JPH01109302A - Production of color filter - Google Patents

Abstract

PURPOSE:To improve the accuracy and spectral characteristics of a color filter by using a photosensitive compsn. contg. a specific azo metal chelate compd. CONSTITUTION:The photosensitive compsn. dissolved or dispersed with the azo metal chelate compd. expressed by formula I, for example, negative type photoresist, is first coated on a substrate of the color filter to be used for a solid-state image pickup element, liquid crystal display element, etc. The resist layer is then exposed through a photomask and is developed to form a dye pattern. The different dye patterns can be formed on the same substrate by repeating the above-mentioned stage. In formula, Z, Z' denote the atom group necessary for completing the desired ring; G denotes a metal chelating group; M denotes a bivalent hexadentate ligand metal ion; the compd. expressed by formula II is usable for the compd. expressed by the formula. In formula, R3 denotes lower alkyl; R4, R5 denote H, alkyl or 1-25C, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to CCI) (charge coupled device),
Related to a method for manufacturing color filters used for color solid state image sensors such as BBD (valid bricate device), CID (charge injection device), BASIS (base store type image sensor), contact type image sensors, color displays, etc. .

[Conventional technology]

Conventionally, interference filters or dye filters are known as force 2 filters used in this type of element.

Interference filters have a multilayer structure, and there are many manufacturing problems, such as adjusting the film thickness determined by the material (refractive index) used and maintaining the film in a laminated manner when designing the film to match predetermined spectral characteristics. In particular, it is often difficult to suppress these when forming fine pattern patterns. It also had the disadvantage of high cost.

On the other hand, dyed filters have a mordant layer made of a natural or synthetic polymer material such as gelatin, casein, Greeny or polyvinyl alcohol on a transparent substrate, for example.
A method is known in which the mordant layer is colored in accordance with a predetermined pattern. Examples of the coloring method include a dyeing method in which the material is immersed in a dye bath in which a suitable dye is dissolved.

This method has the advantage of being able to use a large number of dyes and being able to match any spectral characteristics required of the filter, but the dyeing process involves immersing the filter in a dye bath in which the dye is dissolved. We use a wet method that is difficult to control, and in addition, each color is dyed according to a predetermined pattern, requiring the creation and peeling of a dye-resistant mask using photoresist for each color dyeing process. Therefore, the yield rate is low, and it cannot be said to be an appropriate method for manufacturing inexpensive color filters. Furthermore, in terms of performance as a filter, color mixtures such as "bleeding" and "blurring" of colors occur at pattern Jung boundaries, making it unsuitable for use in fields that require high precision.

Furthermore, when using dyes, there have been no dyes that are soluble in organic solvents and have sharp absorption, good hue, and durability.

[Problems to be Solved by the Invention J] The present invention provides a new manufacturing method that does not have the drawbacks of the above-mentioned prior art. It has become possible to manufacture color filters with excellent properties and great economic value.

[Means for solving problems]

The present invention provides a method for producing a color filter in which a colored layer is formed on a substrate, in which the following general formula (
This is a method for producing a color filter, which comprises dissolving or dispersing the azo metal chelate compound represented by 1), coating the composition on the substrate, and patterning the composition.

General Formula (1) In the formula, 2 represents a plurality of atoms necessary to complete at least one I to 7-membered aromatic ring or heterocycle.

Hydrogen atoms on these rings can be one or more alkyl groups, alkoxy groups, arylox groups, aralkyl groups, -aryl groups, halogen atoms, cyano groups, nitro groups, ester groups, carbamoyl groups, acyl groups, acylamino groups, sulfonyl groups. crystal, sulfazoyl group, sulfonamido group, amino group, alkylamino group, 2' represents at least one aromatic ring or heterocycle, in which case 2' represents the point of attachment to the azo bond. At adjacent positions, (1) have nitrogen atoms acting as a chelating layer in the ring of the nucleus;
Otherwise, (U) has a carbon atom directly bonded within the ring of the nucleus, which acts as a chelating layer. The hydrogen atom on the aromatic ring or heterocycle of 2' may be substituted with one or more substituents, and the substituents are the same as those of 2. G stands for metal chelation grave. MFi
Represents a J-valent t-coordinated metal ion.

