 0.07 Polymer (Cpd-13) ) ... 0.06 Color image stabilizer (Cpd-22) ... 0.03 Compound (Cpd-23) ... 0.01 High boiling point solvent (Solv-4) ... 0.18

Fifth Layer (First Green Sensitive Layer) Silver chlorobromide (Br: 30%, 0.2μ) spectrally sensitized with a green sensitizing dye (ExS-12, 13) ... 0.30 Gelatin ... 0.80 Yellow coupler (ExY-2) ... 0.57 Anti-stain agent (Cpd-7) ... 0.03 Anti-fading agent (Cpd-12) ... 0.07 Polymer (Cpd -13) ... 0.06 Color image stabilizer (Cpd-22) ... 0.01 High boiling point solvent (Solv-4) ... 0.23

Sixth Layer (Second Green Sensitive Layer) Silver chlorobromide (Br: 30%, 0.2μ) spectrally sensitized with a green sensitizing dye (ExS-12, 13) ... 0.40 Gelatin ... 0.73 Cyan coupler (ExC-1) ... 0.35 Color image stabilizer (Cpd-1) ... 0.03 Color image stabilizer (Cpd-2) ... 0. 07 Color image stabilizer (Cpd-22) ... 0.01 High boiling point solvent (Solv-1) ... 0.18

Seventh Layer (First Blue Sensitive Layer) Silver Chlorobromide (Br: 80%, 0.5μ) spectrally sensitized with a blue sensitizing dye (ExS-14) ... 0.30 Antifoggant (Cpd-20) ・ ・ ・ 0.02 Gelatin ・ ・ ・ 0.68 Cyan coupler (ExC-3) ・ ・ ・ 0.50 Color image stabilizer (Cpd-1) ・ ・ ・ 0.03 Color image stabilization Agent (Cpd-2) ... 0.08 Color image stabilizer (Cpd-22) ... 0.01 High boiling point solvent (Solv-1) ... 0.25

Eighth Layer (Second Blue Sensitive Layer) Silver chlorobromide (Br: 80%, 0.5μ) spectrally sensitized with a blue sensitizing dye (ExS-14) ... 0.10 Antifoggant (Cpd-20) ... 0.01 Gelatin ... 0.32 Magenta puller (ExM-1) ... 0.04 Color image stabilizer (Cpd-4) ... 0.04 Anti-stain agent (Cpd-5) ... 0.01 Anti-staining agent (Cpd-6) ... 0.01 Anti-staining agent (Cpd-7) ... 0.02 Color image stabilizer (Cpd-22) ... 0.01 High boiling point solvent (Solv-2) ... 0.28 High boiling point solvent (Solv-3) ... 0.07

Ninth layer (irradiation preventing dye layer) Gelatin ... 0.50 Irradiation preventing dye (Dye-1, 2, 3, 4 in a molar ratio of 10: 10: 13: 15) ... 0.04

Tenth Layer (Protective Layer) Gelatin 0.70 Colloidal silver emulsion (average particle size 0.02 μ) 0.20 Polymer (Cpd-25) 0.29 Surfactant ( Cpd-14) ... 0.06 Hardener (H-1) ... 0.20

When the light-sensitive material C was processed in the same manner as in Example 2, as in Example 2, the blue portion, the green portion, and the red portion exhibited high transmittance, and had a desired pixel arrangement and shape.

Example 4 Example 1 of Invention Technical Disclosure Technical Report No. 94-6023
A surface treatment was similarly carried out using PEN-1A described in 1 above, and after further gelatin subbing, a multi-layer simultaneous coating of the first layer to the ninth layer having the constitution described below was carried out to prepare a color light-sensitive material D. The same halogen emulsions, couplers and additives as those used in the above-mentioned examples were used.

First Layer (Release Layer) Hydroxyethyl Cellulose ... 0.72 Terminal Alkyl Modified Polyvinyl Alcohol (Silicitation Degree 98 Mole%, Polymerization Degree 300) ... 0.15

Second layer (adjacent layer to gelatin) gelatin ... 0.50

Third Layer (Blue Sensitive Layer) Silver chlorobromide (Br: 80%, 0.5 μ) spectrally sensitized with a blue sensitizing dye (ExS-14) ... 0.37 Gelatin ... 1 .14 Yellow coupler (ExY-1) ... 0.55 Anti-fading agent (Cpd-12) ... 0.07 Anti-staining agent (Cpd-7) ... 0.03 Polymer (Cpd-13) .. 0.06 High boiling point solvent (Solv-4) ... 0.18 Color mixing inhibitor (Cpd-22) ... 0.01

Fourth layer (intermediate layer) Gelatin: 0.63 Color mixing inhibitor (Cpd-3): 0.08 High boiling point solvent (Solv-1): 0.05 High boiling point solvent (Solv) -2) ... 0.12 UV absorber (Cpd-1) ... 0.01 UV absorber (Cpd-8) ... 0.02 UV absorber (Cpd-9) ... 0. 06 UV absorber (Cpd-10) ... 0.04 Polymer (Cpd-11) ... 0.05 Yellow dye (YF-1) ... 0.15

Fifth Layer (Green Sensitive Layer) Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-12, 13) (Br: 30%, 0.2μ) ... 0.28 gelatin ... -1.21 Magenta coupler (ExM-1) ... 0.35 Anti-fading agent (Cpd-4) ... 0.23 Anti-staining agent (Cpd-5) ... 0.01 Anti-staining agent (Cpd) -6) ... 0.02 Anti-fading agent (Cpd-7) ... 0.03 High boiling point solvent (Solv-2) ... 0.49 High boiling point solvent (Solv-3) ... 0. Thirteen

