JPS61172104A - Color filter - Google Patents

Abstract

PURPOSE:To obtain a color filter having the excellent durability of the completed color filter to light and heat and small browning of a dye by forming a colored pattern to an image forming layer which is coated on a substrate and contains a polymer having a specific unit. CONSTITUTION:This color filter is constituted by forming the colored pattern on the image forming layer which is coated on the substrate and contains the polymer having the unit expressed by the formula. More specifically a photocrosslinkable polymer soln. is prepd. by mixing the above-mentioned polymer and a photocrosslinkable material and in some case, binder. Such soln. is coated on the surface of the photodetecting part to form the coating layer of the photocrosslinkable polymer. The light past an exposing pattern is irradiated to the surface thereof to form the crosslinked part. Such layer is then cleaned with a suitable solvent by which the mosaic or stripe-shaped crosslinked polymer layer is obtd. The polymer layer is dyed with the dye by which the color separating filter element is formed.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a color filter used in color image sensors, liquid crystal displays, etc. [Background Art] Conventionally, as a method for manufacturing this type of color filter for color separation, For example, a dyeing method as described in Japanese Patent Publication No. 52-17375 has been adopted.

That is, a photosensitive liquid made by imparting photosensitivity to a water-soluble resin is uniformly applied to a predetermined substrate such as glass or a device, dried to form a photosensitive film, and then photolithography is used to form stripes, mosaics, etc. A relief image of a desired pattern is formed, and this relief image portion is dyed using a dye having predetermined spectral characteristics. Subsequently, a transparent intermediate layer is applied (or a fixing process is carried out). Furthermore, in order to form color filters for the second and subsequent colors, the same operations as for the first color are repeated to form a predetermined colored image, and then a transparent protective layer is formed as the top layer to form color filters.

At this time, the dyeing base materials include water-soluble resins such as gelatin, zein, $9 vinyl acetate/derivatives, cellulose derivatives, polyacrylamide derivatives and their derivatives, weight salts, diazo compounds, diazide compounds, etc. A water-soluble photosensitive composition (photosensitive liquid) composed of a photosensitizer (photocuring agent) and a photosensitizing agent (photocuring agent) is used. Properties required of a photosensitive liquid include coating properties, adhesion to a substrate, dyeability, resolution, noturn reproducibility, and sensitivity. As materials that satisfy these requirements, gelatin, polyvinyl alcohol, casein, etc. are often used.

For example, gelatin aqueous solution added with dichromate to impart photosensitivity can be sufficiently exposed with a high-pressure mercury lamp.
Furthermore, although K has photosensitivity in the visible range, the absorption in the visible range disappears after development, and it has extremely good properties as a dyeing base material. However, the currently used photosensitive solutions made of water-soluble resins such as gelatin, casein, and polyvinyl alcohol have poor storage stability, insufficient dyeing properties, and the need to heat the solution to a certain temperature during coating or dyeing. It is said that it is difficult to control the production because it requires heat (there are some shortcomings).

On the other hand, a method has been proposed in which a synthetic polymer compound is mixed and used as a water-soluble resin for color filters. For example, JP-A-53-47227, which includes a copolymer latex, and JP-A-58-1346, which includes a polymer mordant.
Specification No. 11 and the like are known. However, products using these polymer compounds may have insufficient dyeing density, or may be difficult to use due to the combination of the polymer compound and photohardening agent (e.g. dichromate).
These polymer compounds and the gelatin, casein, polyvinyl alcohol, etc. described above may not be compatible with each other, and when mixed, phase separation or aggregation may occur, resulting in a uniform coating. To obtain [i was.

〔the purpose〕

The present invention has been devised in view of the above problems, and its object is to provide a color separation filter for use in image sensors, liquid crystal displays, etc., which does not have the above-mentioned drawbacks. It is therefore an object of the present invention to provide an improved color filter.

Another object of the present invention is to melt, apply, develop, and
An object of the present invention is to provide a color filter using a dyeable polymer and a method for producing the same.

Another object of the present invention is to provide a color filter made of a hydrophilic polymer that has good film properties and exhibits extremely high dyeability.

Another object of the invention is that dichromate, gelatin,
An object of the present invention is to provide a color filter using a photosensitive composition for a color filter, which is made of a polymer having good miscibility with polyvinyl alcohol, casein, etc., and can form a uniform film.

Still another object of the present invention is to provide a completed color filter which has excellent durability against light and heat and whose dyes are less prone to fading. This is achieved by a color filter characterized by forming a colored/R-turn on an image forming layer containing a polymer having a unit represented by the following general formula, which is coated on a substrate.

