JPH08248219A - Production of color filter - Google Patents

Abstract

PURPOSE: To provide a process for simultaneously production plural sheets of the color filters on one sheet of the substrate which has the frame edges of color filters with insulating parts exposed with a substrate surface to be provided with electrodes, etc. CONSTITUTION: Only the parts 2 to be formed with color filter layers of a flexible base are first peeled after adhesion of a color photosensitive material provided with color photosensitive layers via release layers on the flexible base onto a light transparent substrate 1 and thereafter, the photosensitive material is subjected to exposing to a pattern form, then to a hardening treatment, followed by peeling the base of the frame edge parts 3 and peeling at least the photosensitive layers in the frame edge parts by washing. Only the frame edge parts 3 of the flexible base are otherwise first peeled after the adhesion, and thereafter, at least the photosensitive layer of the frame edge parts is peeled by washing, then the flexible base of the parts 2 to be formed with the color filter layers is peeled, following by pattern exposing and the hardening treatment. Either case, the photosensitive material is subjected to color developing and desilvering treatment, by which the color filter layers are formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color filter, and more particularly to a method for easily and efficiently manufacturing a color filter having excellent spectral transmission characteristics.

[0002]

2. Description of the Related Art Color filters are color face plates for CRT display, photoelectric conversion element plates for copying,
It is used in filters for single-tube color TV cameras, flat panel displays using liquid crystals, color solid-state image sensors, and the like. The commonly used color filters are
The three primary colors of blue, green and red are arranged regularly, but if necessary, there are also four or more hues. 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 internal development method using a silver halide color light-sensitive material (see, for example, Japanese Patent Laid-Open Publication No.
2-148952, 62-71950, 63-
261361) and an external mold developing method (for example, Japanese Patent Laid-Open No.
No. 6342), a method for producing a color filter was investigated. However, the latter method requires color development at least three times, and it cannot be said that the processing steps are simple. Further, both methods require a photosensitive material having a multi-layered structure, and spin coating is repeated in order to apply a photosensitive layer on a hard support such as a glass substrate.

On the other hand, the present applicant has improved the above-mentioned various drawbacks, does not require complicated steps, is suitable for mass production, and provides a light-sensitive material for a color filter excellent in spectral transmittance and a method for producing the same. Provided (Japanese Patent Application No. 6-303977)
issue). That is, a first object of the invention is to provide a method for easily producing a color filter on a light-transmissive substrate, and a second object is to provide blue, green and It was to provide a highly accurate color filter having a red part and a black part having excellent spectral absorption characteristics.

[0006]

On the other hand, in the case of a color filter, on the other hand, the frame edge portion of the color filter may require an insulating portion for exposing electrodes such as a glass surface. It was necessary to manufacture not only one color filter but also many color filters on the glass substrate, but this was not possible with the invention of Japanese Patent Application No. 6-303977.

The object of the present invention is to solve the problems of the prior art, to provide an insulating portion on the frame edge of a color filter where the substrate surface for exposing electrodes and the like is exposed, and a plurality of substrates can be provided on one substrate. An object of the present invention is to provide a method of simultaneously manufacturing a single color filter.

[0008]

The above object of the present invention is to provide a color light-sensitive material having a color light-sensitive layer provided on a flexible support with a release layer interposed therebetween, after the color light-sensitive material is adhered onto a light-transmissive substrate. After peeling off only the portion of the flexible support that forms the color filter layer, after pattern exposure and hardening treatment, the support of the frame edge portion that does not form the color filter layer is also peeled off, and the frame edge portion of the flexible support is washed. After peeling at least the photosensitive layer, color development and desilvering are performed, or after pattern exposure, after hardening treatment, developing treatment and desilvering, at least the photosensitive layer is washed by removing the support at the frame edge portion. A method for producing a color filter, which comprises peeling to form a color filter layer. A color photosensitive material having a color photosensitive layer provided with a release layer on a flexible support is adhered to a light-transmissive substrate, and then the flexible support is not provided with a color filter layer. Only a frame edge portion. After peeling off, at least the photosensitive layer in the frame edge portion is peeled off by washing, the flexible support in the portion forming the color filter layer is also peeled off, and after pattern exposure, a film-hardening treatment is carried out, and color development, A method for producing a color filter, which comprises decolorizing and forming a color filter layer. Achieved by

