JPS58116506A - Preparation of color filter - Google Patents

Abstract

PURPOSE:To obtain a color filter superior in dying density, uniformity of film thickness, resolution, etc., by using a water-soluble photosensitive a specified cattle bone peptide resin obtained from a cattle bone collagen, and a photosensitive agent causing photocross-linking on irradiation of active rays. CONSTITUTION:A cattle bone collagen is hydrolyzed in specified conditions to give a peptide resin having 10,000-50,000wt. average mol.wt. (Mw) and <=2 mol.wt. dispersion degree (Dzw=Mz/Mw, Mz being Z average mol.wt.). A photosensitive layer contg. said resin and a water-soluble photosensitive agent, such as bichromate or diazonium salt, capable of coordinating COOH, NH2, OH, and CO groups of the peptide resin is formed on a glass base 6. It is patternwise exposed, developed, and dyed with a first color dye to obtain a relief pattern 7 of the first color. Then, a dyeing-resistant film 8 of transparent polyester is formed on the pattern 7, and a photosensitive layer is again formed in contact with the film 8 likewise to form a pattern 9 dyed to a second color and a dyeing-resistant film 10, and further likewise a pattern dyed to a third color, and finally, an overcoat layer 12 is formed, thus permitting dyeability, etc. to be enhanced as compared with the conventional filter.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a color filter by forming a color separation filter.

Traditionally, the manufacturing methods for color filters used in color television cameras include inorganic filters in which a coloring substance Z is deposited on a glass substrate using a vapor deposition method and patterned; The process of selectively dyeing and decolorizing layers is repeated to form different colored resin layers, or a resin layer in a relief pattern is provided on a glass substrate, and the resin layer is dyed with a dye or the like to form a colored resin. There are organic filters that are made by repeating the process of forming one color multiple times as many times as the number of colors required by the filter (this method is sometimes referred to as the relief dyeing method). Generally, in the production of organic filters, water-soluble dyes such as acidic, direct, and basic dyes are used to dye the resin layer, depending on the spectral wavelength characteristics such as color purity and concentration of the colored resin layer. be done. In addition, the material for the resin layer should be water-soluble polymers due to occupational health issues and material costs. Traditionally, these water-soluble polymers include water-soluble natural polymers such as gelatin, casein, Finsch blue, and egg white, as well as water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide. It has been known.

However, when considering the dyeing power of a coloring layer for water-soluble dyes, the dyeing layer for water-soluble dyes, that is, the adsorption seat of a water-bathable polymer object, for example, for direct and acid dyes having sulfonic acid groups in the molecule. is an amine group,
In addition, carboxyl groups are involved in basic dyes that have amino groups in the molecule, but when we look at the number of these amino groups and carboxyl groups that exist in water bathable polymers, we find that each natural polymer has a While the water-soluble synthetic polymer has 0. It can be seen that the synthetic product has a staining density of about 1710 meq/P due to ionic bonds of about 1710 compared to the natural product. For this reason, photosensitive materials made of water-soluble natural polymers are desired, but natural polymers have large variations from loft to loft due to problems in their manufacturing process, and as a result, photosensitive materials made of these materials have low sensitivity and It is extremely difficult to maintain stability in terms of photosensitive characteristics such as image quality. In addition, gelatin, casein, etc. have a high average molecular weight and therefore have a high gelling temperature (setting point) and low solubility in water. However, even if the above are satisfied, the sharpness, resolution, or photosensitivity of the pattern may be affected as a result of increasing the thickness of the colored resin layer in order to obtain the spectral wavelength characteristics as a color filter. It has been extremely difficult to obtain fine patterns with appropriate photosensitivity due to the deterioration of the photosensitivity.

The present invention provides a water-soluble photosensitive material that improves the drawbacks of such water-soluble photosensitive materials, has uniform coating thickness and high resolution even in a working environment at room temperature, and has excellent dyeing properties against water-soluble dyes even in thin films. A color relief dyeing method that uses photosensitive materials, and if necessary, is combined with a transparent interlayer film with good stain resistance, or is treated with stain resistance treatment such as hardening the dyed resin layer. The present invention relates to a method for manufacturing a filter.

