JPS5979246A - Resist composition for color filter - Google Patents

Abstract

PURPOSE:To form a color filter pattern without requiring complicated steps by using a resist compsn. composed of polyvinyl acetate of >=60% saponification rate contg. photocross-linkable structural units. CONSTITUTION:The herein used resist compsn. is composed of a polyvinyl acetate deriv. having >=60% saponification rate contg. photocross-linkable structural units represented by the shown general formula in which R is H or alkyl; X<-> is a halogen ion, sulfuric acid ion, methyl sulfate ion, or p-toluenesulfonic acid ion; and (m), (n) are each optional integer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a resist composition that can be used when forming a color filter on a solid-state image sensor.

[Technical burden of the invention and its problems]

Conventionally, XY address system (trios)'ET, C
ID).

Solid-state imaging devices such as signal transfer type (CCD) and combination type (CPD) are used to form color filters, which are exposed to hydrophilic polymers such as casein, gelatin, fish greens, polyvinyl alcohol, and polyvinylpyrrolidone. A photosensitive resin aqueous bath solution containing dichromate, chromate, or diazo compound as an agent is applied to the transparent support layer formed on the solid-state imaging 1"1 probe, and After exposure to ultraviolet light, 1α
This layer is treated to form a predetermined pattern to form a colored layer.
<A method of coloring it to make a color filter is known.

In this method, the photosensitive resin resist for color filters currently most widely used is casein i 7.
'Ci-j: Secitin-JL Chromium ammonium salt is a photosensitive composition, but because the dark reaction after application is fast, it is difficult to use during the strip-making process]-! There was a problem with jj, and the cultivation quality was poor. In addition, casein and gelate contain natural protein molecules such as a) sodium ions and potassium ions. It had spread throughout the children and had a serious impact on Motoko's religious beliefs. difference,
Furthermore, hexavalent chromium ions are harmful to the human body,
From the standpoint of the company, coating residues and developer waste had to be collected, treated, and then disposed of, making the process a complicated process.

On the other hand, the use of polyvinyl alcohol having 11 sterylpyridium groups as a fully aqueous/li'% photosensitive resin is known as seen in Japanese Patent Publication No. 5761/1983. The polyvinyl alcohol resin has no defects and may be used as a resist on the side of the mirror. However, the above photosensitive resin is hydrophilic]
It has a strong texture and swells during development, making it difficult to obtain a clear pattern according to the inventors' EIKEN test.

[Objective of the Invention] The present invention was made in order to eliminate the drawbacks of the conventional fL method, and provides a resist that can form a clear color filter pattern without requiring complicated steps. One purpose is to

[Summary of the invention]

The present invention is based on the general formula:
- represents a halogen ion, sulfate ion, methyl sulfate ion, or P-1 luenesulfonate ion, m,
n represents an arbitrary integer. This is a resist composition for a color filter comprising a polyvinyl acetate 1 derivative containing a photocrosslinkable structural unit having a styrylpyridium group represented by the following formula and having a Ken ratio of 60% or more.

Next, the present invention will be explained in more detail.

The polyvinyl acetate derivative having a sterylpyridium group of the present invention is obtained by introducing a sterylpyridium group into a partially or completely saponified product of polyvinyl acetate and adding an aldehyde, and it has the following repeating unit 1, Jl
, ■ Furthermore, it consists of ■ as an 1P component.

H3 O\10 CI-1 ■ CH2-Cl-1-Ill H CH, -CH-IV () CH,CO The preferred ratio of each repeating unit as the resin for the resist material of the present invention is such that the repeating unit I is 0. 01-10 mol%, repeating unit (■) is 10-50 mol%, repeating alignment (■) is 5θ~
90 mol%, and the repeating unit (■) is not more than Xo mol%. The proportion of repeating units l having stilpyridium groups is
If it is less than 0.01 mol%, the required photosensitivity cannot be achieved, and even if it exceeds 10 mol%, not only can no longer be expected to improve the photosensitivity, but the water affinity is extremely low. It cannot be reduced to an aqueous resist solution. However, if the proportion of the repeating unit (2), which is an aldehyde adduct, is less than 10 mol %, water A'l in fJ: in the resin is strongly absorbed, and the swelling side phenomenon during development cannot be prevented. Furthermore, if the proportion of the repeating unit (3) exceeds 50 mol %, the resin becomes partially water-insoluble and gels, making it unsuitable for use as an aqueous resist solution.

