JPH0237581B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of manufacturing a color filter in which a plurality of color separation filters are formed in an arbitrary pattern on a substrate. Conventionally, the manufacturing methods for color filters used in color television cameras include inorganic filters in which a colored substance is deposited on a glass substrate by vapor deposition and patterned, and a resin layer is provided on a glass substrate and the resin layer is Either repeating the process of selectively dyeing and decolorizing the glass to form different colored resin layers, or providing a resin layer in a relief pattern on a glass substrate and dyeing the resin layer with a dye or the like to form a colored resin layer. Some organic filters are made by repeating the forming process 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. Ru. In addition, photosensitive materials made of water-soluble polymers are used as materials for the resin layer due to occupational health issues and material costs. Water-soluble natural polymers such as blue, egg white, polyvinyl alcohol,
Water-soluble synthetic polymers such as polyvinylpyrrolidone and polyacrylamide are 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 on the water-soluble polymer side, for example, direct dyes and acid dyes that have sulfonic acid groups in their molecules. For basic dyes having an amino group in the molecule, carboxyl groups are involved, but when focusing on the number of these amino groups and carboxyl groups present in a water-soluble polymer, While natural polymers each have approximately 1.0meq/g,
Since water-soluble synthetic polymers possess approximately 0.1 meq/g, it can be seen that synthetic products can only be expected to have a staining density due to ionic bonds that is about 1/10 that of natural products. For this reason, photosensitive materials made of water-soluble natural polymers are desired, but natural polymers have large variations from lot to lot due to problems in their manufacturing process, and as a result, photosensitive materials made of these materials have poor sensitivity and resolution. It is very difficult to maintain stability in terms of photosensitive properties such as image quality. In addition, gelatin, casein, etc. have a high average molecular weight, so their gelation temperature (setting point) is high and their solubility in water is low, so they must be handled under heated conditions, causing problems in workability. It's coming. However, even if the above requirements are satisfied, the pattern sharpness, resolution, and
Alternatively, it has been extremely difficult to obtain fine patterns with appropriate photosensitivity due to the reduction of photosensitivity properties such as photosensitivity. The present invention improves the drawbacks of water-soluble photosensitive materials and improves the uniformity of coating film thickness even under working conditions at room temperature.
It uses a water-soluble photosensitive material that has high resolution and has excellent stainability with water-soluble dyes even in thin films, and is combined with an interlayer film that is transparent and has good stain resistance as necessary. Alternatively, the present invention relates to a method for manufacturing a color filter using a relief dyeing method in which a dyeing-resistant treatment such as hardening the dyed resin layer is added. To explain the present invention in more detail, the water-soluble photosensitive material used is a natural protein having a peptide bond in its molecular chain, which was previously proposed by the present inventors in Japanese Patent Application No. 162141/1986. , alkali, enzymes, etc., and the number average molecular weight n is 2000 to 30000 and 40℃,
Intrinsic viscosity [η] (hereinafter simply referred to as intrinsic viscosity) in 0.15 mole citrate buffer is 0.060 to 0.155 dl/g.
We are further developing a photosensitive material whose resin component is a water-soluble peptide made from a hydrolyzate of mammalian collagen that can maintain the ability for molecular chains to unwind firmly in the region set between This was obtained as a result of research. Uniform film thickness, high resolution, high contrast,
It is a water-soluble peptide resin photosensitive material that has characteristics such as high dyeability and is designed to stably obtain a highly accurate relief pattern on a substrate without any problems in a working environment at room temperature through pattern exposure. Bovine bone collagen, which has peptide bonds in its molecular chains, is hydrolyzed with acid, alkali, enzymes, etc., and its weight average molecular weight w is 10,000 to 50,000.