An example of this method will be described in detail below.

First, the general formula (1) is applied on a substrate made of glass, resin, etc.
A photosensitive composition, such as a negative photoresist, in which an azo metal chelate compound represented by the formula is dissolved or dispersed is laminated by a method such as coating. This resist layer is coated with a desired pattern.

A dye/setane consisting of a dye-containing resin can be obtained by exposing to light through an odomask in a known manner and developing with a developer.

If further different dyes/41 turns are to be formed on the same substrate, the above steps may be repeated while shifting the position of the photomask according to the pattern.

By repeating these steps as many times as there are different colors, it is possible to produce products with a plurality of pigments and e-turns.

Only a portion of the filter of one color may contain the azo metal chelate compound of the general formula (I) of the present invention, and the rest may use known dyes and pigments. For those using pigments, JP-A-47-
It is disclosed in Publication No. 10110j.

Next, the azo metal chelate compound of the present invention will be explained.

Among the rings formed by z and z' in general formula (17), preferred are a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, a pyrazole ring, a thiophene ring, an indole ring, or a pyrazolotriazole ring. Among these ring substituents, preferred are Cl=C2B optionally substituted alkyl group, 08 to C25 optionally substituted alkoxy group, halogen atom, cyano, nitro group, C
1-C25 optionally substituted alkylsulfamoyl group, C6-C3o optionally substituted phenylsulfamoyl group, Cl-C25 ester group, Cl-C25 carbamoyl group, C1-C2! Acyl group of i, C1 to C25
acylamino group, c8-C2B sulfonyl (R1,
R2 represents a hydrogen atom, an optionally substituted alkyl group of Cl-C25, or a phenyl group, R, and R2 taken together! Alternatively, a t-membered ring may be formed. An alkylamino group, an arylamityl group, or a hydroxyl group represented by

Among GO, preferred are hydroxide ion, carboxylate, sulfonamide ion, sulfamoyl ion, amino group, or alkylthio group, and particularly preferred is hydroxyl ion.

Among M, preferred are nickel ([34 lead (■) and cobalt (117), and particularly preferred are nickel (
U).

The compound represented by general formula (I) used in the present invention preferably has at least 1% oil-solubilizing group in order to increase oil solubility.

An oil-solubilizing group is the number of carbon atoms that are bonded to the pigment body in order to dissolve the pigment in non-aqueous solvents. ~30 unsubstituted or substituted (substituents include alkyl groups, alkoxy groups, aryloxy groups, aralkyl groups, aryl groups, halogen atoms,
77) Examples include a nitro group, an ester group, a carbamoyl group, an acyl group, an acyl, an amino group, a sulfonyl group, a sulfamoyl group, a sulfonamide group, an amino group, an alkylamino group, an arylamino group, or a hydroxyl group. Good alkyl group or carbon number io~3! represents an aryl group substituted with (the substituents are the same as above).

These alkyl groups or aryl groups may be bonded directly to the dye moiety main body, or may be bonded via an ester group, carbamoyl group, acyl group, acylamino group, sulfamoyl group, sulfonamide group, amino group, or alkylamino group. You can.

It is preferable that the compound represented by the general formula (1) used in the present invention does not contain a group that is likely to cause a redox reaction or a hydrolysis reaction that impairs the stability of the compound.

Particularly preferred compounds of the present invention are represented by the following general formula (...) or (UN).

In the formula, R3 represents a hydrogen atom or a lower alkyl group. R
4, R6 represents a hydrogen atom, an alkyl group which may be substituted with C1-C251Dll, and a phenyl group which may be substituted with C6-C3o. However, the total number of carbon atoms in R4 and R5 is 1 or more, preferably 1 or more, particularly preferably 10 or more.