Sixth layer (intermediate layer) Gelatin ... 0.53 Color mixing inhibitor (Cpd-3) ... 0.08 High boiling point solvent (Solv-1) ... 0.05 High boiling point solvent (Solv-1) -2) ... 0.13 Anti-irradiation dye (Dye-1, 2, 3, 4 in a molar ratio of 10: 10: 13: 15) ... 0.02

Seventh Layer (Red Sensitive Layer) Silver chlorobromide (Br: 25%, 0.2 μ) spectrally sensitized with a red sensitizing dye (ExS-11) ... 0.35 Gelatin ... 0 .90 Cyan coupler (ExC-1) ... 0.30 Cyan coupler (ExC-2) ... 0.20 Anti-fading agent (Cpd-1) ... 0.05 Anti-fading agent (Cpd-2) ... 0.10 High boiling point solvent (Solv-1) ... 0.28 Color mixing inhibitor (Solv-22) ... 0.02 Compound (Cpd-23) ... 0.01

Eighth Layer (Intermediate Layer) Gelatin ... 0.30

Ninth layer (protective layer) Gelatin 0.73 Colloidal silver emulsion (average particle size 0.02 μ) 0.20 Polymer (Cpd-25) 0.29 Surfactant ( Cpd-14) ... 0.06 Hardener (H-1) ... 0.12

When the light-sensitive material D was exposed and processed in the same manner as in Example 2, a yellow portion excellent in transmittance and hue,
A color filter having a magenta portion and a cyan portion and having a desired pixel pattern was obtained.

[0138]

According to the present invention, it is possible to provide a method for producing a color filter having RGB or YMC, which does not require complicated steps, is suitable for mass production, and has excellent spectral transmission characteristics and hue. Further, it has a method of easily manufacturing a color filter having a pixel arrangement and a shape matching various types of liquid crystal displays to be incorporated in a short time, and RGB or YMC having excellent spectral transmission characteristics and hue obtained thereby. Can provide color filter.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an aspect of an exposure apparatus used in the method for manufacturing a color filter of the present invention.

FIG. 2 is a graph showing a characteristic curve of a photosensitive material that can be used in the present invention.

FIG. 3 is a schematic view showing one embodiment of a BGR color filter of the present invention.

FIG. 4 is a schematic view showing one embodiment of the layer structure of a photosensitive material that can be used in the present invention.

FIG. 5 is a schematic view showing one embodiment of a YMC color filter of the present invention.

[Explanation of symbols]

 1 light source 2 color filter 3 liquid crystal display panel 4 emulsion layer 5 light transmissive substrate 6 liquid crystal layer 7 alignment film 8 light transmissive substrate 9 light transmissive substrate 10 transparent electrode 11 transparent electrode 12 sealant 13 deflector 14 deflector 15 photosensitive material

Claims (5)

[Claims] 1. RGB for pattern exposure, color development and decolorization of a light-sensitive material having at least three silver halide emulsion layers having different color sensitivities on a light-transmissive substrate.
Alternatively, in the method for producing a YMC color filter, the method for producing an RGB or YMC color filter, wherein the pattern exposure is performed by any one of the following methods (a) and (b). (A) A liquid crystal display panel in which a white light source is provided on the back surface and the photosensitive material is provided on the front surface, and the color sensitivity of the photosensitive material is provided between the liquid crystal display panel and the light source or the photosensitive material. Three color filters are sequentially inserted, and correspondingly, light of a desired pixel of the liquid crystal display panel is transmitted according to an arbitrary arrangement, and exposure is sequentially performed three times. (B) A liquid crystal display panel in which three light sources having different wavelengths are provided on the back surface in correspondence with the color sensitivity of the light-sensitive material and the light-sensitive material is installed on the front surface, and the light sources are sequentially turned on. Light of a desired pixel of the liquid crystal display panel is transmitted according to an arbitrary arrangement, and exposure is sequentially performed three times. 2. The silver halide emulsion layer of the light-sensitive material comprises:
Sensitizing at least two couplers forming substantially different dyes among at least three couplers forming a dye of any one of yellow, magenta and cyan by a coupling reaction with an oxidized product of a developing agent. 2. The method for producing a color filter according to claim 1, wherein the silver halide emulsion layers having different properties are contained in the respective layers to develop blue, green and red colors, respectively. 3. The silver halide emulsion layer of the light-sensitive material comprises:
At least three kinds each of which is composed of at least two unit layers, and each of these at least two unit layers forms a dye of any one of yellow, magenta and cyan by a coupling reaction with an oxidant of a developing agent. 7. The couplers according to claim 1, each containing a coupler having a different dye to be formed from each other, and each silver halide emulsion layer having a different color sensitivity is a layer exhibiting blue, green and red, respectively. 1. The method for producing a color filter according to 1. 4. An at least three silver halide emulsion layers having different color sensitivities are provided on a release layer coated on an arbitrary support, and the emulsion surfaces are adhered onto a light-transmissive substrate. ,
The method for producing a color filter according to claim 1, wherein after the support is peeled off and removed, the emulsion surface is subjected to the pattern exposure, color development and desilvering. 5. A color filter produced by the method according to any one of claims 1 to 4.