JPH0462660B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition for a color filter used in a solid-state image sensor or a color liquid crystal display device. Conventional technology Color solid-state image sensors (such as CCD, CID, BBD, and MOSFET) are in high demand as VTR cameras.
Due to the trend toward lighter and thinner imaging ICs),
The color filters used in color liquid crystal display devices, etc., which are undergoing a transition from the CRT method, are
It is formed by providing fine areas colored in different hues or more on a solid-state image sensor or a transparent substrate. In order to form a fine substrate film to be colored in two or more colors, a photosensitive resin is used because it is easy to form fine patterns and is relatively easy to color. For example, a photosensitive resin made by adding ammonium dichromate, a diazo compound, etc. as a photosensitive material to a protein such as gelatin or casein or a hydrophilic resin such as polyvinyl alcohol or polyvinylpyrrolidone is coated on a transparent substrate, and a predetermined shape is formed on the photosensitive resin. UV rays are irradiated through a mask with an aperture pattern to photocure the exposed areas, a predetermined pattern is formed through development processing, and then this is dyed with a water-soluble dye, etc., twice with different dyes. By repeating the above steps, transparent substrates and the like having fine patterns colored in two or more different hues have been manufactured. However, the method of using such dichromates and diazo compounds as photosensitive materials has problems in waste liquid treatment, and when gelatin is used, since it is a natural product, its quality is inconsistent and coloration is uneven. There was a drawback that it was easy to occur. To improve such shortcomings, the formula (In the formula, R represents a hydrogen atom, an alkyl group, or a lower hydroxyalkyl group, and X represents an anion of a strong acid.) A photosensitive resin has been proposed, which has good sensitivity to light and is highly sensitive to light. Although it does not use chemicals that are difficult to handle, such as chlorate, it has the disadvantage that the dyeing property, especially with green water-soluble dyes, is not good. Recently, formulas have been developed to improve these shortcomings. (However, in the formula, R is an aminoalkyl group, R' is a methyl group or an ethyl group, and X is chlorine, bromine, iodine,
Perchloric acid, acetic acid, methyl sulfate, sulfuric acid, nitric acid or p
- an ion of trienesulfonic acid, l, m, and n are arbitrary integers) It was proposed to use a photosensitive resin represented by Although the photosensitive resin disclosed in 1987-29740 was successful in improving the dyeability, it was revealed that it had the following drawbacks. (1) The heat resistance of the photocured resin is insufficient. (2) Dyeing group on polyvinyl alcohol

[Formula] and photosensitive group

The complexity of manufacturing is that [Formula] must be reacted. (3) A photosensitive resin with excellent dyeing properties and photosensitivity cannot be obtained unless the dyeing group and the photosensitive group are appropriately arranged, but it is complicated to design such a molecular structure. Means for Solving the Problems The present inventors have conducted extensive studies to solve the above-mentioned drawbacks, and as a result, have arrived at the present invention. That is, the present invention is based on the formula [In formula (), X is

[Formula] or

[Formula] (In these formulas, R ₃ represents a hydrogen atom or an alkyl group, and A represents a halogen ion, sulfate ion, phosphate ion, p-trienesulfonate ion, methylsulfate ion, or hydroxy ion), n, m
and l represents any integer. However, n+m+l is
400 to 3000, and the proportion of l in n+l is 0.2 to
10%, and the ratio of n+l to n+m+l shall be 75% or more. It is characterized by containing a hydrophilic polymer () selected from a polyvinyl alcohol derivative represented by () and water-soluble nylon, polyvinylpyrrolidone, a copolymer consisting of a hydrophilic or hydrophobic monomer and a nitrogen-containing monomer, or a salt thereof. A photosensitive resin composition is provided. The present invention will be specifically explained. The polyvinyl alcohol derivative represented by the formula () is a known compound, and for example, based on the method of Japanese Patent Publication No. 56-5761, polyvinyl alcohol or partially saponified polyvinyl acetate (hereinafter both are collectively referred to as polyvinyl alcohol derivative) is prepared by the following formula. (In formulas () and (), R ₃ is a hydrogen atom or an alkyl group (preferably a C _1-4 alkyl group, more preferably a methyl group or an ethyl group)
A represents a halogen ion, sulfate ion, phosphate ion, p-trienesulfonate ion, methylsulfate ion or hydroxide ion). In this case, the polyvinyl alcohol derivative to be reacted has a degree of polymerization of 400 to 3000, preferably 500.
Partial saponification of ~2000 polyvinyl acetate (saponification degree
75%, preferably 85% or more is used. photosensitive group