General Formula (I) In the formula, human represents one monomer unit derived from a copolymerizable ethylenic monomer. R1 represents an alkyl group containing one hydrogen atom. R2 represents an alkyl group or an aralkyl group. Xo represents an anion (for example, a halogen ion), X is 0 to 80 mol%, 7 is 20 to 100 mol%, and z is O to 80 mol%. Each seven unit may contain two or more types of monomers.

Examples of ethylenically unsaturated monomers are ethylene, propylene, 1-butene, isobutyne, styrene, alpha-methylstyrene, potassium styrene sulfinate, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), Esters of ethylenically unsaturated mono- or dicarzenic acids (e.g. methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-
Butyl methacrylate, n-hexyl methacrylate,
n-octyl acrylate, benzyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate), monoethylenically unsaturated compounds (e.g. acrylonitrile), dienes (e.g. butadiene, isoprene), N-vinyl compounds (e.g. N-vinylpyrroliP)
N-vinyl acetamide, Murahashi, Imoto, etc., "Synthetic Polymer ■", Asakura Shoten (1971), pages 1 to 51).

The polymer of the present invention is produced by Otsu and Imoto, "Experimental Methods of Polymer Synthesis" (Kagaku Doujin) (1971), Chapter 5, pp. 125-15.
It can be synthesized by ordinary radical polymerization (or copolymerization) as described on page 4.

Examples of the polymers of the present invention are shown below.

Compound example (1) + CH2CI (+, 00 Compound example (2) +CH2CH+1r.

Compound example (3) Compound example (4) CH2CH20H Compound example (5) Compound example (6) Compound example (7) Compound example (8) CH.

Compound Example (9) Compound Example (10) Compound Example (11) Compound Example (12) U Table 1-t2υh Compound Example (13) Compound Example (14) In the present invention, [the polymer is preferably used alone or in the following combinations] A layer is formed with the main goo and provided on the support. The main ingredients include gelatin, aldimine, casein,
Cellulose derivatives, agar, sodium alginate, sugar derivatives, I-lipinyl alcohol, polyvinylpyrroli-P,
I-reacrylamide, and others. These nonoin as needed! A compatible mixture of two or more of - is used. The thickness of the imaging layer is preferably in the range of about 0.1 to about 5 .mu.m, and particularly preferably in the range of about 0.3 to about 2 .mu.m.

In the present invention, for example, the following method can be used to form a colored e-turn in the polymer-containing image forming layer.

Firstly, there is a method in which the image forming layer is formed in a pattern (dots, mosaics, stripes, etc.) and dyed by directly immersing this layer in a dye solution.

The second method is to form a dyeing mask in a no-turn shape on the image forming layer, and then dye the layer by directly immersing it in a dye solution. A third method involves transferring or vapor depositing dyeing distributed in an A-turn pattern onto the image forming layer.

In order to form the image forming layer in a notan shape in the above-mentioned first method, there is a method of adding a photosensitive photocrosslinkable diazo resin as described in JP-A-54-65027, or a method of adding a photosensitive photocrosslinkable diazo resin as described in JP-A-54-65027.
The method of adding potassium dichromate to step 5 as described in No. 143429 can be used. Also, JP-A-58-1
3'4611, page 3, upper right column, line 6 to lower left, line W5, can also be applied. Good results are obtained with dichromate.

In either case, the polymer of the present invention is present in the main material remaining on the support as an image as a result of the development process, and a filter is produced by dyeing the inder and polymer with the dye using a dyeing solution, etc. can do.

As the substrate of the color filter of the present invention, glass or a wafer for a solid-state image sensor can be used. At that time, the color filter of the present invention can be formed directly on the substrate, but it can also be formed after applying an organic or inorganic undercoat layer.

As a method for manufacturing a color filter, for example, the following method can be used. A photocrosslinkable polymer solution is prepared by mixing the polymer, a photocrosslinkable substance, and optionally a main glue. This photocrosslinkable polymer solution is applied to the surface of the light-receiving part of a glass or solid-state image sensor to form a photocrosslinkable polymer coating layer, and then on the surface! ! The polymer coating layer KP is irradiated with light that has passed through Noricin to form dot-like mosaic or stripe-like crosslinked portions. Next, this layer is washed with a suitable solvent to dissolve and remove uncrosslinked portions, thereby obtaining a mosaic or striped crosslinked polymer layer.

Next, this crosslinked polymer layer is dyed with one of red, green, blue, cyan, magenta, or yellow dyes to form a color separation filter element (colored polymer film) I.

Preferred dyes used for this dyeing include various acid dyes, direct dyes, and reactive dyes.

The dyes particularly preferably used in the present invention include:
Non-alkali metal dyes, general formula (I) as described in the specification of Japanese Patent Application No. 57-139856: D CC80sX) (I) (where D is an azo dye, a bisazo dye, a phthalocyanine dye, etc. (X is a cation consisting of a plurality of nonmetallic atoms, and m is an integer from 1 to 6) and is substantially free of alkali metals.

Similarly preferred non-alkali metal dyes include the same (Japanese Patent Application No. 57-154503 and Patent Application No. 57-1
The above general formula (I
), examples include those in which X is a hydrogen atom, and those in which X is a mixed system of a cation consisting of a plurality of nonmetallic atoms and a hydrogen atom.

In addition, the dyeing solution used for dyeing the polymer film in the present invention can also contain a buffering agent provided with a buffer system suitable for the dye used.

Various buffer systems are used depending on the purpose. Various compositions are known as buffering agents, but most of them consist of a combination of a compound containing an alkali metal such as sodium and an acid, or a combination of multiple compounds containing an alkali metal. It is.

Further, in the present invention, it is preferable to use a non-alkali metal buffer instead of these alkali metal-containing buffers. Such non-alkali metal buffers can be obtained, for example, by replacing the alkali metal moiety of the compound forming the alkali metal-containing buffer with ammonia or various organic amines.

That is, for example, a buffer composition (PJ (=3.6 to 5.6) consisting of acetic acid and sodium acetate is changed to a buffer composition consisting of acetic acid and ammonium acetate, so that the buffering capacity is not significantly changed. It can be used as a non-alkali metal buffer without causing any damage.

Similarly, a buffer composition (pH = 3.94 to 11.37) consisting of sodium carbonate and sodium hydrogen carbonate can be made into a buffer composition consisting of ammonium carbonate and ammonium hydrogen carbonate, and A buffer composition (pi(=
2.2 to 8.0) can be made into a buffer composition consisting of citric acid and ammoium hydrogen phosphate, so that each can be made into a non-alkali metal buffer without significantly changing the buffering capacity. .

Incidentally, the above-mentioned buffering agent can be easily selected in consideration of a region suitable for the dye to be used.

After the above staining operation is completed, a washing operation is performed using a rinsing solution, and examples of buffers used for this purpose include those mentioned above.

By incorporating a buffering agent into the staining solution and rinsing solution as described above, the spectral transmission characteristics of the colored polymer film can be improved, and the durability of the dyeing solution and rinsing solution in use (one stability in repeated use) can be improved. is significantly improved.

Next, a color pollution prevention layer (intermediate layer) is formed on the color separation filter element formed in this way, and a colored polymer film is further formed thereon in the same manner, and another pattern for brightness is formed on the surface of the colored polymer film. The polymer layer is irradiated with light that has passed through the polymer layer to form additional dot-like, mosaic-like, or stripe-like crosslinked portions. Then, in the same manner, the uncrosslinked resin portion is removed, and the layer of the uncrosslinked resin is dyed with another dye to form a color separation filter element (colored resin film) (2). In addition, if necessary. After repeating the operations for forming color separation filter elements to form a desired color separation filter group, the formation of the micro color filter is completed by finally forming a surface coating layer (protective layer).

Surprisingly, the photosensitive composition containing the polymer of the present invention and a photocrosslinking agent can be produced using just the polymer without any other A-ing or photocrosslinking group (e.g., OH group of PVA, gelatin, etc.). A good relief is formed by Idemitsu crosslinking that forms a film. Therefore, it is not necessary to use the polymer of the present invention in combination with other photocrosslinkable resins, but they may be used in combination to control dyeing density or adhesion (depending on the type of polymer). During or before or after each of the above-mentioned operations, operations such as exposing the binding A/P portion necessary for circuit formation may be included, but these operations are not directly related to the present invention. Therefore, the explanation will be omitted.

Further, by subjecting each colored polymer film to a surface modification treatment for preventing color staining, the provision of the color stain preventing layer (intermediate layer) described above can be omitted.

This color stain prevention treatment method involves treating the surface of the colored polymer film obtained by dyeing with an aqueous solution of tannic acid and acetic acid and an aqueous solution of antimonyl tartrate alkali metal salt.
A method for preventing color staining of the colored polymer film can be mentioned. Note that by changing the alkali metal salt of antimonyl tartrate to ammonium antimonyl tartrate, it is possible to more effectively prevent alkali metal contamination of the solid-state imaging device. A non-alkali metal buffer may be added to this color stain prevention treatment solution. Also,
Prior to such color stain prevention treatment, it is also preferable to perform a hardening treatment using a hardening agent aqueous solution and/or a heat treatment. The colored polymer film that has been subjected to color stain prevention treatment may be washed using a non-alkali metal buffer-containing rinsing solution in the same manner as in all cases after the dyeing treatment described above.

