JPH0432803A - Color filter - Google Patents

Abstract

PURPOSE:To improve heat resistance and the smoothness on the surface of the filter by incorporating one kind of the coupling reaction products of a specific precursor compd. and the oxidant of a color developing agent into picture elements of one color. CONSTITUTION:At least one kind of the coupling reaction products of the precursor compd. expressed by formula 1 and the oxidant of the color developing agent are incorporated into the picture elements of at least one color. In the formula 1, R denotes an aliphat. group, arom. group or heterocyclic group; X denotes a hydrogen atom or the group which can be eliminated by the coupling reaction with the oxidant of the color developing agent; n denotes 0 or 1. The color filter which has the excellent smoothness and associates no problems in heat resistance is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color filter, and more particularly to a color filter suitable for use in a color liquid crystal display.

[Background of the invention]

As a color filter, there is one produced by an external color development method using a color silver salt photographic material, as disclosed in JP-A No. 55-6342.

However, in the method described in the above-mentioned patent, steps were created between pixels having different spectral characteristics, resulting in a problem in smoothness as a color filter.

Similarly, as a color filter based on the external color development method, as shown in JP-A-63-194257, a compound that produces a substantially colorless compound by a coupling reaction with an oxidized form of a color developing agent is used. There is a method of intentionally creating a relief using a color filter, but the color filter created by this method provides good smoothness, but has a problem with heat resistance.

[Purpose of the invention]

An object of the present invention is to provide a color filter that has excellent smoothness and no problems in heat resistance.

[Structure of the invention]

The above object of the present invention is to provide a color filter consisting of three primary colors of light on a light-transmitting substrate, in which at least one of the cambling reaction products of a precursor compound represented by the following general formula (I) and an oxidized color developing agent is produced. This is achieved by a color filter containing at least one type of color in each pixel.

General formula (I) %Formula% In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group, and
represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent.

n represents 0 or 1.

The coupler of the general formula (I) used in the present invention has t
: Added and used in the form of at least a portion dissolved in a developer. A developer containing a coupler of general formula (I) is
It is the same as an external color developer or a black and white developer for silver dye bleaching. However, if the developer is the same as the black and white developer, the developer must necessarily contain a color developing agent.

Next, the coupler represented by the bifurcated type (I) used in the present invention will be explained.

R represents an aliphatic group, an aromatic group, or a heterocyclic group, preferably an aliphatic or aromatic hydrocarbon group having 1 to 30 carbon atoms, and these may be substituted.

Examples of aliphatic groups include methyl, butyl, hexadecyl, allyl, chlorohexyl, and 2-fluorynyl.
It means any linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group, which may have one or more substituents as described below, and when two or more may be the same or different.

Typical examples of aromatic groups include phenyl and naphthinodine; representative examples of heterocyclic groups include 2-pyridyl, 2-imidazolyl, 2-furyl, and 6-quinol. , may have one or more substituents described below.

The substituent groups that R may have are as follows, and these substituents may be further substituted with one or more groups selected from this substituent group. Aliphatic groups, aromatic groups, heterocyclic groups, aliphatic oxy groups (e.g. metquine, 2-methquinethoquino, 2-probenyloquino), aromatic oxy/groups (e.g. 2-chlorophenoxy/, 4-/anophenoxy), anlu groups (e.g. acetyl, benzoyl), ester groups (
For example, butoki-7carponyl, fenoquine carbonyl yloquine, )+ki/sulfonyl, toluenesulfonyloki/), amide group (e.g. acetylamino, methanesulfonamide), carbamoyl group (e.g. ethylcarbamoyl, diethylcarbamoyl), Sulfamoyl group (
For example, butyl sulfate moyl), garbage groups (e.g., succinimide, hytantoynyl), ureido groups (e.g., phenylurei, ;'methylureido), sulfamoylamino groups (e.g., dipropylsulf7 moylamino), fatty acids. aliphatic, aromatic or heterocyclic sulfonyl groups (e.g. methanesulfonyl, phenylsulfonyl), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio), substituted amine groups (e.g. diethylamino,
Anilino), /lyl group (eg, trimethylfuryl), hydroquinyl group, cyano group, carbonyl group, sulfonic acid group, nitro group, thionanato group, halogen group (fluorine, chlorine, bromine, iodine), and the like. Note that two or more substituents further substituting these substituents may form one or more cyclic structures (e.g., 3,4-dimethyn-oquino-7-ninyl, ], ]2.3.4 - Tetrahydronaft).