Specific examples of compounds used in the present invention are shown below.

In addition, when specific examples are represented by general formulas (IV) to (Vl), specific example substituents of each general formula are shown in Tables 7 to 3.
Shown in the table. (Numbers on the benzene ring indicate substitution positions) General formula (IV) 3! General formula (■) CH3 to 13 Table 3 and below show examples of synthesis of compounds used in the present invention.

Synthesis example 1 Compound! Synthesis of 14/1-/ Intermediate 1-/Synthesis of crosssulfonyl-2-(copyridylazo)-/-f phthol JP-A-13-31
Hiro-Hydroxy-3 synthesized by the method of Publication No. 113
-(2-pyridylazone-/-7phthalenesulfonic acid/
01/% sulfolane/DO- and phosphorus oxychloride/
Internal temperature is 181! ! The mixture was stirred at ~6!0C for 3 hours. After the reaction mixture was cooled to room temperature, it was poured into 1 liter of ice water, and the resulting crystals were washed with water. The yield of the target product obtained by air drying was io, ig.

I
Synthesis of -pyridylazo)-/-naphthol 3-(co,j-di-tert-amylphenoxinepropylaminecoOI and N,F4-dimethylacetamide 70- obtained in 1-7 with stirring at room temperature) 7 g of intermediate were gradually added. After stirring for 1 hour, the reaction mixture was poured into a mixture of 3 ml of concentrated hydrochloric acid and 1 liter of methanol. Crystals were precipitated as water was poured slowly. After washing with methanol water 10:/l and air drying, the yield of the target product obtained was 10:/l/.

1-3 Compound vR/l61) Synthesis: Add nickel chloride to a solution consisting of hydrate I and N,N-dimethylacetamide l-O- Intermediate tg obtained in Synthesis Example 1-2 and N,N-dimethyl Formamide 1001
A solution consisting of 11 was added at room temperature with stirring. 1
After stirring for an hour, glacial acetic acid 20081-water 2! Add to
The precipitated crystals were washed with water. The crystals were purified by silica gel chromatography using chloroform-ethyl acetate (lO:l) as a developing solvent to obtain 5.3 g of the desired product.

m-p, ri/70-/7%'('.

As the dye used in the present invention, the azo metal chelate compound of general formula (I) can be used alone or as a mixture of this and other dyes, as appropriate.

When only a portion of the color filter of one color contains the azo metal chelate compound of general formula (I), the other colors are, for example, JP-A-61-Kota-xi.

No. 1, JP-A No. 1973-Co If-PI No. 3, JP-A No. 7, No. 1973
Dyes and pigments described in publications such as RI2RI03 can be used.

It is also possible to form an intermediate layer made of a transparent resin prior to forming each dye pattern.

Photosensitive rfJc materials used in the present invention include resins in which ammonium chromate is added as a photosensitizer to casein, gelatin, Fischglier, etc., resins in which diazo compounds are added to polymeric base materials such as polyvinyl alcohol and polyvinylpyrrolidone, and Various resist materials can be mentioned.

When using a resist material, a positive type resist may be used, but an expanding negative type resist is preferable. Examples of negative resists include photopolymerizable resists and photocrosslinkable resists. Typical photoresists (product names) include "OMR-xi, ri, t!, 17J,"
"O8R" and "TPS" made by Tokyo Ohka, "wayc
eat-HNR.

) ill ivy, Negative) tR, Ic, Ty
pe JIG.

, S, V) iRJ or more hunt back, ``Micro
resist-732,74'7.7!2'' or more Kod
Manufactured by ak, “Photoretsuk RW-10/%RF-GJ
The above are manufactured by Sekisui Fine Chemical, the above rJsRCIR series are manufactured by Japan Synthetic Rubber, the above 5electilux N are manufactured by Merck, and the ultraviolet resists include rODUR-to.
o%/20. Examples of resists for electron beams include those made by Tokyo Ohka Chemical Co., Ltd., such as 1"0EBR1ooJ and above.

