JPH05232310A - Production of color filter - Google Patents

Abstract

PURPOSE:To produce a color filter without forming an intermediate layer by incorporating a specified N-alkoxy methyl(meth)acrylamide as a copolymer component. CONSTITUTION:Monomers having N-alkoxyalkyl groups are used as the copolymer component of a resin having a structure of tertiary amine or quaternary ammonium salt to form a relief pattern. This resin is dyed with a dye having an anion group, then treated with a soln. of a compd. comprising a polyvalent phenol deriv., and then subjected to heat treatment. In this process, the base body to be dyed is obtd. by copolymn. of monomers having a structure of tertiary amine or quaternary ammonium salt with monomers expressed by formula, and other monomers by an usual method. In formula, R is H or CH3 and (n) is an integer 1-4. Thereby, enough fixing effect of the dye can be obtd. by heat treatment at low temp.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a color filter used for colorizing a solid-state image pickup device, a liquid crystal display, etc. More specifically, it is a synthetic method superior to natural products in terms of sensitivity and stability. The present invention relates to a method for manufacturing a color filter using the photosensitive resin described in (1) above, which does not require an intermediate layer.

[0002]

2. Description of the Related Art A color filter is manufactured by a method generally called a relief dyeing method, in which a step of dyeing and coloring a fine relief pattern formed of a dyeable resin is repeated by a required number of colors.

In this method, a fine pattern can be easily formed by making the dyeable resin itself photosensitive.
In addition, since a dye is used for coloring, the coloring pattern shows a transparent and sharp spectral transmittance curve, and since dyes can be selected from a large number of types, the degree of freedom in design is great. Is the way.

As the dyeable photosensitive resin used in the relief dyeing method, conventionally, an aqueous solution of a natural protein such as gelatin, casein or fish glue is sensitized with dichromate. However, since these photosensitive resins have low sensitivity, the productivity cannot be improved, and there is a problem in stability as the photosensitive resin.

In order to solve these problems, many synthetic dyeing bases in which a cationic group is introduced as a dyeing site in a resin have been proposed. In particular, those in which a tertiary amine or quaternary ammonium salt is introduced as a cation group show good dyeability, and sufficiently stable properties can be obtained.

By the way, several methods have been proposed for sensitizing a cationic polymer having such a tertiary amine or quaternary ammonium salt introduced therein.

First of all, a photosensitive group such as chalcone which causes photocrosslinking is introduced into the polymer (for example, JP-A-59-48758), and secondly, light of an azide compound or a diazo compound is introduced into the polymer. Adding a cross-linking agent (for example, JP-A-58-199342 and JP-A-59-15).
5412, JP-A-62-127735, etc.).

Thirdly, a polymerizable monomer and a photopolymerization initiator are added (for example, JP-A-60-221755), and fourthly, a photopolymerizable unsaturated bond is introduced into a side chain to carry out photopolymerization. Crosslinking with an initiator (for example, JP-A-63-1)
No. 44346).

[0009]

A problem common to the above-described synthetic photosensitive resins is that when the next colored pattern is formed on the substrate on which the colored pattern is formed, There is a need for an intermediate layer for protection.

That is, if the intermediate layer is not present, (1) the dye of the previous color is dissolved in the solution of the photosensitive resin when the photosensitive resin of the secondary color is applied. (2) When the relief pattern of the next color is dyed, the pattern of the previous color causes color mixing. Such a trouble occurs.

Therefore, when the synthetic photosensitive resin is used, the intermediate layer is indispensable, but this causes an increase in manufacturing cost and a decrease in yield due to an increase in the number of manufacturing steps of the color filter.

When a natural material such as gelatin or casein is used as a photosensitive resin for forming a relief pattern, a dyeing pattern resisting treatment method has been established, and production without an intermediate layer was possible. .. That is, generally, the relief pattern after dyeing was dipped in an aqueous solution of tannic acid and then in an aqueous solution of antimony potassium tartrate solution, whereby elution and color mixing of the dye could be prevented even without the intermediate layer.