In general formula (I), when X is not a hydrogen atom but represents a coupling-off group (hereinafter referred to as a leaving group), the leaving group is coupled via an oxygen, nitrogen, sulfur or carbon atom. A group that binds a ring activated carbon to an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic/aromatic or heterocyclic sulfonyl group, an aliphatic/aromatic or heterocyclic carbonyl group, /・Rogen atom , aromatic azo group, and the aliphatic/aromatic or heterocyclic group contained in these leaving groups are:
It may be substituted with the substituent described for R, and when there are two or more of these substituents, they may be the same or different.

Specific examples of leaving groups include halogen atoms (e.g. fluorine, chlorine, bromine), alkoxy groups (e.g. ethquin, methoxyethylcarbamoylmethoxy, carboxylpropyloxy, methylsulfonylethoxy), aryloxy groups (e.g. 4-chlorofequin, 4 -methoxyphenoquine, 4-carboxyphenoquine), alkoxy groups (e.g. acetyloxy, benzoyloxy), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), anrulamino groups (
e.g. dichloroacetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfonamide groups (
methanesulfonamide, p-toluenesulfonamide)
, alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy, penzyloxycarbonyloxy), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy), aliphatic/aromatic or heterocyclic thio groups (e.g., ethylthio, phenylthio, tetrazolylthio), carbamoylamino groups (e.g. N-methylcarbamoylamino, imidazolyl, pyrazolyl, triazolyl, 1,2
-dihydro-2-oxo-1-pyridyl), imido groups (e.g. scunnimit, hydantoinyl), aromatic azo groups (e.g. phenylazo), etc., and these groups are further substituted with the substituents described for R. It's okay. or,
Bis-type couplers bonded via a carbon atom and obtained by condensing a 4-equivalent coupler with an aldehyde or ketone as a leaving group are also available in the present invention. The leaving group may include development inhibitors, development accelerators, and other photographically useful groups.

Typical specific examples of the coupler represented by the general formula (I) according to the present invention are described below, but the present invention is not limited thereto.

(Exemplary Compound) O2 M [Example] Next, the present invention will be explained in more detail with reference to Examples. Note that % in the examples represents weight % unless otherwise specified.

(Example 1) Preparation of silver halide photosensitive material An iodine containing 4 mol% silver iodide was prepared by simultaneously adding an aqueous silver nitrate solution and an aqueous solution containing potassium bromide and potassium iodide to a 10% aqueous solution of gelatin. A silver bromide emulsion (average grain size + 0.05 μm, gelatin concentration 9%) was prepared.
:. Addition conditions were regulated to obtain a Lippmann emulsion with an average grain size of 0.05 μm! :.

The resulting silver iodobromide emulsion contained 28.3 mg per mole of silver.
of sodium thiosulfate pentahydrate was added thereto and chemically aged at 59.5°C for 45 minutes.

Then, to the above emulsion were added l-phenyl-5-mercaptotetrazole and 1-carboxyethyl-3,4°5-hydroquinebenzene, each at 14% per mole of silver,
In addition to adding 5 mg and 340 g, the following compound 5C-1
An emulsion coating solution was prepared by adding 15.9 g of the following compounds per mole of silver, and further adding 40 mg and 5 mg of the following compounds H-1 and H-2 as hardeners per Ig gelatin, respectively.

SC-] ((C)1.=CH5O2CH2), CCH, 5O2C
HICH2)! The emulsion coating solution obtained in NCH, CH, SO was coated on a transparent borosilicate glass substrate (30 cm x 30 cm) with a thickness of 1.1 mm to a dry film thickness of 3 μm to form an emulsion layer. A silver halogenide photosensitive material was prepared. The amount of silver coating was 1.5 g/m', and the amount of pigment coating was 0.24 g/m'.

This silver halogenide photosensitive material has a backing layer on the surface of the borosilicate glass substrate opposite to the surface having the emulsion layer.

The formation of this backing layer will be explained next.

A dispersion of the following compound Y-1 was added to an aqueous gelatin solution, and 4 Q mg of each of hardeners H-1 and H-2 were added.
mg was added. Here, the amount of gelatin added to the gelatin aqueous solution was adjusted in advance to be 5%. Further, the amount of Y-1 added to 100 ml of gelatin aqueous solution was 1.35%.

Compound Y-1 Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a backing layer. Y-
The applied amount of No. 1 was lomg/dm''.

