JPS5833208A - Photosensitive material for production of color filter - Google Patents

Abstract

PURPOSE:To obtain gelatin based photosensitive liquid which does not gel at room temp. and is easily dyeable with acid dyes by using acid treated low molecular gelatin. CONSTITUTION:After 1,000cc water, 400g acid treated gelatin (5,000-20,000 mol.wts.), 40g ammonium dichromate, 60cc alcohol, 50cc benzoic tincture, 20cc chrome alum (0.2% aq. soln.) are thoroughly mixed, the mixture is cooled down to 20 deg.C and is left standing overnight. As a result, the mixture does not gel and the viscosity is 140cps at room temp. The mixture has good dyeing property with acid dyes.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive material for manufacturing color filters.

Traditionally, water-soluble photosensitive substances include egg white and gris.

There are hydrophilic resins such as casein, polyvinyl alcohol, and gelatin with addition of east chromate, chromate, or diazo compound as a photosensitive main agent (photopolymerization initiator), and all of them are negative type.

On the other hand, these photosensitive substances (hereinafter referred to as photosensitive liquids) can be used for etching masks for shadow masks of color cathode ray tubes, or as colored bases for manufacturing color stripes and mosaic filters used in image pickup tubes and solid-state imaging of color television cameras. It was used for both printing and collotype printing.

Among them, the following process (Japanese Patent Publication No. 62-17375, Japanese Patent Publication No. 5J-17376, etc.) is used for manufacturing color filters.

Namely, ■ Adjustment of photosensitive liquid base, ■ Addition of photosensitive main agent, ■ Coating onto substrate, ■ Prebaking, ■ Mask exposure, ■ Hot or cold water phenomenon, ■ Burning, ■
Each step of dyeing (usually with acid dyes) is carried out in sequence.

Incidentally, since the pot life of the photosensitive liquid is short, the suitable photosensitive main agent is generally added immediately before use.

However, in the conventional gelatin photosensitive solution for manufacturing color filters, the main ingredient gelatin is cylindrical gelatin with a molecular weight of 160,000 to 260,000 (for photography) obtained by treating cow bones with lime and then extracting them with hot water. gelatin, general industrial gelatin, edible gelatin, etc.), most of the amides in gelatin were converted to carboxyl groups during the lime treatment process, resulting in a low isoelectric point. In other words, with the conventional photosensitive solution using lime-treated gelatin, the dyeing position (
That is, there are few amino groups), and therefore, in order to obtain the dyeing density necessary for a color filter, a coating film thickness of about 2 to 3 μm is required. However, in recent years, with the increasing precision of color mosaic filters for solid-state image sensors, there has been a demand for producing mosaic filters with a pattern size of approximately 6 μm, but sufficient pattern accuracy can be achieved with a coating film thickness of 2 to 3 μm. I couldn't do that.

On the other hand, gelatin has a high molecular weight of 160,000 to 260,000, so if the gelatin concentration is 10 to 20%, it will almost gel at 30 to 40°C. It does not gel at about 26-°C±5°C.)

Therefore, if the gelatin photosensitive solution is applied at room temperature (26±6°C1), gelation may occur during coating even if the photosensitive solution is heated in advance, making it difficult to coat smoothly or controlling the film thickness. was also very difficult. Therefore, coating work is generally carried out at a constant temperature of 40 to 46°C, but if you consider operating a constant temperature room of 40 to 46°C and rationalizing the coating process, gelation will occur even near room temperature. There is a long-awaited need for a gelatin-based photosensitive solution that does not

The present invention has been made in view of the above-mentioned drawbacks of gelatin-based photosensitive liquids, and its purpose is to create a gelatin-based photosensitive liquid that is easy to dye, that is, it has many amine groups in its molecules and can be used at room temperature. An object of the present invention is to provide a photosensitive material for producing color filters that does not gel even at 5°C (25°C).

Generally, the process shown in FIG. 1 is known as a gelatin manufacturing process, but the major difference between acid-treated gelatin and lime-treated gelatin is that the resulting products have different isoelectric points. That is, acid-treated gelatin has a pH of 7 to 9.
On the other hand, lime-treated gelatin has an isoelectric point pH of about 4.8 to 6.1 because most of the amine groups in lime-treated gelatin change to carboxyl during the lime treatment process. Ly! Processed gelatin has more dyeing positions (that is, amino groups) for acidic dyes and has the property of being easily dyed.