More specifically, 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, gelatin is used because it has a relationship with the peeling layer. Advantageously, other hydrophilic polymers can also be used. As the hydrophilic polymer, for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl butyral, poly-N-vinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyvinyl imidazole,
Polyvinylpyrazole, carrageenan, gum arabic,
Further examples include homo- or copolymers of hydroxyalkyl cellulose, carboxymethyl cellulose, cellulose sulfate, cellulose acetate hydrogen phthalate and cellulose derivatives such as sodium alginate.

Further, a graft polymer of gelatin and other polymers may be used. As the gelatin-graft polymer, gelatin is added to acrylic acid, methacrylic acid, their derivatives such as esters and amides, 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.

Typical synthetic hydrophilic polymer substances include, 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.

Preferably, the layers other than the release layer of the light-sensitive material are composed of a binder containing gelatin (including its derivative) as a main component, and the release layer is composed of a layer containing a polymer other than gelatin (including its derivative) as a main component. To be done. A gelatin-based binder means that about 80% or more of the binder is gelatin or a gelatin derivative. Similarly, the release layer contains about 80% of the hydrophilic polymer other than gelatin.
% Or more is included. 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, 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 desirable 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 . The total coating amount of the binder (hydrophilic polymer) other than the release layer of the light-sensitive material of the present invention is 20 g / m ² or less, preferably 10 g / m ² or less, and particularly ^{2 to 8} g
/ M ² is preferred.

The light-sensitive material that can be used in the present invention is
The following are preferred. They are an external color reversal film capable of obtaining a positive image by color reversal processing, an internal color reversal film, a color negative film by color negative processing, a display color film, an auto positive color film and the like. Regarding these, Science Handbook (top) (Maruzen) pp. 559-564, 569
Page, The Theory of the Photographic Process, 4th Edition, edited by TH James. In addition, as described in JP-A-63-261361, 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 those described in JP-A-63-261361. As described in No. 79701, it is also possible to use an external color light-sensitive material which is developed by using a developer containing two or more kinds of couplers showing different colors with respect to the same photosensitive silver halide and a developing agent.

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 include 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 that 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 halide 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 amount of silver halide used is
The theoretical equivalent of the coupler is preferably 1 to 5 times, and 1 to 3 times.
Double is especially preferred.

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 page 649 page right column 868 to 870 and stabilizer 6 light absorber, page 25 to page page 649 right column 〜873 Luther dye, Purple 650 page 650 Left column External absorber 7 Stain inhibitor 25 page Right column 650 Page left 〜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 page 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 may 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 preferable to a four-equivalent color coupler having a hydrogen atom in terms of reducing the amount of coated silver. 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 the magenta coupler which can be used in the present invention include oil-protected type, preferably 5-pyrazolone type and pyrazoloazole type 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. 3,446,62.
No. 2, No. 4,333, 999, No. 4,451, 5
No. 59 and No. 4,427,767, etc., and phenol 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-based couplers and carbostyryl-based couplers described in Japanese Patent Application No. 6-84315 are preferable from the viewpoints of fastness to temperature and humidity desired as a color filter, coloring hue and the like.

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 No. 2,092
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 is provided in European Published Patent 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-based 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 the compound (G), which forms a chemically inactive and substantially colorless compound in response to the oxidant of the aromatic amine-based developing agent, simultaneously or solely, for example, storage after processing. It is preferable for preventing 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 according to 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 amount of the high boiling point solvent used is 10 g or less, preferably 5 g or less, and more preferably 1 g to 0.1 g per 1 g of the coupler. Further, 1 g or less, more preferably 0.5 g or less, and particularly 0.3 g or less is suitable for 1 g of the binder. 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-A-63-81337, 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 (color fog prevention). Agents, anti-fading agents, dyes, etc.) are respectively described on pages 28 to 30 of the same specification.