The above-mentioned dispersion was prepared by dissolving 11 g of Y-1 into tricresyl phosphate Ig and 4.29 mff of ethyl acetate, followed by 0.83 g of gelatin and triisopropyl-β.
- 5% aqueous solution of sodium naphthalene sulfonate 2.6
The mixture was added and mixed into an aqueous solution containing 3 cc and 8.4 a of water, subjected to ultrasonic dispersion at 50° C., the ethyl acetate was removed, and water was added to make a total of 17.6 a12.

Preparation of color filters As shown in Figure 1, 3 (blue), G (green), and R (red) are prepared.
A method for producing a color filter having a color mosaic pattern will be described below. The size of each pixel is 15
It is 0/7m×150μ■.

A chrome mask for a color filter having a square opening of 150 μm on each side was placed on top of the photosensitive material, and a first exposure was performed using a mercury lamp.

Exposure was carried out at a position corresponding to part B in FIG.

The exposed photosensitive material was immersed in the following magenta color developer and red color developer at 23° C. for 3 minutes.

Magenta color developer composition Magenta coupler (M-0)...1, 13g
1-(2,4,6-trichlorophenyl)-3-(p-
nitroanilino)-5-virazoloneveis coupler (
WE-1) ...0.21g1-(2,4,6-
trichlorophenyl)-3anilino-4-methyl-5-
Pyrazolone developing agent・・・・・・・・・・・・ 1,
0g 4-amino-3-methyl-N,N-diethyl-aniline hydrochloride Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3.00m (dianhydrous sodium sulfate... ...20.0g sodium bromide
・・・・・・・・・ 1.0g sodium sulfite...
...IO, Og Ethylene J Cole...
...IO, 0mΩ polyethylene glycol...
・・・ Add 2.0g water・・・・・・・・・・・・
II2 Note that sodium hydroxide was added to the above magenta color developer to adjust the pH value at 25° C. to 12.0.

Red color developer composition Magenta coupler (M-0) 1.25g
1-(2,4,6-)lichlorophenyl)-3(p-nitroanilino)-5-Hilazo O-on Yellow Kabra...
・・・・・・・・・ 0.47gσ-(4-carboquinphenoxy)-σpivaloyl-2,4-dichloroacetanilide vacuole (WE-1)・・・O,]00
3g1-2,4.6-trichlorophenyl)-3anilino-4-methyl-5-pyrazolone developing agent...
・・・・・・・・・ 1.2g4-amino-3-methyl-
N,N-diethylaniline hydrochloride sodium nitrilotrimethylenephosphonate (40%)
3.00m12 Anhydrous sodium sulfate 20.0g Sodium bromide 3.0g Sodium sulfite
・・・・・・・・・ IO, 0g ethylene glycol・・
・・・・・・IO, oO+nQ polyethylene glycol・・・・・・ Add 2.0g water・・・・・・・・・
... 1gAdditionally, sodium hydroxide was added to the above red color developing solution so that the pH value at 25°C was 1260.
I adjusted it so that

Next, the substrate was washed with water for 1 minute, immersed in a silver source white liquor (2) having the following composition for 3 minutes to perform bleaching, washed with water for 1 minute, and then dried to form a blue area on the substrate (No. 1 treatment).

Silver source white liquor (2) Composition: Iron ethylenediaminetetraacetate (I [[) ammonium salt.
・・・・・・・・・ 200.0g Ammonium bromide・・・・・・ IO, 0g Glacial acetic acid・・・・・・・・・・・・ 10.0+nff Add water to make 1a , adjust the pH to 6.0 using aqueous ammonia.

Next, another chromium mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was part G in FIG. 1, and a second exposure was performed.

The photosensitive material that had been exposed for the second time was immersed in a yellow color developing solution having the following composition for 3 minutes at 23°C.
The substrate was washed with water for a minute, then bleached, washed with water, and dried in the same manner as the first time to form a green part on the substrate f- (second treatment).

Yellow color developer composition Yellow color... 1.5gα-(
4-carboquinphenoxy)-, -pivaloyl-2,4
-For dichloroacetanilide development pressure...
... 2,0g 4-amino-3-methyl-N-ethyl-N-β methanesulfonamide ethylaniline 11
/2 Sulfate I hydrate Sodium nitrilotrimethylene sulfonate (40% aqueous solution) 3-3-0O anhydrous sodium sulfate 20.0g Sodium bromide・・・・・・・・・ 3.0g sodium sulfite・・
・・・・・・・・・ 10.00g ethylene glycol・・
・・・・・・ 10. Omρ polyethylene glycol・
・・・・・・ Add 2.0g water・・・・・・・・・
... IOIncidentally, by adding sodium hydroxide to the above yellow color developing solution, the pH value at 25°C was 12.
It was adjusted so that it became 0.