On the other hand, it is known that the gelatin temperature decreases as the molecular weight of gelatin decreases. Therefore, we first treated the collagen in the skin and bones with hydrochloric acid to remove unnecessary organic matter.
Furthermore, decomposition and extraction with proteolytic enzymes are performed, and 6oo
Acid-treated low-molecular gelatin with a molecular weight of about 0 to 70,000 is produced.

This acid-treated low-molecular-weight gelatin has almost the same characteristics as general lime-treated high-molecular gelatin, except that it is easily dyed with acid dyes and has a low gelation temperature, and can be soaked in water at room temperature. It is possible.

Therefore, using the acid-treated low-molecular-weight gelatin described above, a photosensitive solution for manufacturing color filters was prepared and heated to room temperature (26±
A gelatin-based photosensitive liquid was obtained that did not gel even at 6°C and was easily dyed with acid dyes.

Hereinafter, photosensitive materials for producing color filters in Examples of the present invention will be shown.

(Example 1) After thoroughly mixing and dissolving the following substances (so ~ 60°), it was cooled to 20°C and placed in an apparatus for -1 day, but gelation did not occur and the viscosity was 14009S at room temperature. . In addition, after performing ultraviolet light exposure and cold water phenomenon (3 minutes) using a chromium mask with a coating film and a test pattern formed on a glass substrate, the 80'0110
The pattern shown in FIG. 2(a) was obtained after staining for several minutes. Note that the thickness of the photoresist film at this time was 0.68 p.

(Example 2) In Example 1, the amount of ammonium chromate, which is a photosensitive main agent, was changed to 40 g, gelatin lime-treated low molecular weight gelatin (
When the same conditions were used except that 3001 (with a molecular weight of 10,000 to 20,000) was used, gelation did not occur, the viscosity was about 2100 pm, and a similar pattern was formed. 80'C at Red RE
, p1 after staining for 10 minutes as shown in Figure 2(b).
Even though the thickness of the photosensitive film was <0.7 μm, which is the same as in Example 1, the dyeing was not as great as in Example 1. The visible spectral characteristics are shown in Figure 3.

(Example 3) In Example 1, the amount of ammonium dichromate, which is a photosensitive main agent, was 25 g, and gelatin was lime-treated (molecular weight 100,000 to 2
The experiment was conducted under the same conditions except that photographic gelatin 150p (60,000) was used, but it remained completely gelled even at room temperature of 26°C.

Therefore, after remelting at 60°C, coating, exposure, and phenomenon were performed. Although the phenomenon was performed in cold water for 10 minutes, a sharp pattern was not formed.

The results after staining are shown in Figure 4.

(Example 4) After thoroughly mixing the following substances, 2o''C
Although the mixture was cooled to a temperature of 100.degree. C. and left for one day, gelation did not occur and the viscosity was 1600 pS. Furthermore, when a glass substrate was coated and exposed to ultraviolet light using a chrome mask on which a test pattern was formed, a pattern up to about 3 μm dil could be formed. Furthermore, when dyeing was carried out under the conditions of Examples 1 and 14, the same level of dyeing as in Example 1 was achieved.

(Example 6) Even if the same conditions as in Example 4 were used except that acid-treated gelatin (molecular weight 5,000 to 20,000) 300II was used as the gelatin, gelation did not occur, and the viscosity [14ocp
The pattern is similar to that of Example 4 at about s.

Staining was obtained.

(Example 6) In Actual Example 4, general industrial lime-treated gelatin (molecular weight so, ooo ~ 260,000) was added to Ze9tin.
When conducting an experiment under the same conditions except for using BOf, gelation occurred at around 3°C until ammonium dichromate was added, but gelation did not occur after the addition of ammonium dichromate. Ta. On the other hand, the pattern formation and dyeing density were the same as in Example 2.

In addition to the above examples, acid-treated low-molecular gelatin (molecular weight 5,000-20,000) K acid-treated tiu lime-treated high-molecular gelatin (molecular weight 100,000-20,000)
), we were able to prepare a photosensitive solution that does not gel at room temperature, has a high viscosity, and stains well with acid dyes.

(Example 7) In Example 1, acid-treated low-molecular-weight gelatin (
300 g of molecular weight s, ooo ~ 20,000) and lime-processed polymer gelatin (molecular weight 100,000' ~ 20
When the experiment was conducted under the same conditions except that a mixture of 0.000) 40f was used, the viscosity at room temperature was 250 cps.
Other than that, the same results as in Example 1 were obtained.