[Formula] is the vinyl alcohol group of polyvinyl alcohol derivative

It is preferable to introduce the compound at a ratio of 0.2 to 10%, more preferably 1 to 5%, based on the number of [Formula], from the viewpoint of sensitivity to light, developability, etc. On the other hand, in the present invention, as the dyeable hydrophilic polymer, water-soluble nylon, polyvinylpyrrolidone, a copolymer consisting of a hydrophilic or hydrophobic monomer and a nitrogen-containing monomer, or a salt thereof is used. Water-soluble nylons include those containing a water-soluble piperazine derivative as a copolymer component;
A polyamide resin into which a sulfonic acid group or a carboxyl group has been introduced is used, and these are easily available on the market. Next, specific examples of each monomer for synthesizing a copolymer consisting of a hydrophilic monomer (A) or a hydrophobic monomer (B) and a nitrogen-containing monomer (C) include the following. First, as the hydrophilic monomer (A), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, maleic acid,
Fumaric acid, itaconic acid, vinylbenzenesulfonic acid, etc. are used as hydrophobic monomers (B), acrylic esters, methacrylic esters, acrylonitrile, etc. are used as hydrophobic monomers (B), and N, N- as nitrogen-containing monomers (C). Dimethylaminoalkyl acrylic acid or its acid amide (however, the alkyl number is 0 to 3 carbon atoms), N,N-dimethylaminoalkyl acrylic acid or amide (however, the alkyl number is 0 to 3 carbon atoms), Examples include N-vinylprolidone and vinylpyridine. The copolymer or salt thereof used in the present invention can be obtained by copolymerizing these monomers according to a known method. The photosensitive resin composition of the present invention is usually prepared by adding an aqueous solution of a hydrophilic polymer to an aqueous solution of the polyvinyl alcohol derivative of formula (1) at a ratio of the polyvinyl alcohol derivative to the hydrophilic polymer of 1:0.1 to 1.5, preferably 1:0.2 to
It is prepared by mixing it so that it becomes 1.0. The viscosity of the resin composition of the present invention is adjusted with water or an organic solvent such as methanol or ethanol as necessary, and the resin composition of the present invention is used as a coating liquid for manufacturing a color filter. The general method for making the color filter used is as follows. First, the composition of the present invention is uniformly applied onto an image sensor or substrate whose surface has been smoothed using, for example, a spinner. Next, a prebaking process is performed at 50 to 80°C for 5 to 60 minutes, and then light is irradiated through a mask having a desired pattern. Next, the pattern formed by the development process is immersed in a dye solution and dyed, for example, at a temperature of about 50 to 90°C for 3 to 30 minutes. As the dye for dyeing the pattern obtained from the resin composition of the present invention, water-soluble dyes having a sulfonic acid group, particularly direct dyes and acid dyes, are suitable. EXAMPLES The present invention will be explained in more detail by way of examples. In the examples, unless otherwise specified, "part" means "part by weight" and "%" means percent by weight. Example 1 N-methyl-γ-(p-formylstyryl)pyridinium methosulfate was added to partially saponified polyvinyl acetate with a degree of polymerization of 1700 and a degree of saponification of 87% based on the number of vinyl alcohol groups (number of moles). A photosensitive resin composition of the present invention was obtained by mixing 50 parts of a 10% aqueous solution of a polyvinyl alcohol derivative reacted with 1.8 mol% and 50 parts of a 10% aqueous solution of water-soluble nylon (manufactured by Toray Industries, Inc., product A-90). . This photosensitive resin composition was placed on a transparent glass plate at 1 μm.