More preferably, the index D _ZW (D _ZW = _Z / _W , where _Z : Z average molecular weight, _W : weight average molecular weight), which indicates the breadth of the molecular weight distribution on the high molecular weight side of the molecular weight distribution curve, is 2 or less. This is a water-soluble bovine bone peptide resin photosensitive material made of bovine bone peptide resin. The bovine bone peptide resin used here is obtained by hydrolyzing the peptide bonds of collagen obtained from bovine bones.The hydrolysis conditions are a temperature of 80℃, a time of 3 hours, and a concentration of bovine bone collagen of 20% under normal pressure. %, various bovine bone peptide resins can be obtained by setting the concentration of hydrochloric acid added as follows (Table 1). According to Table 1, the concentration of hydrochloric acid added is 0.80 to 1.50× per gram of bovine bone collagen.
You can see that the range of 10 ^-3 moles can be set.

[Table] Table 2 also shows the physical property values of the above bovine bone peptide resin sample.

[Measurement items 1 to 3]

Weight average molecular weight w, Z average molecular weight _Z , and
D _ZW , phosphate buffer (0.1M Na ₂ HPO ₄ +0.1M
The sample concentration of each bovine bone peptide resin was adjusted to 10 mg/ml (mg peptide resin/ml buffer) using KH ₂ PO ₄ , PH 6.8), and after passing through a 0.22μ filter, the molecular weight distribution was measured under the following conditions. . Measuring equipment High performance liquid chromatography HLC-802UR manufactured by Toyo Soda Kogyo Co., Ltd. Inspection method Differential refractometer IR-8 64×10 ^-8 RIUFS Column Precolumn GSWP+G4000SW+
G3000SW Flow rate 1.00ml/min Chart speed 5.0mm/min Sample injection volume 100μl Measurement temperature 40℃ Also, the calibration curve for determining the relationship between retention time and molecular weight was prepared using polyethylene glycol as the standard substance under the same conditions as above. It was determined by the method. The molecular weight distribution curve obtained in this way is
As shown in the figure. _W , _Z , and _DZW are determined by analyzing the molecular weight distribution curve shown in FIG. 1 using the following method. _W = ΣHiMi / ΣHi _Z = ΣHiMi ₂ /ΣHiMi D _ZW = M _Z /M _W where Mi: Molecular weight Hi: Height of the molecular weight distribution curve at molecular weight Mi [Measurement item 4] Number average molecular weight n By Van Slyke method I did it. [Measurement item 5] Intrinsic viscosity [η] 0.15mole citric acid buffer (sodium citrate +
Various bovine bone peptide resin sample solutions (40°C) were prepared using citric acid (pH 3.7), and the intrinsic viscosity [η] was obtained from the following relationship. [η]=1im c→oη−ηo/ηo/c where η: Viscosity of bovine bone peptide resin solution ηo: Viscosity of citric acid buffer C: Concentration of bovine bone peptide resin solution g/dl [Measurement item 6] Gelation temperature (Setting point) The gelation temperature (setting point) of various 10 weight percent solutions of bovine bone peptide resin was measured. [Measurement item 7] Photosensitive liquid viscosity As the composition of various bovine bone peptide resin liquids, the viscosity change over time at 23°C of a photosensitive liquid consisting of peptide resin / 1 mole ammonium dichromate aqueous solution / pure water: 50 g / 40 ml / 250 ml. The viscosity values are shown when the photosensitive liquid was prepared and after being left in a 23°C environment for 3 days. Measuring device B-type viscometer [Measurement item 8] Optical rotation [α] _D citric acid buffer (sodium citrate + citric acid PH
6.8) Various bovine bone peptide resin solutions adjusted to a concentration of about 1% by weight were rapidly changed from a 40°C atmosphere to a 2°C atmosphere, and the value was read after 180 minutes to measure the optical rotation [α] _D. Measuring device Rudolph type polarimeter [α] _D = (1000/C・X/l) °C: Bovine bone peptide solution concentration (wt%) l: 20cm (optical path) X: rotation angle (degree) D used Line λ=589nm [α] The value of _D means that as the absolute value increases, the ability to form collagen hold increases. [Measurement Item 9] Specific Sensitivity This is an index of the amount of light indicating the photocrosslinking property of the bovine bone peptide photosensitive solution shown in Measurement Item 7, and the smaller the value, the higher the photosensitivity. Photosensitizers that cause a photocrosslinking reaction with bovine bone peptide resin when irradiated with active light include dichromates, such as ammonium dichromate, sodium dichromate, potassium dichromate, etc., and diazonium salts, such as P- Diazophenylamine, 1-diazo-4-dimethylaminobenzene
Photosensitive agents include, but are not limited to, hydrofluoroborate, 1-diazo-3-methyl-4-dimethylaniline sulfate, 1-diazo-3-monoethylnaphthylamine, etc., and their paraformaldehyde condensates. -COOH, -NH ₂ , -OH, - in the peptide resin by actinic light.