Suitable supports usable in the light-sensitive material of the present invention are, for example, RD. No. 17643, page 28,
And No. 18716, page 647, right column to page 648, left column. The surface of these supports may be subbed. Further, glow discharge, corona discharge, UV irradiation or the like may be applied. 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 the 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 the color filter of the present invention, in addition to the above-mentioned color coupler, a diffusible dye corresponding to the reaction in which silver halide is reduced to silver or vice versa is used. 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-63-20.
1653, European Patent EP220,746B, US Pat. Nos. 4,500,626 and 4,639,408,
4,783,396, 4,232,107, 4,619,884, 4,450,223, 4,503,137, 4,559,290, etc. Has been done. A light-sensitive material containing such a dye-donating compound in the present invention is disclosed in US Pat. No. 3,923,510.
, West German Patent OLS-2,916,582, JP-A-5
It is possible to form a color filter with the dye-donor compound which is processed according to the method described in Japanese Patent Application No. 4-143230, Japanese Patent Application No. 5-205554, etc. and remains in the light-sensitive material.

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.

The exposure method applied to the present invention includes a surface exposure method and a scanning exposure method. As a scanning method, a line (slit) scanning or a point scanning method using laser exposure can be applied. As the light source, a tungsten lamp, a halogen lamp, a fluorescent lamp, a mercury lamp (such as a three-wavelength fluorescent lamp), a laser beam, or a light emitting diode is used. Particularly, a halogen lamp, a fluorescent lamp, and a laser beam are preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixture is removed, and color reproducibility is significantly improved.

When a direct positive type color light-sensitive material is used in the present invention, an aromatic primary amine-based color developing agent is used after imagewise exposure, after or while being subjected to fogging treatment 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 which 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].

Regarding 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. This is the end of the description of the color light-sensitive material used in the present invention.

Next, as the light transmissive substrate used in the present invention, those which are transparent, have optical isotropy and have sufficient heat resistance are preferable, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polystyrene. , Polycarbonate, polyether sulfone, cellulose acetate, polyarylate, soda glass, borosilicate glass, non-alkali glass, quartz and the like. 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.

In the present invention, when the binder of the layers other than the release layer is mainly composed of gelatin, the preferred adhesion method is to previously apply a liquid containing gelatin and colloidal silica to the adhesion surface of the substrate (especially glass substrate) 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., the pressing force is 1.8 to 8 kg / cm ² , and the heating time can be set arbitrarily, but 0.1 second to 60 seconds is preferable. Further, the heat bonding may be performed in the presence of a small amount of water.

In the case of the present invention, since the flexible support is peeled off only at the portion where the color filter layer is formed or at the frame edge where the color filter layer is not formed after the adhesive is cooled, the flexible support is After heat-bonding, it is necessary to make a break in the boundary line between the filter layer and the frame edge portion.

In the case of claim 1, after heating and bonding, the flexible support is peeled off only at the portion where the color filter layer is formed. At this time, in order to suppress the generation of static electricity, a relative humidity of 5 is used.
It is desirable to control the humidity to 0% or more. After pattern exposure,
Hardening treatment is carried out. After that, the support at the frame edge portion is also peeled off and at least the photosensitive layer at the frame edge portion is peeled off by washing, or the development treatment and the desilvering treatment are carried out first. 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. The concentration of the hardener solution is 1 to 50%, and the hardening time is 10
Seconds to 10 minutes. After hardening, excess hardener is removed by washing with water.