However, when a synthetic photosensitive resin is used, the effect of the above-mentioned tannic acid / potassium antimonyl tartrate treatment is recognized, but it is not sufficient to omit the intermediate layer, and other effective dye-proofing is possible. No treatment method was found.

Therefore, the inventors of the present invention have disclosed in Japanese Patent Laid-Open No. 3-100.
No. 602, a monomer having an N-alkoxyalkyl group is used as a copolymerization component of a resin having a structure of a tertiary amine or a quaternary ammonium salt for forming a relief pattern, and dyed with a dye having an anion group. rear,
A method of manufacturing a color filter without an intermediate layer was devised by treating with a solution of tannic acid and then performing heat treatment.

However, according to this method, some dyes do not exhibit a 100% fixing effect unless they are immersed in a tannic acid solution and then heated at 190 to 200 ° C. as a fixing treatment. The heating temperature of 200 ℃ is
Since this is the upper limit temperature in view of the thermal discoloration of the dye, it is required to lower the heating temperature in order to increase the allowable range in the manufacturing process.

Even in the above method, if the heating is carried out for a long time, the treatment temperature can be lowered, but the productivity is lowered.

[0017]

In the present invention, as a copolymerization component of a resin having a structure of a tertiary amine or a quaternary ammonium salt for forming a relief pattern,
The above problem was solved by using a monomer having an N-alkoxyalkyl group, dyeing it with a dye having an anion group, treating with a solution of a compound consisting of a polyphenol derivative, and then performing heat treatment.

The dyeing base material used in the present invention comprises a monomer having a structure of a tertiary amine or a quaternary ammonium salt, a monomer represented by the above-mentioned (Chemical formula 1) and other monomers in a usual manner. It is obtained by copolymerizing with.

As the monomer having a tertiary amine structure, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, etc. are used. Can be done.

As the monomer having a quaternary ammonium salt structure, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, methyl chloride which is a monomer having the structure of the tertiary amine,
A quaternary compound such as dimethylsulfate and methyl P-toluenesulfonate can be used.

The monomer having a tertiary amine or quaternary ammonium salt structure must be incorporated in the copolymer in an amount of 10 to 50% by weight in order to obtain sufficient dyeability.

The monomer represented by the formula (1) is added to the copolymer in an amount of 10 to 50 in order to achieve a sufficient fixing effect.
It is necessary to introduce by weight%. Further, n in the formula is 1 to
A range up to 4 is suitable. For example, N-methylol (meth) acrylamide with n = 0 can be expected to have the same fixing effect, but the reactivity is too high and the polymerization and patterning become unstable, and n = When it is 5 or more, there is a problem in compatibility with other monomers.

The other monomers used in the copolymer of the present invention are selected mainly from the viewpoint of sensitizing the copolymer. There are various methods for sensitizing the copolymer as described in [Prior Art].
-Methacryloyloxychalcone, N-vinylpyrrolidone,
Hydroxyethyl methacrylate, glycidyl methacrylate, citraconic acid mono (methacryloylethyl) ester and the like are used. The present inventors have also found that the introduction of tetrahydrofurfuryl (meth) acrylate is also useful for sensitizing the copolymer. The copolymer into which tetrahydrofurfuryl (meth) acrylate is introduced becomes a highly sensitive photosensitive resin by adding a bisazide compound.

To form a color filter by the method of the present invention, a relief pattern formed by using such a photosensitive resin is dyed with a dye having an anion group such as a sulfonic acid group or a carboxylic acid group, and then polyvalent. The dye pattern is treated with a solution of the phenol derivative. After 15
Heat treatment is performed at about 0 to 200 ° C. By repeating the above steps, the color filter can be formed without the intermediate layer.

