JPS5972410A - Manufacture of color light separating filter - Google Patents

Abstract

PURPOSE:To lower a gelation temperature and to obtain a good filter by using a casein - gelatin mixture as a film forming agent of a photosensitive material, in a method for manufacturing a color light separating filter by dyeing a patterned photosensitive material film. CONSTITUTION:A photosensitive liquid is prepared by mixing a photosensitive agent (for example, bichromate, water soluble bisazide compound) in a solution containing 100wt.pts. gelatin and about 10-90wt.pts. casein as a film forming agent. Subsequently, said photosensitive liquid is applied on a substrate (for instance, glass plate), a photosensitive film is prepared by drying it at about 70 deg.C for 10min or so, and subsequently, ultraviolet rays are irradiated through a mask formed as desired. Subsequently, an unhardened part of the photosensitive film is melted and removed, and thereafter, an obtained relief picture is dyed to a desired color, and a color light separating filter which is used for a color image sensor, etc. is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a color photoresolving filter used in color image sensors, etc., and more specifically, a mixture of gelatin and casein is used as a film-forming agent, and a dichromate or a water-soluble bisazide compound is used as a film-forming agent. An image is formed using a photosensitive material as a photosensitizer, and the image is colored in a desired color by a method such as dyeing.
- A method for producing a color photoresolving film.

Conventionally, these color photo-separation filters use water-soluble natural and synthetic polymeric substances having hydrophilic groups such as hydroxyl groups, carbonyl groups, and amino groups as film agents.
, 71'j ammonium chromate, potassium dichromate
Image formation is carried out using a photosensitive solution containing a water-soluble bisazide compound such as , Kasa's Juchrono, Acid J-bon, or ;r,4'-diazide spoolben 2,2'-disulfonic acid as a photosensitizer. The three primary colors of red, green, and 7r and their complementary colors, nan, magenta, and a: f, are dyed using dyeing techniques.
Many methods are being adopted to manufacture the material by coloring it in a desired color, such as wax.

Generally, gelatin is used as a film-forming agent from the viewpoint of dyeability and manufacturing process, etc. (among them, photographic gelatin is often used), and as a photosensitizer, it is used for reasons such as achieving high sensitivity. Ammonium romate r[7] is mainly used.

1^1 As you know, gelatin is made by hydrolyzing collagen found in the connective tissue of animal skin and eyes, and is a giant linear molecule made from the repeated bonds of more than 10 different amino acids. It is made from 8 intertwined molecules to form one delicate polymer, and the molecular weight is C.
) is 100,000 yen, which is above. Although gelatin is water-soluble, it generates heat when it dissolves in water, so it must be immersed in cold water to swell and then gradually heated to dissolve, making the operation complicated. Additionally, an aqueous gelatin solution of around 10% gelatinizes at around 30°C, so when applying a gelatin-dichromate photosensitive solution directly to a glass substrate or image sensor, it is necessary to raise the temperature of the solution. Moreover, a sudden drop in temperature after dropping the photosensitive liquid can cause uneven coating, so measures must be taken to prevent this. Furthermore, gelatin has strong protective colloidal properties and is hydrophobic.
It has properties such as promoting emulsification and dispersion stability in line with other substances,
In addition, even low-concentration solutions have relatively high viscosity, so it is difficult to remove dust and foreign substances that are mixed in when dissolving gelatin or preparing photosensitive liquids by filtration. It took a long time for defoaming.

On the other hand, stripe, mosaic, and other color light separation filters used in color image sensors, etc.
-1-1m There are image defects caused by dust, foreign matter, air bubbles, etc., and 4-color unevenness (caused by ζ masterpiece unevenness, etc.), which is not acceptable.

In order to solve this problem, the authors first investigated the use of low-molecular-weight gelatin in 1 to 4, and a t + th agent.
ノ, 1 e: Ll, 2 (!', 'i condyles Showa 56-; Showa 5
December 25, 2016 [III-I+: II). Generally, when the molecular weight of gelatin is decreased, the gelation temperature is 1!:l-i+:
Since the temperature is low, it is easy to maintain the 941 sol state even at room temperature, and not only film formability but also bi-transmission properties are improved. However, low molecular weight gelatin/i8'+light liquid d1,
! It was found that although the chromaticity and decomposition were good, the ``IQ'' decreased toward f and 11, and productivity was impaired.

The present invention has been developed based on the above points, and in manufacturing a color light separation filter for use in image sensors, etc., dyeability and resolution are determined according to the requirements.
Maintaining the performance of 1', gelling ρ1 without deterioration of sensitivity.
．． The purpose is to provide an agent that suppresses the attack.

[Note 4] C'5 was achieved by using a mixture of geladin and casein as a film-forming agent. Casein is a type of phosphoprotein extracted from milk, and the powder is white, tasteless, and odorless. Gelatin and other ingredients are sparingly soluble in water, but soluble in dilute alkaline solution and remain liquid at room temperature (sol state).

The chromate casein photosensitive solution has a photosensitive film strength Klljj corrosion resistance and light resistance immediately after heat treatment. Because of this, it is used as a water-soluble photoresist for human feet in the field of photo-egging, which performs precision processing of thin metal sheets, including the production of shadow masks for color televisions. However, it was used as a film-forming agent for color photoresolving filters for image sensors, etc.
However, there are difficulties in dyeing properties with gelatin, and the dyeing conditions are stricter than with gelatin, and problems remain from a productivity standpoint.