Furthermore, if the proportion of the repeating degree (3) exceeds 40 mol%, there is a drawback that the thermal properties of the resin decrease.

In addition, in the repeating unit I, the vinylpyridium group may be bonded to either the meta or para position of the benzene nucleus, and in the photosensitive resin, those bonded to the meta or para position coexist. You can leave it there.

Such a photosensitive resin is synthesized, for example, as follows. That is, polyvinyl acetate into which sterylpyridium groups have been introduced (polymerization degree 24oO, saponification rate 60%)
above) and an aldehyde such as formaldehyde, acetaldehyde, propionaldehyde or butyraldehyde in an aqueous solution for 0.5 to 1 hour in the presence of a small amount of sulfuric acid.
By carrying out a heating reaction, In'< poly 1.1'l having a steryl pyridium group as a base and added with aldehyde = yeast vinyl-induced barrel photosensitive 1iQ ll'r
will be 44J.

The resist of the present invention can be removed by dissolving the above-mentioned photosensitive 4N↑ fat in water, but by adding a 72-in coupling agent to the resist, it can be removed by dissolving the photosensitive 4N↑ fat in water. 711 properties can be modified and a more vivid pattern can be obtained.In this case, the addition of the silane cassilling agent is preferably in the range of 1 to 5% with respect to the resist. As the silane coupling agent, commercially available ones can be used, such as KBM602 and KBfvi603 (both manufactured by Shin-Etsu Chemical Co., Ltd.) are preferred.

〔Effect of the invention〕

When the resist material of this invention is applied to the formation of a color filter for a solid-state image, swelling of the pattern after development can be prevented and a highly precise and clear pattern can be formed.

[Embodiments of the invention]

Synthesis Example In a dark container, add 10 g of polyvinyl acetate into which 1 mol % of steryl pyridium groups have been introduced (degree of polymerization 2400, saponification rate 60% or more), 8 ml of methanol, and 10 g of sulfuric acid to 100 ml of distilled water. Mix well. Add 4g of butyraldehyde to this,
A heating reaction was carried out at about 70° C. for about 30 minutes. After further adding 60 m7 of hot water to this reaction system, 0.3 I of sulfuric acid was added dropwise, and the mixture was stirred for about 1 hour. After the reaction, the precipitated resin was filtered and thoroughly washed with distilled water.

The resin was further washed with dilute alkaline solution and dried.

The butyraldehyde concentration in the resin thus obtained was about 50 mol%. By changing the ratio of butyraldehyde to saponified vinyl of polyacetic acid, the addition rate of butyraldehyde can be changed as desired. In addition, formaldehyde, butyraldehyde,
Acetaldehyde.

Propionaldehyde can be added to the polyvinylacetate as well.

Photosensitivity 9jlih 4 obtained by the ffL synthetic force method in the example
g was dissolved in 100 g of distilled water to prepare a color filter dyeing resist. 5% KBM6 was added to this resist.
After adding 65 mL of an aqueous solution of 02 (manufactured by I8 Etsu Kagaku), a 1 μm thin film was formed on the solid-state imaging device substrate using a spinner. After pre-baking at 50℃, mask h's
UV light of 120 ``vV/cm'' was applied using the optical method.
, rinse with distilled water, rinse with methanol,
A clear pattern for the layer to be colored was obtained, with no traces of Butter 7 observed.

The photosensitive resin disclosed in the above-mentioned Japanese Patent Publication No. 56-5761+j was used. For lj4 go, the r form az of divine fat after development.
A modification of the pattern due to this was named it+ by Mehannei.

Claims (1)

[Claims] The following general formula (wherein R represents a water atom or argyrun-2, and
- represents a halogen ion, sulfate ion, methyl sulfate ion, or P-toluenesulfone 1 wave ion, m
, n represents an arbitrary integer. ) A resist composition for a force 2 filter comprising a polyvinyl acetate derivative having a saponification rate of 60% or more and containing a photocrosslinkable structural unit represented by the following formula.