In the present invention, since the colored polymer film can easily maintain a desired μ value, its spectral transmission characteristics are improved, and it is possible to stably maintain its excellent spectral transmission characteristics for a long period of time.

Furthermore, the polymer of the present invention and, if necessary, a polymer material with a highly reduced alkali metal ion content are used as the base material of the colored polymer film formed on the solid-state image sensor, and the dye is not used. When alkali metal dyes are used and aqueous solutions containing non-alkali metal buffers are used in the dyeing operation, the resulting color solid-state image sensor is particularly effectively protected from contamination by harmful alkali metal ions, This greatly contributes to improving the reliability of color solid-state image sensors, and therefore makes it possible to manufacture excellent color solid-state image sensors for practical use.In addition, it is possible to provide a protective layer on the formed color filter. I can do it. As the protective layer, an organic polymer that does not absorb light in a wavelength range that is transmitted by the color filter can be used. Among them, visible to ultraviolet, Deep U
So-called photoresists, which are sensitive to V 1 electron beams or the like, are advantageously used.

Next, examples of the present invention will be shown.

Example 1 Comparative Example 1 A photosensitive liquid having the following composition was applied onto a transparent glass substrate using a spinner coating material so that the film thickness after drying was + (0 microns) and dried for 15 minutes at room temperature to form a filter forming material. It was created.

A turn mask consisting of a mosaic pattern was placed on top of this filter forming layer and adhered in vacuum, and then exposed to light using a 500W high pressure mercury lamp for 40 seconds.
It was immersed in warm water at 3° C. for 10 minutes, and developed to dissolve and remove the non-crosslinked portion of the filter forming layer to create a mosaic photocrosslinked relief image.

Next, this photocrosslinked relief image was immersed in a cyan dyeing solution having the following composition at 43° C. for 8 minutes to perform dyeing.

Staining liquid composition Steel phthalocyanine (tetra) Pyridinium sulfonate (tetra) m 0.5I! i
I - Buffer solution of about 6 11 water 1! Next, this cyan-colored filter material containing 29.69 m of ammonium acetate and 0.96 m of acetic acid per bottle was washed by immersing it in a rinsing solution (1 part of water containing 1.5 d of acetic acid) for 30 seconds, and dried to obtain a cyan filter ( 1) (Comparative Example 1) was created.

Comparative Example 2 A cyan filter 2 (Comparative Example 2) was prepared in the same manner as in Comparative Example 1, except that a photosensitive liquid having the following composition was coated on a transparent glass substrate to a film thickness of 1 micron after drying. did.

Photosensitive layer composition However, the development conditions and staining conditions were changed as follows.

Development conditions: 25° C., 5 minutes Dyeing conditions: 25° C., 8 minutes Cyan filters 3 to 7 were prepared in the same manner as in Comparative Example 1, except that a photosensitive solution having the following composition was applied onto the glass substrate described above. However, the developing conditions were 23° C. for 2 minutes.

Composition of photosensitive liquid
The spectroscopic optical density at 630 nm was measured (MMSP microspectrophotometer manufactured by Olympus Co., Ltd.), and Table 1
I got the result.

Table 1 2 PVA O,21,00,203 Compound 1)
2.26 0.55 4.114' (2)
1.830.603.055 p (311,7
90,553,256p f4) 1.770.60
2.957 1(5) 1.680.60 L80 As is clear from these results, the staining index (D/μ staining concentration per unit film thickness) is lower in the method of the present invention than in the comparative one.
is found to be extremely high. As a result, it was found that the filter film thickness could be made thinner to 173 to 176 mm compared to filter (1).◇By making the film thinner, the resolution was significantly higher and the noturn reproducibility was excellent. It was found that the processing time could be further shortened.

Example 2 Cyan filters 8 and 9 were prepared in the same manner as cyan filters 3 to 7 in Example 1, except that a photosensitive liquid having the composition shown below was applied onto a transparent glass substrate.

Photosensitive liquid composition Cyan filter 8 Compound (1) 20% 5-Water
15m ammonium dichromate 10% 0.4m cyan filter 9 Compound (5) 20% 5 Go water
1011t1 Ammonium dichromate 10% 0.2IL1 The staining index was determined in the same manner as in Table 1 and shown in Table 2.