To explain the present invention in more detail, the water-soluble photosensitive material to be used is disclosed in Japanese Patent Application No. 55-162, which was previously proposed by the present inventors.
141, the peptide bonds are hydrolyzed with acids, alkalis, enzymes, etc., and the number average molecular weight n is 2000 to 2000.
30000 and 40C, 0. Intrinsic viscosity [η] in 15 mole citrate buffer (hereinafter simply referred to as intrinsic viscosity)) 10.060 to 0.155 d1/f! A water-soluble peptide resin made from a hydrolyzate of mammalian collagen that can maintain the ability to firmly unwind molecular chains (hereinafter referred to as collagen hold-forming ability) in the region set between - This material was obtained as a result of intensive research into photosensitive materials.It has characteristics such as uniform film thickness, high resolution, high contrast, and high dyeability, and can be printed with high precision on the substrate by pattern exposure. This is a water-soluble peptide resin photosensitive material designed to stably obtain a relief pattern in a working environment at room temperature without any problems.
Hydrolyzed by alkali, enzymes, etc., and its weight average molecular weight Mw is 1ooo.

~500001'2m, more preferably an index Dzw (Dzw = Mz / l) indicating the breadth of the molecular weight distribution on the high molecular weight side in the molecular weight distribution curve.
It is a water-soluble bovine bone pegtide resin photosensitive material made of a bovine bone bebutide resin having a weight average molecular weight (Mz: Z average molecular weight, W: weight average molecular weight) of 2 or less.

The bovine bone peptide resin used here is obtained by hydrolyzing the peptide bonds of collagen obtained from bovine bones, and the hydrolysis conditions are a temperature of 80C for 1 hour and 3 hrs under normal pressure and a bovine bone collagen concentration of 20%. However, various bovine bone peptide resins can be obtained by setting the concentration of hydrochloric acid added as follows (Table 1).

Table 1 Table 2 also shows the physical property values of the bovine bone pebutide resin sample.

Table 2 Note that these measurements were performed using the following method.

[Measurement items 1 to 3] Weight average molecular weight 1;? w, Z average molecular weight Mz, and Dz
lol.

Phosphate buffer (0, IM Na, HPO4+ 0.
The sample concentration of each bovine bone peptide resin was adjusted to iomy/mβ (bebutide resin mP/buffer solution) using 1 M KH, PO, pH 6, 8, filtered through a 0.22μ filter, and filtered under the following conditions. The molecular weight distribution was measured.

Measuring equipment High performance liquid chromatography manufactured by Toyo Soda Kogyo ■ HLC-802UR Inspection method Differential refractometer IR-864X10-11RI
UFS column precolumn GSWP+G40
008W+G3000SW flow speed 1. O
Om8/m1n Chart speed 5.0H/min Sample injection amount 100μ! Measurement temperature: 40C A calibration curve for determining the relationship between retention time and molecular weight was determined using polyethylene glycol as a standard substance and using the same method as the above conditions.

The molecular weight distribution curve thus obtained is shown in Figure 1. By analyzing the molecular weight distribution curve shown in FIG. 1 by the following method, Mw, wealth 2 and DZW) are determined.

Nishi-'''' 卦州ΣH1 凱 = .

[Measurement item 5] Intrinsic viscosity [g] 0, 15 mole citrate buffer (citric acid +
Various bovine bone peptide resin sample solutions (4otl:')Y were prepared using citric acid) PHs and y, and the intrinsic viscosity [η] was obtained from the following relationship.

[η] = lim +7-η/ □ C C10η0 where η: Bovine bone peptide resin solution viscosity η0: Citrate buffer solution concentration C: Bovine bone peptide resin solution concentration P/de [Measurement item 6
] Gelation temperature (setting point) The gelation temperature (setting point) of various 10 weight percent solutions of bovine bone pegtide resins was measured.

[Measurement item 7] Viscosity of photosensitive liquid Various bovine bone pegtide resin Photosensitive liquid composition: Pegtide resin/1 mole 11% ammonium dichromate aqueous solution/pure water: 50,! i'/ 40 m13/
This is a change over time in the viscosity at 23C of a photosensitive solution consisting of 25Qm4, and the viscosity values are shown at the time of preparing the photosensitive solution and after being left in a 23C environment for 6 days.

Measuring device B-type viscometer [Measurement item 8] Optical rotation [α] 9 Citrate buffer (sodium citrate + citric acid pH 6,8
) Various bovine bone pegtide resin solutions adjusted to a concentration of about 1% by weight were rapidly changed from an i40.C atmosphere to a 2C atmosphere, and the value after 180 minutes was read to measure the optical rotation [α]D.

