JPH01173028A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To avert the problem of the function fault of an image pickup element without incorporating halogen ions into the title resin compsn. as well as to improve sensitivity and resolution and to facilitate quality control by using a resin having an allyl group of prescribed components and a photosensitive resin compsn. contg. prescribed compds. as the compsn. of a photosensitive resin for color sepn. filters. CONSTITUTION:The resin having the allyl group obtd. by bringing polyethylene imine, allyl ether (formula I) or 1-diallylamino-2,3-epoxy propane (formula II) into reaction is designated as a component 1. The compsn. contains 1 or >=2 compds. selected from the group consisting of the 4,4'-diazide stilbene-2, 2' sodium or potassium disulfonate expressed by formula III, the 2,6-di(4'- azidebenzal)cyclohexanone expressed by formula IV and the 2,6-di(4'- azidobenzal)-4-methylcyclonexanone expressed by formula V as a component 2. The photosensitive resin compsn. which averts the function fault of the image pickup element without incorporating the halogen ions therein and has good sensitivity and high resolution is obtd. In formula, Z is Na or K.

Description

[Detailed description of the invention] #! The present invention relates to a novel photosensitive resin composition,
More specifically, it is a photosensitive resin composition that is sensitive to light, can be developed with water, lower alcohols, methylcellosolve, etc., and has a photocured film that can be easily dyed, making it suitable as a color separation filter. It is something to do.

1. Color separation filters are used to colorize liquid crystal televisions or solid-state image carriers. This color separation filter conventionally uses a photosensitive resin made by adding ammonium dichromate to an aqueous solution of natural proteins such as casein and gelatin, and creates a pattern on a glass substrate using lithography technology, and then adjusts the pattern to specific spectral characteristics. It is made by staining.

However, since natural materials such as casein and gelatin are proteins, they are susceptible to deterioration due to spoilage and have a short shelf life.Also, due to variations in raw material sources depending on the season, the quality is inconsistent, which requires a lot of effort to control the quality of filters. The current situation is that we are forced to do so. Furthermore, in the dyeing process, the photocured product of this natural protein is easily peeled off by hot water, so there are restrictions on the dyeing temperature. Furthermore, since ammonium dichromate is used as a photocuring agent, various types of A1 are used in wastewater treatment.
Accompanied by 11 approx. For this reason, there has been a demand for the development of an easily dyeable photosensitive resin using synthetic polymers instead of natural proteins such as casein and gelatin.

In recent years, as synthetic polymer-based photosensitive resins for color separation filters, for example, there is one disclosed in JP-A-59-155412. This resin is a terpolymer of N-vinyl-2-pyrrolidinone, a monomer with a quaternary ammonium salt structure and an unsaturated bond, and a methallylic acid ester or an acrylic acid ester, in which a water-soluble bisamide is added. Shitachi no guru.

The three characteristics required for photosensitive resins for color separation filters are (1) high sensitivity, good resolution, and (3) good dyeability. In order to balance the above, the composition ratio of the above terpolymer is quite limited, which makes it difficult to constantly control and synthesize the resin with the required composition ratio of the terpolymer. Furthermore, since the molecule has a structure of a quaternary ammonium salt, it contains halogen ions, and there is a possibility that the halogen ions may interfere with the function of the solid-state imaging device.

As a photosensitive resin for color separation filters, JP-A-6
0-221755, but since this also has a quaternary ammonium salt in its molecule, it is thought that halogen ions may cause dysfunction of the solid-state Li imaging element = In this way, a synthetic polymer-based color separation filter However, there is no photosensitive resin that satisfies the requirements such as sensitivity, resolution, dyeability, storage stability, and no functional impairment in solid II images. The current situation is that development is eagerly awaited.

Problem 1 to be Solved: The object of the present invention is to provide a new photosensitive IM resin that overcomes the drawbacks of photosensitive resins for color separation filters as described in F.

Means to Solve the Problems As a result of intensive research by the Ministry of Invention and others, the above objectives are (i)
Borien imine and allyl glycidyl ether (1
1 or 1-diallylamino-2,3-epoxypropane+10 and a resin containing an allyl group (component 1), (ii! Sodium or potassium diazidostilbene-2,2'-disulfonate, 2,6-di(4'-azidobenzal)cyclohexanone, represented by the structural formula The present invention has been completed by discovering that the present invention can be achieved by a photosensitive resin composition containing one or more compounds (component 2) selected from the group consisting of That is, an object of the present invention is to provide the above photosensitive resin composition.

The resin of component 1 can be synthesized by reacting polyethyleneimine with allyl glycidyl ether or 1-diallyl 7minor 2°3-epoxypropane.

The polyethyleneimine used in the present invention has intermolecular 1,
000 to ioo and ooo are preferred, and more preferably 2.000 to 50.000. (I) or■
The epoxy resin of the compound easily reacts with the amino group of poly(1-ethyleneimine) to form an adduct with the allyl group remaining.

The introduction of these compounds into polyethyleneimine is 20 to 75% based on the amino groups of polyethyleneimine.
It needs to be the same amount. In order to make the resin water-soluble, in the case of allyl glycidyl ether f1), it is necessary to make the introduction ratio less than 53% equivalent, and in the case of 1-diallylamino-2,3-epoxypropane + ID, must be less than 60%.

Among the photocrosslinking agents of component 2, sodium or potassium 4.4'-diazidostilbene-2,2'-disulfonic acid is dissolved in water, methanol, methylcellosolve, etc., and 2.6-
di(4'-azidobenzal)cyclohexanone and 2
．． 6-di(4'-7didobenzal)-4-methylschiff0
Hexanone is soluble in organic solvents such as methanol.

When the resin composition according to the present invention is exposed to light, C is component 1.
and component 2 in a common solvent for both, such as water, methanol,
It may be dissolved in methyl cellosolve or the like and mixed. Ingredient 1
The mixing ratio of component 2 is 1.100 parts of component and component 2.
is preferably in the range of 3 to 20 parts, more preferably 4 to 15 parts.
% range.

Generally, 4 times or more is required for melting 1 part of the component.

The photosensitive resin solution thus obtained is applied to a suitable substrate such as a wafer, dried, and irradiated with light to obtain a transparent photocured film.

A photosensitive resin composed of components 1 and 2 has sufficient sensitivity, but if you want to increase productivity, further increase sensitivity, and shorten the exposure Q4 time, use a known sensitizer such as Michler's ketone or 1-nitropyrene. Just add it. When the resin in the unexposed areas is removed using a solvent in which component 1 is soluble, such as water or methanol, a transparent film is formed in the exposed areas, and a clear and fine <K image 4q is formed.

When the photocured film thus obtained is dyed with acid dyes, direct dyes, reactive dyes, etc., it can be easily dyed and exhibits sufficient performance as a photosensitive 484 resin for color filters.

The present invention will be explained with reference to the following examples, but of course the present invention is not limited only to the examples.

Example 1 22.5 g of polyethyleneimine (Evomin 5P-200 manufactured by Nippon Shokubai Kagaku Nippon Kogyo Co., Ltd.) with an average molecular weight of mi oooo was dissolved in 127.39 g of isopropyl alcohol to make a solution with a concentration of 15%.

29.8 ff of allyl glycidyl ether (50% equivalent to all 7 mino groups in polyethyleneimine) was added dropwise to the above solution while stirring at room temperature.

After stirring at 40°C for 24 hours, the mixture was concentrated to about 1/3 using a vaporizer.

The concentrate was poured into petroleum ether, the resulting slurry precipitate of polymer was thoroughly stirred, and the supernatant liquid was removed by decantation.

Polymer 50.39 was obtained by vacuum drying at room temperature.

Table 1 shows the solubility of this polymer.

Table 1 For reference, Table 2 shows the solubility of the raw material polyethyleneimine.

Table 2 Poly-1-dylenimine is insoluble in ethyl acetate;
The polymer obtained here becomes soluble in ethyl acetate.
The solubility is clearly different.

The IR absorption spectrum of this polymer is 1640t:m
Absorption attributable to carbon-carbon double bonds was observed at , 990cIR-' and 920cm-'.

In addition, -C in the 'H-NMR absorption spectrum is also
Absorption attributable to carbon-carbon double bonds was observed in the range of 4.9 ppm to 6.311E1m. The amount of acrylic glycidyl ether reacted with polyethyleneimine determined from the integrated intensity ratio of this spectrum was 47% equivalent to the total amino groups of polyethyleneimine.