Table 2 9 Compound 15) 2.64 1.00
2.64 As is clear from these results, it can be seen that the polymers of the present invention exhibit sufficient photosensitivity and a high dyeing index even when used alone.

Example 3 A photosensitive solution having the following composition was coated onto a transparent glass plate to a thickness of 0.5 μm.

Photosensitive liquid composition Polyvinyl alcohol 1011Ll Compound (1), 20% aqueous solution Ammonium 5-dichromate 10% 0.81R1 Water
After exposing this filter forming layer of 10 m to ultraviolet light through a mask having a striped nosetan of the filter color element of the first color,
A relief image was created by developing with cold water at .degree. C. for 30 seconds.

Next, a staining treatment was performed at 40° C. for 2 minutes using a staining solution having the following composition.

Staining solution composition Water 1j Suminol Milling Brilliant Sky Blue Sg 0.5.9 Add acetic acid pH 3.0 After dyeing, immerse in rinsing solution for 30 seconds and wash, then perform two treatments: tannic acid treatment and tartar treatment. Resistance treatment was carried out.

Resist dye treatment first treatment: After immersing in an aqueous solution of 2I tannic acid and 10 cc of acetic acid dissolved in water 11 at 25° C. for 2 minutes, it was washed with water for 1 minute.

Second treatment: Next, 5 g of tartarite and 2.5 cc of acetic acid in water 11
The filter element was immersed in an aqueous solution at 25° C. for 2 minutes, washed with water for 1 minute, and dried to prepare a first color filter element.

Next, after baking at 170°C for 20 minutes, apply a photosensitive solution with the same composition as the first color using the same procedure as above.

A second color filter color element was created (dry film thickness 1.0
(applied to μ). However, the staining process was carried out at 25° C. for 4 minutes using the following staining solution.

Staining solution composition Water 11 Chiton Green C-I 9 0.3.9 Direct First Yellow BCO, 5, F Add acetic acid
PH3,4 Furthermore, a third color filter element was created using the same procedure as above (applied to a dry film thickness of 0.7μ).
. However, for the dyeing process, use the following staining solution at 25℃ for 6 hours.
I went for a minute.

Staining Solution Composition Water 1. Add acetic acid to pH 3.0. On top of this, add 1 micron thick PY ethyl ethylene diacrylate and equimolar amount of 1.4-bis(β-hydroxyethoxy)- Copolymer with cyclohexanone (2 as a sensitizer)
- benzoylmethylene-1-methyl-β-naphthotizoline (containing 2% by weight) was formed, followed by pre-baking at 150°C for 10 minutes, and then the Zending No. Ultraviolet lsM light was applied using a mask (exposure no-turn) that covered the top part and the dicing cut part and exposed the pixel area. Next, it was developed with γ-butyrolactone, and the unexposed parts of the resin (TI?ndingmet part and dicing cut part) were
was eluted and lost. Next, a post bake was performed at 170'C for 40 minutes to produce a polychromatic optical filter consisting of blue, red, and green.

Example 4 A CCD image sensor whose surface was smoothed using a photosensitive resin having the same composition as the oat ζ-coat of Example 3 was prepared. A color filter layer was formed on the smooth surface of this CCD image pickup device in the same manner as in the three examples. Next, this CCD image sensor was cut and separated into each color solid-state image sensor using a diamond P cutter while being showered with water. The cut and separated color solid-state imaging device was ultrasonically cleaned using a solvent such as water, trichlene, or freon to remove chips and oily substances adhering to the surface. The color imaging device thus obtained is then transferred to the wire winding process, but when it was observed under magnification under a microscope before the wire winding, it was found that the O2-coat layer and the colored resin film had no film on them. No changes to the filter, such as peeling, elution, decolorization, color mixing, or opacity, were observed. Next, this was left in an oven at 200° C. for 3 hours, a thermotest was performed, and then observed under a microscope, but no change was observed here either. Therefore, it was found that the color filter layer according to the present invention also has excellent heat resistance. This is wired and packaged,
It was installed in a CCD color camera, and as a result of photography, a color image with good color reproducibility was reproduced on a cathode ray tube.

Claims (1)

[Scope of Claims] A color filter comprising a colored pattern formed on an image forming layer coated on a substrate and containing a polymer having a unit represented by the following general formula. General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ In the formula, A represents a monomer unit derived from a copolymerizable ethylenic monomer. R^1 represents a hydrogen atom or an alkyl group. R^2 represents an alkyl group or an aralkyl group. X^■ represents an anion, x is 0 to 8
0 mol%, y is 20 to 100 mol%, and z is 0 to 80 mol%. Each monomer unit may each contain two or more types of monomers.