The photosensitive resin may be of positive type, but negative type is generally preferred, and specific examples thereof include the following.

1) A mixed system of dichromate and a water-soluble polymer substance such as albumin, casein, potassium glue, gelatin, gum arabic, shellac, PvA, etc.

2) Diazo resin (a mixture system of a condensate of p-diazodiphenylamine and formaldehyde and a resin such as PVA, PVA+polyvinyl acetate, etc.).

3) p-7 22lenebisazide, p-diazide benzophenone, #, l-diazide diphenylmethane, #
, 3'-Diazidostilbene, 4c, 3'-Diazidochalcone, co, t-di(4c'-azidobenzanecyclohexane, co, b-di(u I-azidobenzal)-
Reference-methylcyclohexanone, 4C,l-diazidostilbene-2゜21-sodium disulfonate, 1. ! −
Azide compounds such as diazidonaphthalene-sodium 3,7-disulfonate and natural rubber, synthetic rubber, fluorinated rubber, P
A mixed system with resins such as VA, polyvinylpyrrolidone, diacetone acrylamide, methyl cellulose, and vinyl alcohol-maleic acid copolymer.

4) Azide group-containing polymers such as polyazido vinyl benzoate, polyazido vinyl heptatarate, polyvinyl azido benzal acetal.

5) Polymers containing cinnamic acid groups such as polyvinyl cinnamate, polyvinyl cinnamate 7-thalerate, polyvinyl cinnamylidene acetate, polyvinyl acetate-cinnamylidene acetate.

6) A monomer, oligomer or polymer having an ethylenically unsaturated bond such as acrylic acid, methacrylic acid, methyl methacrylate, coethylhexyl acrylate, 2°-hydroxyethyl acrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate and benzoin, Benzoin methyl ether, benzophenone, Michler's ketone, thioxanthone,
A mixed system with a photopolymerization initiator such as anthraquinone sulfonate. Note that the ratio of the photosensitive resin and the azo metal chelate compound in the photosensitive layer is suitably about o, or-1 mOwtTo. Also, the thickness of the photosensitive resin layer is Q.

Approximately 10 μm is appropriate.

If the azo metal chelate compound of general formula (I) is difficult to dissolve in the solvent of the photosensitive resin, the photosensitive resin and the azo metal chelate compound are placed in a ball mill, roll mill, etc. and mixed to finely disperse the azo metal chelate compound.

The substrate used in the present invention is not particularly limited, and various substrates can be used depending on the purpose of use as long as they can be coated with a resin. Specifically, the following can be used.

For example, glass plates; optical resin plates; gelatin; resin films such as polyvinyl alcohol, hydroxyethyl cellulose, polymethyl methacrylate, polyester, polyvinyl butyral, and boriabad. Further, it is also possible to integrally form a substrate with a material to which a notarized color layer can be applied as a color filter. Examples of substrates in this case include the display surface of a cathode ray tube, the light receiving surface of an image pickup tube,
Examples include a contact type image sensor-1 liquid crystal display surface using a Uni JS-1 thin film semiconductor on which a solid-state imaging device such as a CCD, BBD%CID%BASIS, etc. is formed, a photoreceptor for color electrophotography, and the like.

[Effects of the Invention] The color filter containing the azo metal chelate compound of the present invention has sharp absorption and clear colors.

In addition, since it is soluble in organic solvents, it is dissolved in the photosensitive composition or has extremely good dispersibility, and the distribution of optical density in each pixel of the color filter and variation between pixels are small, and it can be used in image pickup devices. There is little noise and a lot of signal when it is used, that is, the S/N is large, and when it is attached to a display element, there is little variation in light between pixels and within a pixel.
The displayed image is clear.

Furthermore, the azo metal chelate compound of the present invention has excellent light resistance, heat resistance, water resistance, light resistance under high humidity, and resistance to air oxidation. There is almost no deterioration.

Furthermore, since the azo metal chelate compound of the present invention has excellent solubility in organic solvents, it has the advantage that a wide variety of photosensitive resins can be selected.