Any material that can form a coordinate bond with a group having a lone pair of electrons such as CONH ₂ or >CO 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. It exhibits complex behavior with the addition of additional elements. In other words, when discussing the photosensitive properties 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. That is,
As can be seen from Table 2, peptide resins with strong collagen hold-forming ability have many apparent cross-links resulting from the collagen hold structure in addition to molecular cross-links with the photosensitizer. It becomes possible to obtain high photosensitivity. In addition, because the crosslinking density per unit volume can be increased, and the collagen hold structure has strong intermolecular bonds from unwinding, it has excellent resolution and clear image lines, and has a strong relief as a membrane. 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 differ due to changes over time from the time of photosensitive liquid preparation, and as a result, the resolution of the relief pattern This means that subtle changes also occur. Therefore, in order to study bovine bone peptide resin in more detail, we measured and analyzed their molecular weight distribution.As can be seen from Table 2, the peak position of the molecular weight distribution curve corresponds to 10000 to 50000 in weight average molecular weight w which means characteristics
_and preferably represents the degree of dispersion on the high molecular weight side of the molecular weight _distribution curve.
It has been found that a photosensitive material made of a bovine bone peptide resin having a small molecular weight distribution of 2 or less has very small changes in viscosity over time (see measurement item 7) and has excellent properties. 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, but bovine bone peptide resin Since it is obtained by hydrolyzing the peptide bonds of bovine bone collagen, the number of amino groups and carboxyl groups at the end of the molecular chain is increased, making dyeing easier. This shows that the bovine bone peptide resin is superior in dyeing properties compared to general natural proteins, and also means that it is excellent in dyeing properties in a thin film pattern. From the above, a water-soluble photosensitive material composed of a bovine bone peptide resin whose weight average molecular weight w is set to 10,000 to 50,000 and whose D _ZW is preferably 2 or less can be used to achieve uniform film thickness, high resolution, high contrast, and high It was found that a relief pattern having characteristics such as dyeability could be stably obtained without any problems in a working environment at room temperature. The water-soluble photosensitive material of the present invention is an aqueous solution in which a photosensitizer is added to bovine bone peptide resin in a weight ratio of 5 to 50%, preferably 10 to 30%. A thin film (0.3 to 2.0 μm thick) is formed on the light-receiving surface of the image sensor using a spin coater, roller coater, etc., and active light is applied via the original mask using a mercury lamp, ultra-high pressure mercury lamp, metal haptic lamp, etc. as a light source. The relief pattern obtained on the substrate by exposure and then water development is used as a resin layer to be dyed with a dye. In addition, in the dyeing process, the relief dyed layer is dyed with a dye having predetermined spectral characteristics, and the dyes used include acidic, direct, and basic water-soluble dyes. Nord Milling Yellow o, Kayanol Cyanine G, Kayanor Milling Red RS, Kayaku Acid Orange (hereinafter manufactured by Nippon Kayaku Co., Ltd.), Mitsui Nylon First Yellow 5G, Mitsui Brilliant Milling Green B, Mitsui Acid Milling Sky Blue FSE (manufactured by Mitsui Toatsu Chemical Co., Ltd.), Suminol Milling Brilliant Green 5G, Acid Brilliant Milling Green B, Suminol Milling Red PG (manufactured by Mitsui Toatsu Chemical Co., Ltd.)