As a matter of course, such fixing treatment may be omitted for the filter layer formed last. Further, an intermediate layer may be formed between some filter layers for the purpose of smoothing or the like.

[0026]

When the resin forming the relief pattern has N-alkoxymethyl (meth) acrylamide represented by the chemical formula 1 as a copolymerization component, the present inventors treat it with a solution of a polyhydric phenol derivative after dyeing. Then, it was found that when the heat treatment is carried out subsequently, a sufficient dye fixing effect can be obtained by the heat treatment at a low temperature as compared with the case of the treatment with the solution of tannic acid. Although the dye fixing mechanism of the present invention has not been sufficiently clarified, the polyhydric phenol derivative infiltrated into the dyed pattern is not reacted with the N- of the resin by the heat treatment.
It is considered that the fixation is achieved by reacting with the alkoxymethyl group and increasing the crosslink density of the pattern.

[0027]

【Example】

<Example 1> A method of forming a color filter of three colors of cyan, magenta, and yellow on a solid-state image sensor based on the method of the present invention will be described.

(A) Synthesis of photosensitive resin 40 g of tetrahydrofurfuryl methacrylate, 30 g of p-toluenesulfonic acid methyl salt of dimethylaminopropylmethacrylamide, 30 g of N-methoxymethylacrylamide were used as a solvent in 400 g of methyl cellosolve, and azobisisobutyrate. Using 0.5 g of ronitrile as an initiator, the mixture was stirred at 70 ° C. for 4 hours under a nitrogen stream to obtain a copolymer solution.

Next, the resin content of the copolymer solution is 10% by weight.
Was diluted with methyl cellosolve so as to obtain 8% by weight of 2,2 ′ bis (N-hydroxypropylsulfamoyl) 4,4′-diazidostilbene based on the resin content to prepare a photosensitive solution. ..

(B) Undercoating of solid-state image sensor FVR (Acrylic photosensitive resin manufactured by Fuji Yakuhin Co., Ltd.) was spin-coated on a silicon wafer on which the solid-state image sensor was formed, and prebaked (hot at 100 ° C. for 5 minutes). After using a plate and using a hot plate for all of the following baking treatments), pattern exposure of 100 mJ / cm ² was performed, and development was performed with a mixed solution of 90 parts of MEK and 10 parts of IPA.
The bonding pad section and the scribe section were exposed by rinsing with MIBK. Then, post-baking was performed at 180 ° C. for 5 minutes.

(C) Formation of Cyan Filter The photosensitive liquid of (A) is spin-coated on a silicon wafer which has been subjected to a base treatment, prebaked at 100 ° C. for 5 minutes, and then 20.
Pattern exposure of mJ / cm ² was performed and ethanol 80
Part and 20 parts of IPA were developed and rinsed with MIBK to form a fine relief pattern.
Then, post-baking was performed at 180 ° C. for 5 minutes.

Next, the silicon wafer having the relief pattern formed thereon was treated at 60 ° C. with a cyan dyeing solution composed of a 0.5% aqueous solution of lanazole blue 8G (manufactured by Ciba Geigy Co., Ltd.).
It was soaked in water for 5 minutes and washed with water.

Then, it was immersed in a 1.5% aqueous solution of nylon dye TH (manufactured by Senka Co., Ltd.), an acid dye fixing agent containing a polyhydric phenol derivative as a main component, at 60 ° C. for 2 minutes,
Washed with water. Furthermore, baking treatment was performed at 180 ° C. for 5 minutes.

(D) Formation of Magenta Filter A silicon wafer having a cyan filter formed thereon was spin-coated with the photosensitive solution (A). At this time, elution of the cyan dye was not observed. Then, as in (C), prebaking, exposure, development and postbaking were performed.