The film was applied to a film thickness of m, dried at 90° C. for 30 minutes (prebaked), and then exposed to light at 200 mj/cm ² through a mask having striped openings. Subsequently, after immersing in pure water for 2 minutes to develop the phenomenon, post-baking at 90℃ for 30 minutes, and then applying a dye bath (acetic acid acid )
It was dyed by immersing it in water for 10 minutes at 60°C. Then, it was washed with water and dried to obtain a colored pattern. The dyeing density (optical density) of this colored pattern is 3.03 (λmax620n
It was m). Example 2 The partially saponified polyvinyl acetate used in Example 1 was reacted with 1.4 mol% of N-methyl-γ-(p-formylstyryl)pyridinium methosulfate based on the number of vinyl alcohol groups (number of moles). 10 of polyvinyl alcohol derivatives
% aqueous solution and 20 parts of a 10% aqueous solution of polyvinylpyrrolidone (manufactured by Tokyo Kasei Co., Ltd., trade name PVPK-90) to obtain a photosensitive resin composition of the present invention. Next, a cured pattern was formed and dyed in the same manner as in Example 1. Staining density (optical density) 2.80
(620nm) coloring pattern was obtained. Example 3 N-methyl-γ-(p-formylstyryl)quinolinium methosulfate was added to partially saponified polyvinyl acetate with a degree of polymerization of 500 and a degree of saponification of 87% based on the number of vinyl alcohol groups (number of moles). of
A photosensitive resin composition of the present invention was obtained by mixing 50 parts of a 10% aqueous solution of a polyvinyl alcohol derivative reacted with 1.6 mol % and 40 parts of a 10% aqueous solution of water-soluble nylon (manufactured by Toray Industries, Inc., product A-90). Next, a cured pattern was formed and dyed in the same manner as in Example 1. Staining density (optical density) 3.25
(620nm) coloring pattern was obtained. Example 4 1.8 mol of N-methyl-γ-(p-formylstyryl)pyridinium-p-toluene sulfate was added to the partially saponified polyvinyl acetate used in Example 1 based on the number of vinyl alcohol groups (number of moles). 80 parts of a 10% aqueous solution of a polyvinyl alcohol derivative reacted with 1:1 copolymer of dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate (molecular weight approximately 20,000).
A photosensitive resin composition of the present invention was obtained by mixing a 10% aqueous solution. Next, a cured pattern was formed in the same manner as in Example 1, and then dyeing was performed. Staining density (optical density)
A colored pattern of 3.02 (620 nm) was obtained. Comparative Example A cured pattern was formed by the same treatment as in Example 1, except that water-soluble nylon (A-90) was not added in Example 1, and the mixture was dyed at 60°C in a dye bath consisting of a 0.5% Green 1P aqueous solution. It was stained by soaking in water for 10 minutes.
Then washed with water and dried to a dye density (optical density) of 0.52.
(620 nm) colored pattern was obtained. Examples 5 to 9 A photosensitive resin composition of the present invention was obtained by mixing the polyvinyl alcohol derivative () and the hydrophilic polymer () shown in the table. When cured patterns were formed using these resin compositions and dyed with water-soluble dyes, excellent dyeing density was exhibited. The resulting colored (dyed) pattern had good heat resistance.

【table】

[Table] Effects of the invention A photosensitive resin composition with good dyeability and excellent photosensitivity and heat resistance was obtained by a simple method. This product is used for preparing color filters and the like by photolithography.

Claims (1)

[Claims] 1 [In _formula (), ion or hydroxy ion),
n, m and l represent arbitrary integers. However, n+m+
l is 400 to 3000, and the proportion of l in n+l is
0.2-10%, the proportion of n+l in n+m+l is
It shall be at least 75%. It is characterized by containing a hydrophilic polymer () selected from a polyvinyl alcohol derivative represented by () and water-soluble nylon, polyvinylpyrrolidone, a copolymer consisting of a hydrophilic or hydrophobic monomer and a nitrogen-containing monomer, or a salt thereof. A photosensitive resin composition.