In the case of claim 1, the support at the frame edge portion of the color filter is also peeled off, but since the support covers this portion at the time of film hardening, the color photosensitive material and the adhesive layer at the frame edge portion are hard films. However, the color photosensitive material and the adhesive layer in that portion can be easily peeled off by peeling and washing the support. The detergent may be water or warm water and may contain an enzyme such as a surfactant, sodium hypochlorite, or actinase. The cleaning method is immersion cleaning, spray cleaning, or the like.

Next, the pre-hardened color photosensitive material remaining on the substrate is developed and desilvered to form a color filter layer. As described above, the color light-sensitive material used in the present invention can be developed by an ordinary method.

According to another method of claim 2 of the present invention, after the color light-sensitive material and the light-transmissive material are adhered to each other,
First, after peeling off only the flexible support, that is, the frame edge portion of the portion where the color filter layer is not formed, the frame edge portion is washed with warm water or with an enzyme such as actinase or an aqueous solution of sodium hypochlorite. Of at least the photosensitive layer, then the flexible support in the portion where the color filter layer is to be formed next is peeled off, and after pattern exposure, the color filter layer is pre-hardened and washed with water, and then color development is performed. , A method of forming a color filter layer by desilvering. Also in this case, "exposure method""fogtreatment"
The "developing method" is also carried out in accordance with the description in the specification of Japanese Patent Application No. 6-303977. As described above, a color filter having a frame edge can be manufactured. An electrode or the like is applied to the frame edge portion of the color filter, and it is used as a part of the liquid crystal display device.

The color filter produced by the method of the present invention has heat resistance, water resistance, organic solvent resistance, and
A resin having a high specific electrical resistivity can be applied as a protective film (overcoat layer). Examples of such resins are U.S. Pat. Nos. 4,698,295 and 4,668,601.
No., European Patent Application EP-179,636A, 55
6,810A, JP-A-3-163416, and 3-1.
88153A, 5-78443, 1-2761
01, JP-A-60-216307, 63-218.
771 and the like. The obtained color filter preferably has as few surface irregularities as possible, for example, ± 0.1 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 plate or a retardation film may be arranged on the surface of the color filter opposite to the emulsion surface of the light transmissive substrate.

[0064]

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) JP-A-63-293348 As described in Examples, a 100-μm-thick polyethylene terephthalate support coated with carbon black dispersed in polyvinyl chloride as a back layer was subjected to gelatin subbing. Then, the first to tenth layers having the constitutions shown below were simultaneously coated in multiple layers to prepare a color light-sensitive material. 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. 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 Absorbent (Cpd-9) ... 0.06 UV absorber (Cpd-10) ... 0.03 Holimer (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-1) ... 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 point solvent (Solv-1) ... 0.25 High Boiling point 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 absorption Agent (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) ... 0.50 Gelatin・ ・ ・ 1.20 Cyan coupler (ExC-1) ・ ・ ・ 0.23 Cyan coupler (ExC-2) ・ ・ ・ 0.25 Yellow coupler (ExY-1) ・ ・ ・ 0.60 color Image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.07 Color image stability Agent (Cpd-21) ... 0.12 Polymer (Cpd-13) ... 0.17 High boiling solvent (Solv-2) ... 0.19 High boiling 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 absorption Agent (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 image-sensitizing dye (ExS-14) (Br: 80%, 0.5 μ) ... 0.47 Gelatin ...・ ・ ・ 1.40 Cyan coupler (ExC-1) ・ ・ ・ 0.25 Cyan coupler (ExC-2) ・ ・ ・ 0.28 Magenta coupler (ExM-1) ・ ・ ・ 0.15 Color image stability Agent (Cpd-1) ... 0.04 Color image stabilizer (Cpd-9) ... 0.05 Color image stabilizer (Cpd-10) ... 0.07 Color image stabilizer ( Cpd-4) ... 0.12 Color image stabilizer (Cpd-22) ... 0.01 Polymer (Cpd-13) ... 0.20 High boiling solvent (Solv-2) ...・ ・ 0.35 High boiling point solvent (Solv-3) ・ ・ ・ ・ 0.16 Layer 9 (Irradiation prevention Postal layer) Gelatin ... 0.50 anti-irradiation dye (Dye-1, 2, 3, 4 a 10:10:13: 1: 5 molar ratio) ... 0.04