Next, another chromium mask for a color filter is placed on the photosensitive material after the above processing so that the exposed area is the R area in FIG. 1, and a third exposure is performed.

The photographic material subjected to the third exposure was immersed in a red color developer having the above composition at 23°C for 3 minutes, and then washed, bleached, washed with water and dried in the same manner as the second exposure, and then placed on a substrate. However, the bleaching solution is silver source white liquor (I
) was used.

Next, a chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was the R area in FIG. 1, and a fourth exposure was performed.

The photosensitive material that has been exposed for the fourth time is processed at 33°C as follows to form red areas (fourth process), resulting in B (blue), G (green), R (red ) A color filter having a three-color mosaic pattern was obtained.

Black and white development 1 minute water wash 1 minute dye bleach 1 minute water wash] Minute silver bleach 4 minutes water wash
Wash for 1 minute
Arrival 1 minute water
Washing: Drying for 4 minutes The bath used for each treatment had the following composition.

Black and white developer composition Sodium sulfite, Hydroquinone, Potassium hydroxide (48% aqueous solution) / Nytylene glycol / Mesone carbonate, Lium, Potassium bromide, Thiacia tool, Add water 10g 0g mQ 0mQ ・ ・ 0.7g・ ・ 20g 2g 0.05g Q 96% sulfuric acid・・・・・・・・・・・・ 40m12
Potassium iodide・・・・・・・・・ 15g2.3
．． 6-Trimethylquinoxaline...Add 2g water...IQ silver silver white liquid 1) Composition Pure water...800mff Sodium ferricyanide...206g Sodium bromide...15g Borax...
・・・・・・・・・ Add 1g water・・・・・・
・・・・・・ Using IQQ potassium oxide aqueous solution 2
pI at 5°C (adjusted to a value of 8.0).

Fixer composition Ammonium thiosulfate...175.0g Sodium sulfite...8.5g Sodium metasulfite...2.3g Add water...・・・・・・・・・ IQ (pH using acetic acid)
Adjusted to =6.0. ) After making the color filter, the backing layer was completely removed by impregnating the backing layer with a 3% aqueous sodium hypochlorite solution and wiping it with gauze.

The color filter thus obtained was used as sample CF-
Set to 1.

In the manufacturing process of sample CF-1, the magenta color developer and the red color developer were prepared using NO32~ shown in Tables 1 and 2.
Color filter samples CF-2 to CF-8 were prepared in the same manner except that the developer No. 8 was used.

Each sample obtained was heated to 180°C using an oven.
A heat resistance test was conducted for 0.2.4 hours. (71) At that time, a microten/tometer (aperture scanning area 250 μm
") was scanned to determine the change in blue light density of the blue light transmitting pixel. The obtained results are shown in Table 3.

Note that the concentration values in Table 3 are shown as relative values, with the concentration of each sample before the heat resistance test being 1.

In addition, the smoothness of the surface of each color filter sample obtained was determined by (
It was determined by Taly Step manufactured by Rank Taylor Hobson Co., Ltd. The level difference between B pixel and R pixel with respect to G pixel is
It is shown as the average value of the values measured at 30 locations for each sample. The results are also shown in Table 3.

As is clear from the obtained results, the color filter of the present invention is excellent in both heat resistance and filter surface smoothness.

Table 1 Magenta coupler in magenta color developer Table 2 Yellow coupler amount and magenta in red color developer Table 3
B density change of B pixel due to heat resistance test

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing an example of a color filter obtained by the manufacturing method of the present invention, and FIG. 2 is a cross-sectional view showing an example of a liquid crystal color display using the color filter obtained by the manufacturing method of the present invention. It is a diagram. 11... Light-transmissive substrate 12... Colored portion 13...
Black portion 24...Color filters 25a, 25b...Polarizing plate 26...Liquid crystal 2
7a, 27b...electrodes

Claims (1)

[Scope of Claims] A color filter consisting of three primary colors of light on a light-transmissive substrate, comprising at least one of the coupling reaction products of a precursor compound represented by the following general formula (I) and an oxidized form of a color developing agent. A color filter characterized in that pixels of at least one color contain seeds. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group,
X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized color developing agent. n represents 0 or 1. ]