Furthermore, since the azo metal chelate compound of the present invention is neutral and has a relatively large molecular weight, it may move from each pixel of the color filter and cause undesirable problems such as blurring of each pixel, blurring around each pixel, and color mixing. Do not cause any phenomenon that does not exist. Furthermore, since the method of the present invention is a simple manufacturing method, the yield of the product is improved.

"Example" The following is a collective explanation of the example, but "parts" in the example
indicates "parts by weight".

Example 1 Negative resist for deep ultraviolet light 0 as photosensitive resin
DUR1toViR (manufactured by Tokyo Ohka) was used. In order to produce a red color, the yellow color go and oi parts of JIJ4 of the present invention,
The magenta color 1gO of the shoulders, the ot part is coated with the above photosensitive resin 20
The solution was dissolved in 0 parts and applied onto a glass plate using a spinner to obtain a door-like film with a dry film thickness of 0.6 μm. tO°C%
Pre-bake for 0 minutes, expose for 2 seconds using a predetermined pattern Jung mask, develop for 7 minutes and 440 seconds using a special developer,
Rinse for 1 minute and then post bake at 0C for 2 minutes.

In order to produce a green color, the 436 yellow pigment of the present invention should be added at 0.0/
Department and special request 1986-1977 Sanhiro? 0.011 part of the following phthalocyanine If color mixture described in Specification No. 7 was used in place of the above red coloring dye.

Expression (■) Note that Pc represents a phthalocanine skeleton.

To produce blue color, use the formula (■) 7 talocyanine pigment 0
．． 0/1 part and 0.0/part of rotten magenta dye of the present invention were used in place of the red color above.

Three color filters consisting of red, green, and blue were prepared by repeating the same steps as the method for preparing the red filter layer, including a green dye pattern, a blue dye, and an e-turn. This was fully satisfactory in fields where high precision is required compared to color filters made by conventional dyeing methods.

The color filter is based on the dye of the present invention and the patent application No. 2-77.
Because the dye described in Reference F7 specification is used,
It has excellent light resistance and light resistance in the presence of moisture, and even when irradiated with a fade meter test at 100,000 lux for an hour, the peak transmittance change was within 71 and the peak wavelength shift was within 11.

The green filter layer of this example has better transparency than the green filter layer of Example 4, which will be described later, and it can be seen that the azo metal chelate compound of the present invention is suitable for color filters.

Example 2 In the same manufacturing process as in Example 1, a wafer on which a solid-state image sensor (for example, a charge transfer device (CCD)) was formed was used instead of glass as the substrate, and R%G, B were formed on the surface in the order I created a color filter directly. The color solid-state image sensor thus produced showed good color reproducibility.

Note that when the CCD wafer surface has irregularities, if a flat layer of polymethyl methacrylate resin was applied first, the pixel pattern of the color filter became sharper.

Example 3 The production of a liquid crystal color display element will be described using an example.

FIG. 1 is a schematic cross-sectional view for explaining an embodiment of forming a color filter on a thin film transistor array by the method of the present invention.

First, an ITO pixel electrode with a thickness of 100 DA was formed in a desired turn on a glass substrate (#701 tan manufactured by Corning Co., Ltd.) by seven etching steps.

Next, AI was vacuum-deposited to a thickness of 100 OA, and a gate electrode layer with a desired pattern was formed by a photorin process.

Next, photosensitive polyimide // was applied to a thickness of 100 DA, and a through hole for contacting the drain electrode 13 was formed by exposure and development.

A 1tooh thick photoconductive layer consisting of an a-8i layer (intrinsic layer =
After forming t II ), an at layer 10 having a thickness of 1000λ was formed thereon by a similar process. Thereafter, it was etched into a desired shape using a dry etching method.

Next, AJ was vacuum-deposited to a thickness of 100A, and a desired /R-turn source electrode 1 and drain electrode 13 were formed by a photolithography process.