10th layer (protective layer) Gelatin ... 0.50 Colloidal silver emulsion (0.02 μ) 0.20 Surfactant (Cpd-14) 0.06 Hard film Agent (H-1) ... 0.25

In each silver halide emulsion layer, 4.0 × 10 ^-6 mol for the blue-sensitive layer, 3.0 × 10 ^-5 mol for the green-sensitive layer and ^{1.10 for} the red-sensitive layer per mol of silver halide. 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. The chemical formulas of the related drugs are shown below.

[0075]

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[0076]

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[0077]

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[0078]

[Chemical 4]

[0079]

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[0080]

[Chemical 6]

[0081]

[Chemical 7]

A transparent borosilicate glass (30 cm × 30 cm) having a thickness of 1.1 mm was used as a light-transmissive substrate, and gelatin and colloidal silica (average particle size 7 to 9 mμ) were used as an adhesive layer on the surface in a weight ratio of 1. : 3 and mixed with saponin as a surfactant. The coating thickness of the dry film was 0.2μ.

The tenth layer of the above-mentioned color light-sensitive material was brought into close contact with the coating surface of this light-transmitting substrate as an adhesive layer. At this time, some moisture was applied to the emulsion surface of the light-sensitive material. After that, a laminator whose temperature was set so that the temperature of the contact surface was about 130 ° C. was used and the particles were passed at a linear velocity of 0.45 m / min.

The polyethylene terephthalate film having a thickness of 100 μm has a boundary between the color filter surface and the frame edge so that four 100 mm × 150 mm liquid crystal color filter surfaces can be obtained with a 25 mm frame edge on the outside. The line is pre-cut.

After laminating and cooling to about room temperature, a flexible support 100 m corresponding to the color filter layer portion is formed.
Only 4 sheets of m × 150 mm were peeled off. The emulsion surface was uniformly adhered to the substrate surface, and no white spots were observed.

Next, a mask for color filters consisting of a blue portion, a green portion, a red portion and a black portion is overlaid on the substrate having the emulsion layer prepared as described above from the emulsion surface side, and pattern exposure is performed using tungsten light. After doing, first 38 ℃
It is dipped in the hardening fluid for 3 minutes and pre-duralized. Subsequently, after washing with water at 35 ° C. for 1 minute, the support of the frame edge portion where the color filter layer is not formed is also peeled off, followed by washing with warm water at 38 ° C. for 5 minutes and an adhesive layer corresponding to the frame edge portion. After peeling off the color light-sensitive material, the exposed substrate is color-developed and desilvered according to the following steps, and B is removed by one operation.
A color filter having three colors of G, R and black was prepared. (Processing step) (Temperature) (Time) Color development 38 ° C. 2 minutes 30 seconds Bleach fixing 38 ° C. 1 minute Water washing-2 35 ° C. 1 minute Water washing-3 35 ° C. 1 minute Water washing-4 35 ° C. 30 seconds Dry 80 ° C. 1 minute (Washing-2, 3, 4 was a 3 tank countercurrent system from 4 to 2.)

The composition of each processing solution is as follows. Hardener Sodium sulphate (anhydrous) 160.0 g Sodium carbonate (anhydrous) 4.6 g Formalin (37%) Add water 1 liter pH (25 ° C) = 10.0 Color developer water 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 Optical brightener (WHITEX4 Sumitomo Chemical 1.0 g sodium sulfite 0.1 g disodium-N, N bis (sulfonatoethyl) hydroxylamine 5.0 g sodium triisopropylnaphthalene (β) sulfonate 0.1 g N-ethyl-N- (β-methane Sulfonamidoethyl) -3-methyl-4-aminoanilino・ 3/2 Sulfuric acid ・ 1 hydrate 5.0g Add water 1 liter pH (25 ℃) = 10.0 Bleach-fixing solution Ethylenediaminetetraacetic acid 5.0g Ethylenediaminetetraacetic acid ・ Ferric ammonium 55.0g 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 Rinse water Deionized water with conductivity of 5 μS or less

As described above, four color filters for liquid crystal were prepared. The obtained color filter has an absorption luminosity of 0.9 for each of cyan, magenta, and yellow components.
~ 1.6, B, G, R, and the absorbance of each component is 2.2
A color filter having a black density of ˜2.9 and free of white spots and peeling defects was obtained.