Next, Kayanor Milling Red 3BW
(Nippon Kayaku Co., Ltd.) was dyed with a magenta dyeing solution consisting of 0.5% aqueous solution at 60 ° C. for 5 minutes, washed with water
2% at 60 ℃ in 1.5% aqueous solution of Nylon Fix TH
After immersion for 1 minute and washing with water, baking was performed at 180 ° C. for 5 minutes. In this magenta dyeing process, no color mixture of magenta on the cyan filter was observed.

(E) Formation of Yellow Filter The photosensitive liquid of (A) was spin-coated on a silicon wafer on which cyan and magenta filters were formed. At this time, neither cyanide nor magenta dye was found to be eluted. Then, similarly to (C), prebaking, exposure, development and postbaking were performed.

Next, Supranol Farft Yellow 4G
It was dyed at 60 ° C. for 5 minutes with a yellow dyeing solution consisting of a 0.5% aqueous solution of Bayer Co., Ltd., washed with water, and baked at 180 ° C. for 5 minutes. In this yellow dyeing process, no yellow color mixture was observed in the cyan filter and the magenta filter.

(F) Formation of overcoat layer FVR was spin-coated on a silaneco wafer on which cyan, magenta, and yellow filters were formed.
Pre-baking, exposure, development, and post-baking were performed in the same manner as above to expose the bonding pad section and the scribe section.

By the method described above, a color filter could be formed without forming an intermediate layer between each filter.

<Example 2> 40 g of N-vinylpyrrolidone and 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride 2 were charged as the monomers.
5 g, N-ethoxyethyl acrylamide 25 g, and methyl methacrylate 10 g, and the exposure amount of the photosensitive resin was 3
Under the same conditions as in Example 1 except that the developing solution was changed to 0 mJ / cm ² and methyl cellosolve, a color filter without elution and color mixture of dyes could be formed without an intermediate layer.

<Example 3> The amounts of the monomers charged were 30 g of hydroxyethyl methacrylate, 25 g of dimethylaminopropyl methacrylamide, 25 g of N-butoxymethyl acrylamide and 2 of N, N'-dimethyl acrylamide.
A color filter without elution and color mixing of dyes could be formed under the same conditions as in Example 1 except that the amount was 0 g and the developing solution of the photosensitive resin was changed to methyl cellosolve.

<Comparative Example 1> Using the photosensitive resin described in Example 1, a relief pattern was formed in the same manner. Then, the silicon having the relief pattern formed thereon was immersed in a cyan dyeing solution composed of a 0.5% aqueous solution of lanazole 8G at 60 ° C. for 5 minutes and washed with water.

Then, a 1% aqueous solution of tannic acid was added at 60 ° C.
It was immersed for 2 minutes at 180 ° C. for 5 minutes and baked.

Next, a magenta relief pattern was formed and dyed in the same manner as in Example 1. As a result, color loss of the cyan pattern and color mixing with the magenta dye occurred.

[0045]

Industrial Applicability According to the method of the present invention, it is possible to manufacture a color filter by using a synthetic photosensitive resin which is superior to a natural product in terms of sensitivity and stability, without forming an intermediate layer. ..

Further, the baking temperature of the dye fixing treatment can be lowered to a temperature at which the thermal discoloration of the dye does not occur, and it is possible to realize the production of a high-quality color filter with little variation in the coloring density of the color filter. It was

Claims (1)

[Claims] 1. A method for producing a color filter, in which a step of dyeing and coloring a fine relief pattern formed of a dyeable resin is repeated by a required number of colors, wherein (a) a tertiary amine or a quaternary amine is provided on a substrate. A monomer having an ammonium salt structure and a monomer represented by (Chemical Formula 1) A step of forming a relief pattern using a resin having as a copolymerization component (b) a step of coloring the relief pattern by dyeing with a dye having an anion group, and (c) a step of coloring the relief pattern with a polyphenol derivative. A step of treating with a solution of an acidic dye fixing agent as a main component (d) a step of heat-treating a substrate on which a treated colored pattern is formed, characterized by comprising the steps (a) to (d) above Method for manufacturing color filter.