Example 2 Stones corresponding to 25% equivalent, 140% equivalent, 55% equivalent, and 75% equivalent of allyl glycidyl ether to all amino groups in polyethyleneimine are dropped into a 15% polyethyleneimine and isopropyl alcohol solution, respectively. Everything else was carried out in the same manner as in Example 1, and polyethyleneimine and allyl glycidyl ether were reacted to obtain a polymer.

Table 3 shows the charging ratio of polyethyleneimine (PEI) and allyl glycidyl ether (AGE) and the yield of the polymer obtained by the reaction, and Table 4 shows the solubility of the polymer.

The IR absorption spectra of all the polymers listed here are 1640 cm-', 990 cm-', 920 cm-'
Absorption attributable to carbon-carbon double bonds was observed in I'',
Further, from the 1F+-NMR absorption spectrum, absorption due to carbon-carbon double bonds was observed in the range of 4.9 ppm to 6.3 ppm.

Furthermore, from the integrated intensity ratio of the H-NMR absorption spectrum, allylglycidyl 1-
I asked for Chill's question. The values are shown in Table 5.

Table 5 Example 3 Allyl glycidyl ether was converted into 1-diallylamino-2,
Change it to 3-epoxypropane and add stones corresponding to 25% equivalent, 40% equivalent, 50% equivalent, 55% equivalent ffi, and 75% equivalent of the total amino groups in li'lyethylenimine to polyethyleneimine, respectively. The same procedure as in Example 1 was repeated except that 1 drop was added to a 15% isopropyl alcohol solution of polyethyleneimine and 1-diallylamino-2,3-epoxypropane to obtain a polymer. l”) and 1-dialino-1-amino-2,3-epoxypropane (DAEP)
The yield of the polymer obtained by the reaction with the charging ratio of 4 is shown in Table 6.

The solubility of the obtained polymers is shown in Table 7.
0as-', 920cIR-' shows absorption due to carbon-carbon double bonds, and in the 1-NMR absorption spectrum, absorption due to carbon-carbon double bonds is 4.0as-' and 920cIR-'.
9+1fl- to 6.3E11)-.

From the integral intensity ratio of this 'l-l-1-N spectrum, 1-diallylamino-2, which reacted with polyethyleneimine,
The reaction rate of 3-evo 4-shibu 0 bread was determined.

Table 8 shows the reaction rate.

Table 8 Example 4 Polymer synthesized in Example 1, polymer of sample number 1.2 synthesized in Example 2, sample number 5 synthesized in Example 3
, 6.7.8, a solution was prepared according to the formulation shown in 2 below.

Solution formulation Silane coupling agent-X-1 manufactured by Nippon Unicar Co., Ltd.
Duplicate solutions were spin-coded at 150 ORPM onto Table 1Tti-treated glass wafers at 100° C.
Dry for a minute.

Next, a photomask was placed on the coating of this glass wafer, and a 250 W over 1 pressure mercury lamp manufactured by Ushio Inc. was used as a light source to illuminate the film at an irradiation intensity of 10.5 W/aR2 for 15 seconds.

The film was developed by immersing it in water at 30° C. for 3 minutes, and was rotated for 30 seconds at 3000 PPM using a spinner to shake off the water as a developer.

All of the polymers used here form a transparent film with a pattern of about 0.5 μm on the exposed area on the glass wafer,
It was a clear image with a resolution of 1.5 μm.

Example 5 The same polymer used in Example 4 was used.

The same operations as in Example 4 were performed except that the solution formulation was changed to the formulation shown in 1ζ and the exposure time was changed to 2 seconds.

Solution formulation All of the polymers used here form a transparent film with a thickness of about 0.5 μm on the exposed area on the glass wafer,
It was a clear image with resolution of 1.5 μm rL.

Example 6 The polymer of sample WI No. 3.4 synthesized in Example 2 and the polymer of sample No. 9 synthesized in Example 3 were used, and 4.4'-diazidostilbene-2,2' was used as a photocrosslinking agent. A solution was prepared using sodium disulfonate, 2,6-di(4'-azidobenzal) Schifolhexanone, and 2,6-di(4'-azidobenzal)-4-methylcyclohexanone according to the formulation shown below.