(manufactured by Sumitomo Chemical Co., Ltd.), Diacid Fastrubinol 3G200%, Diacid First Orange
Examples include NP200 (manufactured by Mitsubishi Chemical Industries, Ltd.) and Guinea Green (manufactured by Tokyo Kasei Corporation). In addition, the dyeing conditions include temperature,
The time etc. are determined. 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 that dyed the relief pattern obtained from the bovine bone peptide resin photosensitive material from migrating to other parts, and protects the colored resin layer, so it does not stain with the dye. 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. Examples of resins that can be used for this purpose include polyester resins, acrylic resins, and epoxy resins.
Ketones such as methyl ethyl ketone, ethyl acetate,
A resin liquid obtained by diluting with one or more mixed solvents arbitrarily selected from esters such as butyl acetate, toluene, xylene, etc. is applied to a film thickness of 500 Å to 0.2 μ by spin coating. After that, it is used by heating and polymerizing it. Of course, the transparent resin is not limited to the above resins as long as it satisfies the above objectives. Further, in the stain resistance treatment step, various properties such as stain resistance and water resistance can be imparted to the colored resin layer by chemically hardening the colored resin layer. This is hardened 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, and it is considered to be effective in preventing dye migration. Treatment agents (fixing agents) that can be used for this purpose include Nylon Fixtures TH (Nippon Someka Co., Ltd.) as a polyvalent phenol derivative, and Nylon Fixes GL (Nippon Someka Co., Ltd.) as a polyvalent phenolsulfonic acid derivative. ), Kayafix NA (Nippon Kayaku Co., Ltd.), etc., but are not limited to these. These fixing agents have a concentration of 0.5 to 1.0% by weight, a pH of 3 to 4, and a temperature of about 50.
The dyed relief pattern is immersed in the aqueous solution for about 5 minutes to obtain a hardening effect. A color filter is manufactured through the steps described above. For example, as shown in FIG. After forming the dye-resistant coating 8 as a film, a first coating is applied thereon.
A relief pattern for the second color is obtained by coating the photosensitive material of bovine bone peptide resin in the same way as for the color, drying, mask exposure, and development. Next, the relief pattern is dyed green to obtain a colored resin layer 9 of a second color. After providing the dye-resistant coating 10, 3
A colored resin layer 11 dyed blue is obtained by the same method for coloring. Finally, colored resin layer 11
An overcoat layer 12 is applied thereon to serve as a protective film. The material of the overcoat layer 12 may be the same as the material of the dye-resistant coatings 8 and 10 described above. Although three colors are shown in the embodiment of FIG. 2, 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 having no color mixture, good spectral characteristics, high resolution due to its thin film thickness, and excellent image sharpening properties. . Next, the present invention will be explained by examples. <Example> Bovine bone collagen was hydrolyzed under conditions of collagen concentration of 20% by weight and hydrochloric acid concentration of 1 g of collagen.
By adding 1.14×10 ⁻³ mole per resin and treating at a temperature of 80° C. and normal pressure for 3 hours, a peptide resin having a weight average molecular weight w of 26838 and a D _ZW of 1.94 was obtained. This peptide resin photosensitive material (aqueous solution) consisting of 20% by weight of peptide resin and 4% by weight of ammonium dichromate was coated on a glass substrate to a thickness of 1.0 μm at 1000 rpm, and after drying, the mask aligner PLA- 500F (Canon Inc.)
A striped relief pattern with a thickness of 0.8 .mu.m was obtained as a resin layer by alignment exposure for 20 seconds with a 15-25.degree. C. cold water spray and development for 40 seconds. This was colored with a first color of red using a red dye and dye conditions as shown below to form a dyed resin layer. Next, as an interlayer film, 10 g of Desmophen 651 (Sumitomo Bayer Urethane Co., Ltd.), a branched polyester containing hydroxyl groups, and an aliphatic polyisocyanate were used.
A mixture of 5 g of Sumidur N75 (manufactured by the same company) and 100 c.c. of a ketone or ester solvent such as methyl ketone was applied at 4000 rpm using a rotary coating machine and dried.The film thickness was
It was 0.1μ. This was heat treated at 160℃ for 4 hours,
Heat cured. After cooling, apply the same peptide resin photosensitive material used for the first color on top of it in the same thickness.