〔α〕ゎ−(counter-sunk・”).

pC: Bovine bone vegtide solution performance (wt%) 13: 2
0011 (optical path)

[Measurement item 9] Silent photometry is an index of the amount of light indicating the photocrosslinking property of the bovine bone pegtide photosensitive solution shown in measurement item 7, and a smaller value indicates a higher photosensitivity.

Photosensitizers that cause a photocrosslinking reaction with the bovine bone pegtide resin upon irradiation with actinic light include dichromates such as ammonium dichromate, sodium dichromate, potassium dichromate, etc., and diazonium salts such as P −
Diazophenylamine, 1-diazo-4-dimethylaminobenzene hydrofluoroborate, 1-diazo-3-
Examples include, but are not limited to, methyl-4-dimethylaniline sulfate, 1-diazo-3-monoethylnaphthylamine, etc., and their paraformaldehyde condensates. , -C'OOH,- in the pegtide resin by actinic light
Any material that can form a coordinate bond with a group having a lone pair of electrons such as Co (NH,, -0H1-CONH,, -0H1-CONH,, ) may be used.

Generally, the photocrosslinking properties of a photosensitive material depend on the average molecular weight of the polymeric substance in the photosensitive material. In other words, it is well known that the higher the average molecular weight, the higher the photosensitivity; however, natural proteins, especially polymers with a specific structure such as collagen, which has the ability to form collagen hold, have an even higher structural strength. With the addition of 9 elements, complex behavior 2 is exhibited.

In other words, when discussing the photosensitive characteristics of a photosensitive material made of a polymer obtained from collagen, it is necessary to pay attention not only to the average molecular weight of the polymer but also to its collagen hold-forming ability. In other words, as can be seen from Table 2, PEGTIDE resins with strong collagen hold-forming ability have many apparent crosslinks resulting from the collagen hold structure in addition to molecular crosslinks with the photosensitizer, so PEGTIDE resins with a smaller average molecular weight This makes it possible to obtain appropriate photosensitivity. In addition, because the crosslink density per unit volume can be increased, and the collagen hold structure has strong intermolecular bonds from unwinding, it has excellent resolution and sharpness of image lines, and has a strong relief as a film. Image formation is possible. However, as a result of stronger unwinding of the collagen hold structure, the viscosity of the photosensitive liquid tends to increase in a time-dependent manner. This means that even if the photosensitive liquid coating conditions are exactly the same in the photosensitive liquid coating process, the coating film thickness tends to vary due to changes over time from the time of photosensitive liquid preparation, and as a result, the resolution of the relief pattern will be different. This means that subtle changes occur in image quality as well. Therefore, in order to study bovine bone PEGTIDE resin in more detail, we measured and analyzed their molecular weight distribution, and as shown in Table 2, the peak position of the bone mass distribution curve corresponds to The weight average molecule, which means viscosity flow characteristics, is
~50000, and preferably represents the dispersity 2 on the high molecular weight side of the molecular weight distribution curve f DZW (=Mz
It has been found that a photosensitive material made of a bovine bone bebutide resin having a small molecular weight distribution with /Mw ) of 2 or less has excellent properties with very little change in viscosity over time (see measurement item 7). In addition, in terms of dyeability, as mentioned above, the presence of an amino group or carboxyl group as a bonding group in the polymer is required for direct, acidic, and basic hydrophilic dyes. Since 4 fat is obtained by hydrolyzing the peptide bonds of bovine bone collagen, the number of amine groups and carboxyl groups at the end of the molecular chain is increased, making dyeing easier. This shows that bovine bone peptide resin has superior dyeability compared to general natural protein, and at the same time, it also means that it has excellent stainability in thin film patterns. be. That's it QN weight average molecular weight Mw
is set to 10,000 to 5oooo, and preferably has a DZW of 2 or less, and is made of a water-soluble photosensitive material made of bovine bone peptide resin, and has characteristics such as uniform thickness, high resolution, high contrast, and high stainability. It was found that patterns could be stably obtained without any problems in a working environment at room temperature.

In the water-soluble photosensitive material of the present invention, the weight ratio of the photosensitizer to the bovine vegtide resin is 5 to 50%, preferably 10 to 3%.
The pebutide resin photosensitive material is coated in a thin film (0.3 to 2
．． The relief pattern obtained on the substrate is exposed to active light using a mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, etc. as a light source through an original mask, and then water development is performed. It is used as a resin layer for dyeing.

In addition, in the dyeing process, the relief dye layer is dyed with a dye having predetermined spectral characteristics;
The dyes used include acidic, direct, and basic water-soluble dyes, such as Kayanol Milling Yellow O, Kayanol Sairyonin G1, Kayanol Milling Red R8, Kayakuryoshito Orange (all Nippon Kayaku).
), Mitsui Nylon Fast Yellow 5G, Mitsui Brilliant Milling Green B, Mitsui Cytomy II y Gesky Blue PSE (manufactured by Mitsui Toatsu Kagaku 1+H), Suminol Milling Brilliant Green 5G, And Brilliant Milling Green B1 Suminol Milling Red PG (manufactured by Sumitomo Chemical), Diacitophers Rubinol 31”
)200%, Diacitfast Orange N)-'2
00 (manufactured by Mitsubishi Chemical Industries, Ltd.), Guinea Green (manufactured by Tokyo Chemical Industry Co., Ltd.), etc. As the dyeing conditions, the temperature, time, etc. are determined according to a predetermined spectral density.

Next, the transparent resin film coated on the colored resin layer in the stain resistance treatment step will be described. This resin film prevents the dye in the colored resin from transferring to other parts of the relief pattern obtained using the bovine bone peptide resin photosensitive material, and protects the colored resin layer. In addition to poor dyeing resistance, it is also required to have various resistances such as water resistance and heat resistance against repeated pattern forming steps. Naturally, it is also important that the material be optically transparent and have the ability to form a thin film. Resins that can be used for this purpose include polyester resin, acrylic resin, epoxy resin, etc.
Resins obtained by diluting these resins with one or more mixed solvents arbitrarily selected from ketones such as a7tone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, and other solvents such as toluene and xylene. It is used by coating the solution to a film thickness of 5008 to 02 μm by spin coating or the like and then heating and polymerizing it. Of course, any transparent resin that satisfies the above objectives is not limited to the above resins.

Further, in the stain resistance treatment step, the colored resin qK can be given additional properties such as stain resistance and water resistance by chemically hardening the colored resin layer. This hardens the film by ionically reacting with cationic groups such as amino groups and amide groups in the relief film. As a result, the wetting effect during dyeing is enhanced, which is considered to be effective in preventing dye migration. The processing agent (fixing agent) that can be used for this purpose is Nylon Fix TH (Nippon Someka ■) as a polyvalent phenol derivative.
, and polyhydric phenol sulfonic acid derivatives such as Nylon Fix GL (Nihon Senka)-, Kaya Fix N
Examples include, but are not limited to, A (Nippon Kayaku @l). These fixing agents have a concentration of 0.5 to 1.
A hardening effect is obtained by immersing the dyed relief pattern into an aqueous solution of 0% by weight, pE (3 to 4, and temperature of about 50 C) for about 5 minutes.

Color filters are manufactured through the steps described above. For example, as shown in Figure 2, a glass substrate (6
) After forming a dye-resistant film (81'?) with the first relief pattern as a red film, a bovine bone peptide resin photosensitive material was applied on top of it in the same way as the first color, dried, mask exposed, and the phenomenon Obtain a relief pattern for a second color.Then, by dyeing the relief pattern in green,
A colored resin layer (9) of a second color is obtained. After providing the dye-resistant coating 0I, an overcoat layer A21W is applied on the colored resin layer (marked) dyed blue by the same method for the third color (to obtain the mark.Finally, the colored resin layer old) is applied to form a protective film. do.

The material of the overcoat layer 021 may be the same as the material of the dye-resistant coating f81 Ql described above.

In the embodiment shown in FIG. 2, only three colors are shown, but the filter is not limited to this, and there is no limit to the number of colors of the filter.

The color filter manufactured by the manufacturing method of the present invention is characterized by no color mixture, good spectral characteristics, high resolution due to its thin film thickness, and excellent image sharpness. .

Next, the present invention will be explained by examples.

<Example> Bovine bone collagen was hydrolyzed under collagen concentration 2.
1 per Li-collagen with hydrochloric acid at a concentration of 0% by weight.
．． By adding 14 x 10-" mole and treating at a temperature of soc and normal pressure for 3 hours, a vegtide resin having a weight average molecular weight Mw of 26838 and a Dzw of 1.94 was obtained. 20% by weight of this butide resin and dichromium Peptide resin photosensitive material (aqueous solution) consisting of 4 parts by weight of ammonium acid was coated on a glass substrate to a thickness of 1.0 μm using a rotary coater at IQOOrpm, and after drying, mask aligner-P1., 'A- 500,F
(Light the alignment g for 20 seconds with Canon ■11,
By developing with cold water spray at 15 to 25 C for 40 seconds, a striped relief turn with a thickness of 08 μm was obtained as a resin layer.