Formulation of solutions These solutions were spin-coated on glass wafers surface-treated with silane coupling agent A-1100 in the same manner as in Example 4, dried at 70° C. for 20 minutes, and then exposed to light for 15 seconds.

C development was performed by immersing it in methanol at room temperature for 1 minute, and the methanol was shaken off by spinning at 3000 PPM for 30 seconds using a spin-boo. All of the polymers used here formed a transparent film on the glass wafer with a film thickness of about 0.5 μm in the exposed area, and it was a clear image with a resolution of 1.5 μm.

Example 7 The same operations as in Example 6 were performed except that the solution formulation in Example 6 was replaced with the following formulation and the exposure time was changed to 2 seconds.

Solution formulation All of the polymers used here form a transparent film with a thickness of about 0.5 μm on the exposed area on the glass wafer,
It was a clear image with a resolution of 1.5 μm.

Example 8 Dye Red 14 for color filters manufactured by Nippon Kayaku Co., Ltd.
Red, green, and blue staining solutions were prepared by dissolving P, Green IP, and Blue 5P in water at a concentration of 1 g/l, respectively.

The glass wafers with clear and fine images produced in Examples 4.5 and 6.7 were heat treated in air at 100° C. for 1 hour. Red these glass wafers.

It was immersed in green and h staining solutions, respectively, and stained at 60'C for 10 minutes.

After dyeing, the glass wafer was thoroughly washed with water and the water was shaken off using a spinner at 3,000 revolutions. Clear images of red, green, and blue dyeing were obtained.

In addition, when we observed this stained image under a microscope, we found that
It was confirmed that there was no #ljI#[ of the coating due to staining, and the image was a fine stained image that was almost the same size as the stained image.

Comparative Example Glass wafer whose surface was treated with silane coupling agent A-1100 (manufactured by Nippon Unicar) using a casein-weight (1 muric acid-based resist for H-Lar filter (Fuji Resist FR-100 Fuji Pharmaceutical Co., Ltd. V)) In accordance with the usage of Fujiresist FR-100, an image with a resolution of 1.5 μm was formed using a film with a film thickness of 0.5 μm and approximately 0.8 μm.The exposure v1151 for forming this image was is 15
It was seconds, which was rather long.

These stainings were performed under the same conditions as the staining and washing shown in Example 8, and the degree of staining and dimensional changes in images observed under a microscope were observed.

gt thickness of about 0.5μm'#! Regarding the I film, there was a slight change in the images before and after staining, and although the thickness of the dyed film was almost the same as that of the dyed film in Example 8, the staining was lighter in color. In particular, the degree of coloring of the green dyed film was extremely low.

In a film with a film thickness of 0.8 μm, the degree of staining was almost the same as that of the dyed film in Example 8, but the swelling of the film during dyeing was significant, and there was a dimensional change in the image before and after staining. There were a lot of particles, and a dyed film with a resolution of 1.5 μm could not be obtained.

Effects of the Invention The photosensitive resin according to the invention has the following effects when used as a color separation filter.

Medium: Good sensitivity and high resolution marks.

(2) Staining is easy and clear images can be obtained, there is no peeling of the coating due to dyeing, and there is no dimensional change before and after dyeing.

(3) Since it does not contain Ha[1 gene ions, it is possible to avoid the problem of dysfunction of the imaging probe due to the same ions.

(4) Since synthetic polymers are used, the problem of decay and deterioration is F! This makes quality control easier.

Claims (2)

[Claims] (1) Component 1: Polyethyleneimine and allyl glycidyl ether (
I) or 1-diallylamino-2,3-epoxypropane (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) Obtained by reacting with Allyl group-containing resin and component 2: General formula (III) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(III) 4,4'-diazidostilbene- (in the formula, Z represents Na or K) 2,2'
Sodium or potassium disulfonate formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼(IV) 2,6-di(4'-azidobenzal)cyclohexanone shown by the structural formula of ben and formula (V) ▲Mathematical formula, chemical formula , tables, etc. ▼(V) A photosensitive compound containing one or more compounds selected from the group consisting of 2,6-di(4'-azidobenzal)-4-methylcyclohexanone represented by the structural formula Resin composition. (2) The photosensitive resin composition according to claim 1, which contains 1-nitropyrene.