The present inventors have discovered that a mixture of gelatin and casein fully exhibits the characteristics of both gelatin and is useful as a film-forming agent for color light separation filters such as image sensors, and has completed the present invention. .

Casein is added to gelatin in an amount of 1'O to 90% by weight, preferably 20 to 70% by weight, mixed and melted to lower the gelling temperature, thereby making it easier to add sugar during film formation. It can be omitted and the handling becomes easier. - Horn j% KF on force, sensitivity by mixing both, resolution, etc.
, Stomach & Jfj: < , Showing good characteristics.

, U below, the present invention &, I
, - Unless otherwise specified, the invention is limited to the following examples.

Example 61 5 (1,0 (l O) 1 water-soluble gelatin l (
Weigh 50'g of new (made by 13 Ze2tin) and add 45% pure water.
0g
% aqueous gelatin solution was prepared eight times. -Power, casein 50
gr was added to a dilute alkaline aqueous solution consisting of 420 gr of pure water and 801 gr of ammonia water (+'), and a milky 10-layer mixture was added. Aqueous casein solution (7f) was prepared. Furthermore, from these gelatin and casein water 'fH71&, 1
A gelatin-casein mixture was prepared by adding 50% by weight of casein to gelatin.

Separately, ammonium dichromate water made by 10 Jyujou WoX L
7, and add 10rrtjB to each of the gelatin aqueous solution, casein aqueous solution, and gelatin-casein aqueous solution.
00 ml, and mix well to prepare gelatin-ammonium dichromate photosensitive solution (sample A), casein-ammonium dichromate photosensitive solution (sample B), and ammonium dichromate photosensitive solution of gelatin/casein mixture. (Sample C
) was prepared. These samples A.

B and C were each coated onto a glass substrate using a spinner to a film thickness of 1 μIn, and dried at 70° C. for 0 minutes to prepare a photoresist film. Then 'I'EG (Te5t 1 reference
Grot, +p)-r irradiation using ultraviolet rays,
hardened. Thereafter, hot water development was performed to dissolve and remove the uncured portions of the photosensitive film to form a relief image, which was then dyed with a dye having predetermined spectral characteristics. The evaluation results are shown in Table 1.

Table 1 ◎Excellent 0 Excellent Δ Slightly Poor × Inferior Based on these results, sample C (gelatin/casein mixture) is suitable as a film-forming agent for creating color light separation filters for image sensors, etc. I understand that.

Example 2 Example 1 using photographic gelatin with a thickness of 100,000
In the same manner as above, the liquid (sample 1) was prepared using Zerabun-weight romic acid ammonium chloride (sample 1). However, when dissolving photographic gelatin in water, a method was adopted in which the photographic gelatin was immersed in cold water of 10°C or less to swell by 4°. On the other hand, in the same manner as in Example 1, a gelatin/casein (=1/1) mixed solution was prepared from a separately prepared 10-weight casein aqueous solution and the photographic gelatin aqueous solution.
Sample E was prepared by adding 31J% of ammonium chromate water.

In both Samples 1) and 44, the amount of ammo-uno dichromate added to the film-forming agent was adjusted to be 10% by weight. Hereinafter, a photosensitive film was prepared on a glass substrate in the same manner as in Example 1, and an image was formed by exposure and development.
It was dyed using an acidic dye with predetermined spectral transmission characteristics.

The evaluation results are shown in Table 2.

Table 2 ■ Sample DVJ: Coating is difficult unless the liquid temperature is kept below 85°C.

It is clear that by using JTI, a film-forming agent made by adding casein to photographic gelatin, not only coating properties but also resolution are improved, and it is suitable for manufacturing color light separation filters for image sensors and the like.

Example 3 In Example 1, a photosensitive solution was prepared by adding water-soluble bisazidized sulfonic acid to the ammonium dichromate used as the photosensitizer. Hereinafter, a photosensitive film was prepared on a glass substrate in the same manner as in Example 1, exposed and developed to form an image, and this was dyed, and the same results as in Example 1 were obtained.

As described in detail below, the photosensitive solution prepared using the film-forming agent of the present invention has improved coating properties and low sensitivity '-'F-
fx, <, eil'a L, fJ+8111, such as color light separation filters for image sensors.

Agent Makoto Kuzuno - Itcho - Itouri 1 (Voluntary) Commissioner of the Japan Patent Office Dr. 1, Display of the matter 91 taka! llj noi57
-18486802, name of Bonmei, method for manufacturing color light separation filters 13, 111, 4 ancient representations of Hitoshi Katayama, 13, representative 5, detailed description of the invention in the specification to be amended, column 6, content of the amendment 4

Claims (1)

[Claims] 1. A step of applying a water-soluble negative photosensitive material onto a substrate to produce a photosensitive film, and a step of irradiating the photosensitive film with light having a predetermined planar shape. , removing the soluble portion of the photosensitive film by development, and dyeing the photosensitive film remaining on the substrate, etc.! A method for manufacturing a color photoseparation filter by coloring it in a desired color, characterized in that a mixture of gelatin and casein is used as a film-forming agent, which is one of the constituent components of the water-soluble negative photosensitive material. A method for producing a color photoresolving filter 2, a film-forming agent consisting of a gelatin/casein mixture, characterized in that casein is chopped into gelatin in an amount of 10 to 90 weight percent, preferably 20 to 70 weight percent. Scope of manufacturing method for a color light separation filter according to item 1 3. Method for manufacturing a color light separation filter according to item 1 of the constituent components of the water-soluble negative photosensitive material 4. Manufacturing method of color light separation filterManufacturing method of color light separation filterSolution method of manufacturing filter