Coat 0.8μ, dry, expose and develop in the same way,
A relief pattern with a thickness of 0.65μ was obtained as a resin layer. This was immersed in a green dyeing solution to obtain a second colored green dyed resin layer. On top of this dyed resin layer for the second color, a polyester resin equivalent to the above-mentioned intermediate film is applied, and the same process is repeated to obtain a third color blue resin layer as a relief pattern with a thickness of 0.8μ, which is then dyed blue. It was colored blue with a liquid, and a polyester resin was applied in the same manner to form a protective film. By the way, as a result of examining the minimum drawing dimension as resolution, a pattern of 3μ was obtained for each color. The composition and dyeing conditions (temperature and immersion time) of red, green, and blue dye solutions are shown below as an example of the dye solution, and these are suitable for a dyed resin layer formed from a peptide resin photosensitive material. Red Kayanol Milling Red RS (Nippon Kayaku Co., Ltd.)
) 10g acetic acid 10c.c. water 1000c.c. 60℃ for 3 minutes Green Suminol Milling Brilliant Brine 5G
(Manufactured by Sumitomo Chemical Co., Ltd.) 3g Acetic acid 10c.c. Water 1000c.c. 60℃ 2 minutes 30 seconds Blue Kayanolcyanine G (Manufactured by Nippon Kayaku Co., Ltd.) 6g Acetic acid 5c.c. Water 1000c.c. 50℃ for 2 minutes

[Brief explanation of drawings]

FIG. 1 is a graph showing the molecular weight of the bovine bone collagen hydrolyzate used in the present invention on the horizontal axis and the amount as height on the vertical axis. FIG. 1 is a schematic cross-sectional view showing an example of a color filter. 1, 2, 3, 4, 5...sample number, 6...
Glass substrate, 7... colored resin layer of first color, 8,
DESCRIPTION OF SYMBOLS 10... Dye-resistant coating, 9... Colored resin layer of second color, 11... Colored resin layer of third color, 12... Overcoat layer.

Claims (1)

[Claims] 1. The peptide bonds in the main chain of bovine bone collagen, which has peptide bonds in its molecular chains, are hydrolyzed under the conditions of adding 0.80 to 1.50×10 ^-3 mole of hydrochloric acid per 1 g of bovine bone collagen. The weight average molecular weight Mw is
10,000 to 50,000, the light intensity [α] _D shows a range of −185° to −290°, and the dispersity of the high molecular weight region in the molecular weight distribution D _ZW (= _Z / _W : where _Z
The substrate is a photosensitive film of a water-soluble photosensitive material consisting of a bovine bone peptide resin whose value (Z average molecular weight) is set to 2 or less, and a photosensitizer that causes a photocrosslinking reaction with the bovine bone peptide resin by irradiation with active light. forming a relief pattern resin layer in a desired shape by exposing and developing the photoresist film in a pattern;
The steps of dyeing the relief pattern resin layer with a dye to obtain a colored resin layer having predetermined spectral characteristics, and performing a dye-resistant treatment on the colored resin layer to prevent it from being repeatedly dyed with a dye. A method for manufacturing a color filter, which comprises forming a color separation filter layer in an arbitrary pattern on a substrate by repeating the process by the number of colors required for the color filter. 2 Claim 1 in which the substrate is a glass substrate
2. Method for manufacturing a color filter as described in Section 1. 3. The method of manufacturing a color filter according to claim 1, wherein the substrate is a light-receiving surface of a solid-state image sensor. 4. The method for manufacturing a color filter according to claim 1, wherein the dye-resistant treatment step is a step of coating a transparent resin film layer on the colored resin layer. 5. Claim 4, in which the transparent resin film is made of polyester resin, acrylic resin, or epoxy resin.
2. Method for manufacturing a color filter as described in Section 1. 6. The method for manufacturing a color filter according to claim 1, wherein the stain-resistant treatment step is a step of chemically hardening the colored resin layer. 7. The method for producing a color filter according to claim 6, wherein the processing agent for hardening is a polyvalent phenol derivative or a polyvalent phenolsulfonic acid derivative.