Red dye pattern/4! is applied on top of this using the same method as in Example 1! Then, a green dye pattern and a blue dye pattern were formed in exactly the same manner as in Example 1 to form a three-color color filter consisting of red, green, and blue.

Next, an insulating film (polyimide resin) imparted with an orientation function was applied to the entire surface to a thickness of 1,000 yen, and heat-cured for 2zo (1c) for 1 hour.

Next, after forming an ITO electrode of 1,000 μm on one surface on another glass substrate (#70! made by Corning), an insulating film (polyoxide resin) with an orientation function was formed on the entire surface.
Liquid crystal was injected between the cured substrate and the thin film transistor array on which the color filter shown in FIG. 1 had been formed, to produce a color liquid crystal display element with good color reproducibility.

Example 4 For the red dye layer, a mixture of 0.01 part of the /Wh36 yellow dye of Example 1 and o and oi parts of the rotten magenta dye was used in the same process as in Example 1 to form a red filter layer on the entire surface of the glass. A red pixel electrode was formed on the substrate on which the electrode was formed. On top of this, 100 parts of photosensitive resin and 1 part of green pigment lead phthalocyanine were kneaded in a Pall mill for 2 hours, and a finely dispersed green pigment was applied with a spinner and dried to form a 0.1 μm -like film. made. Then Example 1
A green filter layer was prepared by performing pre-baking, patterning exposure, development, rinsing, and post-baking as described above.

Using 0.0/2 part of the following metal-free 7 talocyanine (formula (■)) as a blue dye, a blue filter layer was produced in the same manner as the process for producing the red color layer in this example.

On top of this, a polyimide resin imparted with an orientation function was applied to a thickness of 1300 mm over the entire surface and cured. A liquid crystal was placed between this substrate and the thin film transistor of Example 3 prepared on another substrate to produce a bright color liquid crystal display element with good color reproducibility.

In this example, it was also possible to first create a color filter on a glass substrate, create an ITO layer thereon, and then form a polyimide alignment film.

The blue filter layer of this example had better transparency than the blue filter layer shown in Example 1 of JP-A-47-IOr103.

[Brief explanation of the drawing]

FIGS. 1(1) to 1(8) are cross-sectional views showing the steps of manufacturing a thin film transistor array according to the method of the present invention. The numbers indicate the following. /, glass substrate j0 image electrode B, gate electrode 2.1 layer 10, n layer //, insulating layer /2. Source electrode /1. drain electrode l
≠0 dye pattern /! , Insulating layer patent applicant Fuji Photo Film Co., Ltd. Figure 1

Claims (1)

[Claims] In a method for manufacturing a color filter in which a colored layer is formed on a substrate, an azo metal chelate compound represented by the following general formula (I) is dissolved or dispersed in a photosensitive composition, and then, A method for producing a color filter, comprising applying the composition onto the substrate and patterning the composition. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, Z represents multiple atoms necessary to complete at least one 5- to 7-membered aromatic ring or heterocycle. The hydrogen atoms on these rings are one or more alkyl groups, alkoxy groups, aryloxy groups, aralkyl groups, aryl groups, halogen atoms, cyano groups, nitro groups, ester groups,
It may be substituted with a carbamoyl group, acyl group, acylamino group, sulfonyl group, sulfamoyl group, sulfonamide group, amino group, alkylamino group, arylamino group, or hydroxyl group. Z' represents at least one 5- to 7-membered aromatic ring or heterocycle, in which case Z' represents at least one 5- to 7-membered aromatic ring or heterocycle, in which Z', in a position adjacent to the point of attachment to the azo bond, (i) attaches a nitrogen atom to serve as a chelating site to the nucleus; or (ii)
It has a carbon atom in the ring of the nucleus to which a nitrogen atom acting as a chelating site is directly bonded. The hydrogen atom on the aromatic ring or heterocycle of Z' may be substituted with one or more substituents, and the substituents are the same as those of Z. G represents a metal chelating group. M represents a divalent hexacoordinated metal ion.