This was colored with a first color of red using a red dye solution and dye conditions as shown below to form a dyed resin layer. Next, Desmo, which is a branched polyester containing hydroxyl groups, was used as an interlayer film.
phen 651 (Sumitomo) quinyl urethane ■) 1
0? and aliphatic polyinocyanate SumidurN75
(Company) 59-, a ketone, and an ester solvent such as methyl ethyl keto/100 CC were coated at 400 Orpm using a rotary coating machine and dried, resulting in a film thickness of 01 μm. This was heat-treated at 160 t for 4 hours to thermally cure it. After cooling, the same Vegtide resin photosensitive material used for the first color was coated thereon to a thickness of 0.8 μm, dried, exposed and developed in the same manner, and a resin layer with a thickness of 0.8 μm was formed.
A 1J-7 pattern of 65μ was obtained. This was immersed in a green dyeing solution to obtain a second colored green dyed resin layer.

On this dyed resin layer for the second color, a polynisder resin equivalent to the above-mentioned intermediate film is applied, and the same process is repeated to obtain a relief pattern with a thickness of 0.8μ for the resin layer 7 for blue as the third color. It was colored blue with a blue dyeing solution, and a polyester resin was applied in the same manner to form a protective film. By the way, as a result of investigating the minimum depiction size for resolution, it was 6 for each color.
μ's no(turn was obtained.

The composition and dyeing conditions (temperature and immersion time) of red, green, and blue dye solutions are shown below as an example of a dye solution, and these are suitable for products in which a dyed resin layer is formed using bebutide resin sensitizing material. .

Red Color 60C 6 minutes Green Color 60C 2 minutes 30 seconds Blue Color 5002 minutes Figure 1 shows the molecular weight of the bovine bone collagen hydrolyzate used in the present invention on the horizontal axis. Quantity on the vertical axis? FIG. 2 is a graph showing the height, and FIG. 2 is a schematic cross-sectional view showing an embodiment of a color filter obtained by the manufacturing method of the present invention.

fll +21 +31 +41 +51...Sample number (6)...Glass substrate (7)...First color colored resin layer (81QOl...Dye-resistant coating (
9)...Second color colored resin layer Old)...Third color colored resin layer 02...Overcoat layer Patent applicant Kazuo Suzuki Representative of Toppan Printing Co., Ltd.

Claims (8)

[Claims] (1) A bovine bone peptide resin whose weight average molecular weight ΩW was set to 100'00 to 50 [100] by hydrolyzing the main chain peptide bonds of bovine bone collagen that has vegtide bonds in the molecular chain, and activated light irradiation. A photosensitive film of a water-bathable photosensitive material is formed on a substrate, and the photosensitive film is pattern-exposed and developed (2) to form a desired shape. a step of forming a relief pattern resin layer, a step of dyeing the relief pattern resin layer with a dye to obtain a colored resin layer having predetermined spectral characteristics, and a step of superimposing and dyeing the colored resin layer with a dye. A color filter characterized in that a single layer of color separation filter in an arbitrary pattern is formed on a substrate by repeating each step of the dye-resistant treatment process that prevents color separation by the number of colors required for the color filter. Production method. (2) The value of the dispersion degree Dzw (-MZ / quotient W: where Ω2 is the Z average molecular weight) of the polymer dragon region in the molecular sensitivity distribution of the bovine bone peptide resin is set to 2 or less kc11
The method for producing a color filter according to claim 1, wherein the color filter is a bone peptide resin. (3) The method for manufacturing a color filter according to claim 1, wherein the substrate is a glass substrate. (4) The method for manufacturing a color filter according to claim 1, wherein the substrate is a light-receiving surface of a solid-state image sensor. (5) The method for producing a color filter according to claim 1, wherein the stain-resistant treatment step is a step of coating the colored resin layer with a transparent resin film layer. (6) The method for manufacturing a color filter according to claim 5, wherein the transparent resin film is made of polyester resin, acrylic resin, or epoxy resin. (7) The method for producing a color filter according to claim 1, wherein the stain-resistant treatment step is a step of chemically hardening the dyed resin layer. (8) The treatment agent for hardening is a polyhydric phenol derivative or 1
8. The method for producing a karama filter according to claim 7, wherein the kalam filter is a polyhydric phenol sulfonic acid derivative.