(Example-2) The same processing as in Example-1
According to the specifications, a color photosensitive material and a light-transmitting substrate are provided on polyethylene terephthalate 100 μm, and the surface of the color film photosensitive material is placed on the light-transmitting substrate at a temperature of 130 ° C.
3kg / m using a laminator whose temperature is set to
Thermocompression bonding was performed at a pressure of ² . The thickness of 100 μm polyethylene terephthalate film is 300 mm x 400
There are cuts on the boundary line between the color filter surface and the frame edge so that four 100 mm x 150 mm color filter surfaces for liquid crystal can be obtained on the borosilicate glass with a 25 mm frame edge on the outside. Engraved. After laminating and cooling to about room temperature, the flexible support corresponding to the frame edge portion where the color filter layer is not formed is peeled off, immersed in a 10% sodium hypochlorite aqueous solution for 1 minute, and washed with warm water. The adhesive and the color photosensitive material at the frame edge are peeled off at 38 ° C. for 3 minutes. Next, the flexible support corresponding to the portion for forming the color filter layer is peeled off, after pattern exposure, a film-hardening treatment with the same film-hardening solution as in Example-1 is carried out, followed by washing with water, Color development and desilvering were performed under the same conditions as in Example 1 to prepare four color filter layers. The obtained color filter had the absorbance of each of cyan, magenta, and yellow components of 0.9 to 1.6 and the absorbances of B, G, and R of 2.2 to 2.9 as in Example 1. It was possible to obtain a color filter having a black pattern and having no white spots or color bleeding.

[0090]

According to the present invention, a hard light-transmissive substrate such as glass has an insulating portion where a glass surface for exposing electrodes and the like is provided at a frame edge portion where a color filter layer is not formed, In addition, a large number of color filters are created at the same time on a single glass substrate, and they have blue, green, red, and high-concentration black parts with excellent spectral transmission characteristics, and are highly accurate without white spots. Color filter can be obtained.

[Brief description of drawings]

FIG. 1 is a top view on a glass substrate in which each color filter of the present invention has a frame edge portion and a plurality of color filters can be simultaneously obtained on one glass substrate.

[Explanation of symbols]

 1 light transmissive substrate 2 color filter layer portion 3 frame edge portion 4 boundary line break

Claims (2)

[Claims] 1. A color light-sensitive material having a color light-sensitive layer provided on a flexible support with a release layer interposed therebetween is adhered to a light-transmissive substrate, and then the flexible support is formed into a color filter layer. After peeling only the portion to be exposed, after pattern exposure, and after the film hardening treatment, the support at the frame edge portion where the color filter layer is not formed is also peeled off, and at least the photosensitive layer at the frame edge portion is peeled off by washing, and then color development, After desilvering, or after pattern exposure, hardening treatment, development treatment, desilvering, after removing the support at the frame edge, at least the photosensitive layer is peeled off by washing to form a color filter layer. A method for manufacturing a color filter, which is characterized in that 2. A color photosensitive material having a color photosensitive layer provided on a flexible support with a release layer interposed therebetween is adhered on a light-transmissive substrate, and then the flexible support is formed with a color filter layer. After peeling only the frame edge portion, at least the photosensitive layer of the frame edge portion is peeled off by washing, and then the flexible support of the portion forming the color filter layer is also peeled off, and after pattern exposure, a film hardening treatment is carried out. Then, a color filter is formed by performing color development and desilvering.