In the above examples, the case where dichromate was used as the photopolymerization initiator was described, but it is clear that the same effect can be obtained with radical initiators such as diazo compound type or peroxide type. . Note that benzoin tincture, which is an auxiliary agent used in the examples, has a gelatin star control and hardening effect, and alcohol has an effect of preventing foaming and improving spreadability.

According to the above examples, acid-treated low molecular weight gelatin (molecular weight 5,000-30.0001 or 30,000-7
By preparing a gelatin photosensitive solution containing 0,000) as the main component, it is possible to produce a gelatin photosensitive solution that has good dyeability with acid dyes, does not gel even at room temperature, and therefore has a slow viscosity change. It was revealed.

Therefore, by using this photosensitive liquid, even if the coating process is performed at room temperature, the film thickness can be easily controlled and uniform coating can be performed, so that the efficiency of the coating process and the energy saving effect are very large. Furthermore, the developing process can be performed using cold water, which is very advantageous.

Furthermore, by using acid-treated gelatin, the dyeing density per unit thickness can be increased. That is,
Even if the coating film thickness is about 0.6 μm, a sufficient dyeing density for use as a color filter can be obtained, so it is easy to form a fine pattern of about 6 μm.

[Brief explanation of the drawing]

Figure 1 shows a general manufacturing process for ceratin, Figure 2 (IL) shows a microscopic photograph of a pattern formed using acid-treated gelatin in Example 1 of the present invention, Figure 2 (b ) is a diagram showing a micrograph of a pattern formed using a lime-treated gelatin photosensitive solution for comparison with Example 1;
FIG. 3 shows the visible spectral characteristics of the sample dyed after forming a pattern using a photosensitive solution in Example 1 of the present invention and IJ2 for comparison with the method shown in FIG. 10. This is a micrograph showing that an attempt was made to form a pattern using the photosensitive solution of Example 3, but the turn forming ability was not successful in cold water development. Name of agent Patent attorney Toshio Nakao 1 person Figure 1 Figure 2 (α) Figure 3 U * (E Figure 4 Procedural amendment (method) % formula % l Indication of the case 1986 patent Application No. 131178 2 Name of the invention Photosensitive material for manufacturing color filters
Address: 1006 Kadoma, Kadoma City, Osaka Prefecture
i′ [・ (582) Matsushita Electric Industrial Co., Ltd. 7 < 1
J' Toshihiko Yamashita 4 Agent 571 Address 1006 Oaza Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. Details of the amendment (1) Page 11, line 16 to 12, Tei No. 6 of the specification row [
Figure 1 is a general... ] as follows. [Figure 1 shows the T culm for general gelatin production.
Figure (a) shows the pattern formed using acid-treated gelatin in Example 1 of the present invention, and Figure 2 (b) shows the pattern formed using lime-treated gelatin photosensitive solution for comparison with Example 1. An enlarged view of the formed pattern, and FIG. 3 is a diagram showing the visible spectral characteristics of the pattern that was dyed after forming the pattern using the photosensitive liquid in Example 1 of the present invention and Example 2 for comparison. , and FIG. 4 is an enlarged view of a pattern which was attempted to be formed using the photosensitive liquid of Example 3, but which shows that pattern formation did not go well with cold water development. (22 Drawings Figure 2 (a), (b) i Figure 4 is amended as a separate set. Figure 2/a) Figure 4 10 ρ voice m Procedural Amendment 1 Case Display Showa 6C Patent Application No. 131178 2. Name of the invention Photosensitive material for manufacturing color filters 3. Matters to be corrected 1'1 What relationship, patent application
Appointment Address: 1006 Kadoma, Kadoma City, Osaka Prefecture
(582) Matsushita Electric Industrial Co., Ltd. Representative Toshihiko Yamashita 4 Agent 571 Address 1006 Oaza Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. Detailed explanation of the invention in the specification subject to the 6th amendment Drawing 6, Contents of amendment (1) "Additional protein" in the 6th line, line 8 of the specification will be corrected to 1.Additional thermal decomposition or protein. (2) [Shown in Figure 3] on page 7, line 11 of the specification. 1 is shown in Figure 3. In the figure, ta+ is oxidized gelatin, and (b) is lime-treated gelatin.
will be corrected. (3) Correct the drawing Figure 3 as shown in the attached sheet 〇 Figure 3 1'/a Liquid table

Claims (2)

[Claims] (1) A photosensitive material for producing a color filter, characterized in that the main components are acid-treated gelatin and water, and a photopolymerization initiator and an auxiliary agent are added thereto. (2) The molecular weight of acid-treated gelatin is 5ooo to 70,000
A photosensitive material for producing a color filter according to claim 1, which is characterized in that: